University of Pennsylvania

ScholarlyCommons
Senior Design Reports (CBE)

Department of Chemical & Biomolecular

Engineering

4-1-2010

PHOSGENEFREE ROUTE TO TOLUENE

DIISOCYANATE
Nasri Bou-Saba
University of Pennsylvania

Caryl Dizon
University of Pennsylvania

Devi Kasih
University of Pennsylvania

Bryce Stewart
University of Pennsylvania

This paper is posted at ScholarlyCommons. http://repository.upenn.edu/cbe_sdr/16

For more information, please contact repository@pobox.upenn.edu.

PHOSGENEFREE ROUTE TO TOLUENE DIISOCYANATE

Abstract

A Gulf Coast production plant was designed for a phosgene-free route manufacture of 2,4-toluene
diisocyanate (TDI) from toluene diamine (TDA). The process was designed to generate 300 million pounds
of TDI per year within the required process specifications. Two reactors were to be installed in order to
improve the overall yield of TDI, followed by a series of three distillation columns to ensure highly pure
market competitive product. Safety concerns, the start-up process, and other potential considerations are also
included.
The results of economic analysis for the base case of the project returned a Net Present Value (NPV) of
$20,653,700 with an initial rate of return (IRR) of 18.05% and a return on investment (ROI) of 12.03%.
Further analysis on the assumptions made in these calculations may be required before final project approval
is granted.
Disciplines

Biochemical and Biomolecular Engineering

This working paper is available at ScholarlyCommons: http://repository.upenn.edu/cbe_sdr/16


PHOSGENEFREEROUTETO
TOLUENEDIISOCYANATE
NasriBouSaba(UniversityofPennsylvania)
CarylDizon(UniversityofPennsylvania)
DeviKasih(UniversityofPennsylvania)
BryceStewart(UniversityofPennsylvania)

SeniorDesignReport
April13,2010
UniversityofPennsylvania
DepartmentofChemicalandBiomolecularEngineering
FacultyAdvisor:Prof.LeonardFabiano,Dr.DaeyeonLee
Reccommendedby:Mr.BruceVrana,DuPontEngineeringTechnology

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

UniversityofPennsylvania
SchoolofEngineeringandAppliedScience
DepartmentofChemical&BiomolecularEngineering
220South33rdStreet
Philadelphia,PA19104

April13,2010
DearMr.Fabiano,Dr.Lee,andMr.Vrana,

Enclosed is our proposed process design on PhosgeneFree Route to Toluene

Diisocyanate (TDI) problem statement provided by Mr. Bruce Vrana of DuPont Engineering
Technology. Our focus is to design a high yielding process that is both technologically and
economicallyfeasibleinproducing99.95%pureTDIfromtoluenediamine(TDA).Theprocessis
made up of two main process blocks the Reactor System and Separation Process and
achieves the required capacity specified in the problem statement. Included in our
consideration is to design an optimal process by recycling reactants, minimizing utility costs,
andremovingbyproductsinanecofriendlymanner.

The following report details the process, equipment needs and estimated costs,
approximatedpowerrequirements,andadetailedeconomicanalysis.AcompleteASPENPlus
flow sheet is also enclosed for your reference. Due to limited data availability, assumptions
relevant to the process design are also discussed and various non and economic sensitivity
analyseshavealsobeenincluded.
Finally,wewouldliketothankProfessorLeonardFabiano,Dr.DaeyeonLee,Mr.Bruce
Vrana,Mr.SteveTieri,andMr.GarySawyerforthegreatassistance.Kindlycontactthedesign
groupifyouhaveanyquestionsregardinganyaspectofthereport.
Sincerely,

_________________________
NasriBouSaba

_________________________
CarylDizon

__________________________
DeviKasih

__________________________
BryceStewart

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

TableofContents
Abstract.....6

Introduction....7
ProjectCharter...12
InnovationMapandTechnologyDevelopmentSummary..14
MarketandCompetitiveAnalyses...18
PreliminaryProcessSynthesis.......23
ProcessFlowDiagramsandMaterialBalances...32
ProcessDescriptions.....41
EnergyBalanceandUtilityRequirements.....50
ProcessEnergyBalance......51
UtilityRequirements.......57

CoolingWater..........57

Steam.........58

FuelOilandSolidWaste...59

Electricity.......59

UnitDescriptions.....60
UnitSpecificationSheets......75
EquipmentCostSummary...125
FixedCapitalInvestmentSummary..128
OperatingCostandEconomicAnalysis.....132
EconomicAssumptionsandProjectOperations.....133
OperatingCostSummary.......134

VariableCosts......134
FixedCosts.......137

CashFlowandProfitabilityAnalysis..........139

OtherEconomicsUncertainties.....145

OtherIssuesandConsiderations...147
EnvironmentalConcerns...148
PlantSafetyConcerns....149

PlantStartup....152

ConclusionandRecommendations..153

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Acknowledgements.......157
ListofFiguresandTables..........159
Bibliography........162
Appendix.......167

Appendix1......168

Appendix2......187

Appendix3......189

Appendix4......191

Appendix5......193

Appendix6......196

Appendix7......216

Appendix8......231

Appendix9......351

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Abstract

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Abstract
AGulfCoastproductionplantwasdesignedforaphosgenefreeroutemanufactureof
2,4toluene diisocyanate (TDI) from toluene diamine (TDA). The process was designed to
generate 300 million pounds of TDI per year within the required process specifications. Two
reactorsweretobeinstalledinordertoimprovetheoverallyieldofTDI,followedbyaseriesof
threedistillationcolumnstoensurehighlypuremarketcompetitiveproduct.Safetyconcerns,
thestartupprocess,andotherpotentialconsiderationsarealsoincluded.

TheresultsofeconomicanalysisforthebasecaseoftheprojectreturnedaNetPresent

Value (NPV) of $20,653,700 with an initial rate of return (IRR) of 18.05% and a return on
investment (ROI) of 12.03%. Further analysis on the assumptions made in these calculations
mayberequiredbeforefinalprojectapprovalisgranted.

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Introduction

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Introduction

TDI are intermediates in the production of polyurethanes and polycarbonates, which

have many useful properties. Polycarbonates are widely used in the manufacture of CD and
DVD discs, while polyurethanes are used in the production of foams, elastomers, and hard
polymers.WiththeinputofProfessorFabiano,whohadampleexperienceinTDIprocesses,we
wereurgedtocreateaprocesstoproduceTDIwithalmost100%purity.
Thefollowingreportdescribesachemicalprocessforproducingvirtually100%pureTDI
without introducing the widely used component, phosgene. Phosgene is a colorless volatile
liquidorgasthatisproducedbypassingpurifiedcarbonmonoxideandchlorinegasthrougha
bedofporousactivatedcarbon.Itisavaluableindustrialreagentandbuildingblockinorganic
synthesis but is also a highly toxic material. Its leaks have caused several casualties in many
industrialprocesses.
Phosgene was formerly used as a chemical weapon during World War I. At room
temperature(70F),phosgeneisapoisonousgas.Itsgasmayappearcolorlessorasawhiteto
paleyellowcloudanditsodormaynotbenoticedbyallpeopleexposed.Althoughphosgene
wasneverasnotoriousasmustardgas,itisaninsidiouspoisonthathaskilledfarmorepeople.
AmongthechemicalsusedinWorldWarI,phosgenewasresponsibleforthelargemajorityof
deaths,about85%ofthe100,000deathscausedbychemicalweapons.Itssymptomsmaybe

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

slow to be recognized, as phosgene can only be detected at 0.4 ppm, which is four times its
safetyThresholdLimitValue.1
Phosgene reacts violently and decomposes to toxic compounds on contact with
moisture, including chlorine, carbon monoxide and carbon tetrachloride. People may be
exposed to phosgene through skin or eye contact, touching or drinking water, breathing air,
and eating contaminated food. Inhalation can cause fatal respiratory damage as phosgene
reactsheavilywithHClthatisreleasedinitsreactionwithwaterinthelungs.Itcanalsocause
damage to the skin, eyes, nose, throat, and lungs. Today, gaseous phosgene has increasingly
been supplanted by more easily handled reagents. This is why it was extremely important to
removePhosgeneasareactantinourTDIproductionprocess.1
We were charged with creating an economically feasible and environmentally friendly
process design for producing 300 million pounds of TDI per year in high yield from toluene
diamine (TDA). It was our goal to create a design that recycled the majority of unreacted
starting materials as well as disposed any waste material in an economical and ecofriendly
manner.Wewerealsotominimizetheplantsutilityrequirementsinanefforttoincreaseits
sustainability.
The phosgenefree pathway of producing TDI by reacting TDA, oxygen, and carbon
monoxide in the solvent, 2,2,2trifluoroethanol (TFE), was introduced to us as an attractive
alternativetothecommonmethodsofproducingTDI.

1Hazards:Phosgene.CentersforDiseaseControlandPrevention,Sept.2005.Web.28Jan.2010.

10

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Theoverallreactionis:
NCO

NH2
Catalyst

+2C=O+O=O+ 2

NCO

NH2

Arepresentationofthismechanismispresentedbelow:
(1)

NH

NCO
Catalyst

(2)
+ 2

NCO

NH

+ 2

O
O

With further research we concluded that our process most likely includes a twostep
mechanism.Inthefirststep,TDAreactswithcarbonmonoxide,oxygen,andthesolvent,TFE,
to produce the intermediate toluene dicarbamate. In the second step, the dicarbamate is

11

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

degradedtocreatetheTDIproductandthewaterbyproduct.TheTFEsolventisregeneratedin
thisstepaswell.Itisimportanttonotethattheentirereactionmechanismiscarriedoutinthe
presenceofN,N(bis(3,5ditertbutylsalicylidene)ethylenediamino)cobalt(II)[CotBuSalen]
catalyst.2

2Hassan,Abbas,EbrahimBagherzadeh,RayfordG.Anthony,GregoryBorsinger,andAzizHassan.SYSTEMAND

PROCESSFORPRODUCTIONOFTOLUENEDIISOCYANATE

12

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

ProjectCharter

13

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

ProjectName

PhosgeneFreeRoutetoTolueneDiisocyanate

ProjectChampions

NasriBouSaba,CarylDizon,DeviKasih,andBryceStewart

ProjectLeaders

BruceVrana,Dr.DaeyonLee,andMr.LeonardFabiano

SpecificGoals

ToproducehighpurityTDIfromTDAinhighyieldusingan
environmentallyfriendlyphosgenefreeprocess

ProjectScope

Deliverables

ProjectTimeline

Included:
o Productionof300millionpoundsofhighlypure
TDIfromTDAwithoutusingPhosgene
o Creationofanenvironmentallyfriendlyprocess
withhighamountsofrecycleandminimizeduse
ofutilities
o Maintaininganeconomicallyfeasibleprocess
withanacceptableprofitmargin
Excluded:
o Separationofthe2,4TDIfrom2,6TDI(80%and
20%compositionrespectively)
ProcessEfficiencyAnalysis
o ProductPurity
o ProductYield
o UtilityUsage
o SafetyData
EconomicDatatoManagement
o CostAnalysis
o Profits
o ROI
ToproducemarketreadyTDIin12months

ProjectCharter

14

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BouSaba,Dizon,Kasih,Stewart

InnovationMapand
TechnologyDevelopment
Summary

15

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

16

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

InnovationMap

Figure1:InnovationmapofcommercialTDIproduction

17

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

TechnologyDevelopmentSummary

The traditional route for the manufacture of TDI starts with the nitration of toluene

using nitric acid to produce dinitrotoluene followed by catalytic hydrogenation to toluene

diamine. The toluene diamine is dissolved in an inert solvent and reacted with phosgene to
produce a crude TDI solution. Phosgene is made onsite in a simple, single step process by
passing purified carbon monoxide and chlorine gas through a bed of highly porous carbon,
whichactsasacatalyst.Thesubsequentseparationandpurificationoftheproductsofreaction
fromthepolymericbyproductsthatareformedisamultistepprocess.Thehydrogenchloride
thatisproducedasabyproductofthereactionisrecoveredandsoldeitherdirectlyorinthe
form of hydrochloric acid (HCl). On the flip side, HCl, which is produced in stoichiometric
amount as a byproduct, causes corrosion, and thus a stoichiometric amount of NaOH is
requiredtoneutralizetheHCl.(SerranoFernandezetal,2008)3

Eventhoughthistechnologyhasbeenthebasisofcommercialisocyanateproductionfor

many years, numerous attempts have been made to develop even lower cost, non
phosgenationprocessestoproduceisocyanates.Furthermore,asrestrictionsupontheuse of
very toxic materials such as phosgene within the chemical industry have become more
rigorously enforced, there has been increasing interest in developing alternative methods to
phosgeneinthesynthesisofisocyanate.

Bayerhasdevelopedagasphasephosgenation(GPP)processfortheproductionofTDI

from TDA. The main difference from conventional TDI processes is in the use of gasphase

3SerranoFernandez,FranciscoLuis,BeatrizAlmenaMunoz,AnaPadillaPolo,AranaOrejonAlvarez,CarmenClaver

Cabrero,SergioCastillonMiranda,PilarSalagreCarnero,andAliAghmiz.OnestepCatalyticProcessforthe
SynthesisofIsocyanates.REPSOLYPF,S.A.,assignee.Patent7423171.9Sept.2008.

18

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

reactionofTDAandphosgene,asopposedtothesereactantsbeinghandledasdilutesolutions
inasolventsuchasorthodichlorobenzene.Thegasphasephosgenationtechnologyresultsin
significantsavingsonsolvents,leadingtooperatingcostsavingsduetoareductioninenergy
consumption required to process the much smaller volume of solvent during distillative
recovery. The much shorter residence time of TDA and phosgene in the reactor reduces the
required phosgene process inventory considerably. Further benefits are significantly greater
reactor throughput per unit time (spacetime yield) and the ability to downsize key plant
components.Thesesizereductions,leadtoadditionalinvestmentcostsavings.Thegasphase
technologyalsoprovidesimprovedreactionselectivity,generatingfewerbyproducts.Thisroute
avoidstheuseofphosgeneandwasterecoveryproblemsassociatedwithHCl.Processsafetyis
vastlyimprovedbythereductioninbothphosgeneandsolventinventorieswithintheprocess.
A further safety enhancement is the ability to start up and shut down the gasphase process
quickly.

The most recent attempt is the EniChem Urethane Pyrolysis (NonPhosgene) Process:

Here,oxidativecarbonylationofmethanolisusedtoproducedimethylcarbonate(DMC).DMC
is then reacted with TDA to give a urethane intermediate which is then cracked at high
temperatureandlowpressuretogiveTDI.(Nexant,2008)4

ExistingprocessesandproductionfacilitiesforproducingtheTDImixture,inparticular,

are subject to various constraints such as mass flow limitations, product yield, plant size and
energyconsumption.Accordingly,thereiscontinuinginterestinimprovingthewaythatTDIis
produced.

4DevelopmentsinTolueneDiisocyanate(TDI)ProcessTechnology.Rep.Nexant,Inc.,Oct.2008

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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

MarketandCompetitive
Analyses

20

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

MarketandCompetitiveAnalyses
TDI is often marketed as 80/20 and 65/35 mixtures of the 2,4 and 2,6 isomers
respectively.Asoneofthehighlyproduceddiisocyanates,TDIaccountsfor34.1%oftheglobal
isocyanate market in 2000 (ICIS, 2010)5. The main outlet for TDI is in the manufacture of
polyurethane(PU)flexiblefoamsusedinfurniture,bedding,andautomotiveandairlineseats.
This is achieved by the reaction of TDI with a polyol to produce the foam. Meanwhile,
polycarbonates are particularly valued for their optical clarity and impact resistance, and are
usedinCDandDVDdiscsamongmanyotherapplications.
Globally, flexible PU foams constitute by far the largest market for TDI, 88% of the
global demand (30% for transportation, 20% for furniture, 14% for carpet underlay, 11%
bedding, 5% packaging, and 8% for other foam uses). Rigid urethane foams come next,
contributingto4%ofthedemand,followedbyPUadhesivesandsealantswith3%,PUcoatings
andPUelastomersforanother3%and2%respectively(ICIS,2010).5
Polyurethanecoatingsareoneofthefastestgrowingsectorsofthepaintsandcoatings
industry. Despite their relatively high cost, they are suitable for a range of high performance
applications due to their excellent durability, resistance to corrosion and abrasion, and
flexibility. Markets for PU coatings include automotive refinishing, wood finishes and high
performance anticorrosion coatings. On the other hand, PU elastomers are noted for their
toughness,flexibility,strength,abrasionresistance,shockabsorbencyandchemicalresistance.

5"TolueneDiisocyanate(TDI)CASNo:584849."ICIS.com.

21

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Because they are relatively expensive compared to most other elastomers, they are used in
moredemandingapplicationssuchasautomobilebumpercoversandfacias,industrialrollers,
sportsolesandboots,andmechanicalgoods.
Today, the number of global TDI enterprises is over 30 with more than 40 sets of TDI
productionlines,thetotalproductioncapacityis2.1milliontonsperyearandmainlylocatedin
Asia, Europe and the United States. With most of TDIs output going into the furniture and
automotive sectors, demand is sensitive to economic activity. With the economic downturn,
flexiblePUfoamsdemandhasfallenin2009bybetween5%and20%intheUSandwestern
Europe,accordingtoUSbasedconsultantsSRI.Instrongereconomies,thefallhasbeenmore
limitedupto5%.However,SRIexpectsdemandforflexiblefoamswillreturntogrowat2.4%
peryearthrough2011and24%peryearupto2013.

Currently, there are five major producers of TDI serving the global demand, namely
BASF, Bayer, Lyondell, Mitsui Chemicals, and Dow Chemicals. The current US TDI production
levelsexpressedintermsofcapacitydataforseveralproducersaretabulatedbelow.

Company
BASF
Bayer
Dow
Total

Capacity(MMlbsperyear)
350
400
220
970

Figure2:MajorproducersTDIproductioncapacity5

The demand for TDI is still on the increase today. Regionally, Asia contributes to the
fastestgrowthataround8%peryear.ThisismainlyduetoaboominChinasautomobileand
constructionsectors,whichaccountsforthreequartersofTDIconsumption.Automotivesales
22

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

in China passed the 10 million vehicles per year level in 2009 with sales up by 38% in 2009
compared to the previous year, according to the China Association of Automobile
Manufacturers.Moreover,variousproducersinChinaarealsoexpandingtheircapacity.Bayer
MaterialScience is constructing a 250,000 metric tons TDI plant in Shanghai, while Gansu
Yinguang Chemical Industry Group Co., Ltd. and Hebei Cangzhou Dahua Co., Ltd. also have
expansion plans that are scheduled to come on stream in 2010. If these projects can be
completedonschedule,thedemandforTDIinChinaisexpectedtobearound700,000tonsin
2010.6

GrowthintheUSitselfismuchlowerthantheworldaverageandhasbeenadversely

impactedbytheslowdownintheeconomy.FlexiblePUfoamsaccountfor88%ofTDIdemand
in the US with transportation, furniture, carpet and bedding markets being the main outlets.
The ailing US transportation industry accounts for nearly 22% of total PU consumption,
accordingtotheAmericanChemistryCouncil.Thedemand,imports,andexportsgraphforTDI
intheUSisprovidedinthegraphbelow:

6AnalysisandForecastofChinaTDIMarket20092010.ReportLinker.Web.15Mar.2010.

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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Figure3:TDIdemandinUSAshowsamoderateincreasingtrendabove7
Even with the overall recent decreasing demand trend, the TDI installed capacity is
barelysufficienttomeetcurrentUSdomesticdemandandexportvolumes.Neartermdemand
increases will have to be addressed by an increase in imported material or decreasing the
amountexported.Asthereisnoapparentreliefinsightforenergyandfeedstockcostpressure,
pricing will likely remain at the current historical high level of US$1.901.96 per pound,
according to ICIS. Thus, pricing the TDI to US$1.50 per pound as in our project will look very
promising, especially supported by the accelerated growth in automotive and transportation
industries.

7DevelopmentsinTolueneDiisocyanate(TDI)ProcessTechnology.Rep.Nexant,Inc.,Oct.2008

24

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

PreliminaryProcess
Synthesis

25

PhosgeneFreeRoutetoTolueneDiisocyanate

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Preliminaryprocesssynthesis

Rawmaterialsandproductspecifications
Thephosgenefreeroutemanufactureof300millionpoundsofTDIperyearisanovel
processsuchthatinformationregardingthekinetics,theeffectivenessandtheroleofvarious
typesofcatalyst,solvent,andpromoterareverylimited.Therefore,theTDIsynthesisislargely
based on the US patent invented by Fernandez et al, 2007. For this process, a reactant feed
consistingofTDA,oxygenandcarbonmonoxideispassedoverafixedbedofSchiffBaseType
LigandCatalyst,CotBuSalen.Anorganicsolvent,2,2,2trifluoroethanol(TFE)andapromoter,
sodiumiodide(NaI),arealsochargedthroughoutthereactionprocesstoensuretheTDIoverall
yieldof64%isachieved,asspecifiedinthepatent.
The amount required for each of the raw materials and the process enhancers are
derivedfromthelaboratoryscaleratiowithseveralamendmentsforoptimizationmodeledby
Aspen.Therequiredratiosoftherawmaterialsaretabulatedbelow.
Table1:TherequiredratioofrawmaterialsperpoundofTDIproduced.
RawMaterial:
Unit:
Required
Ratio:
Toluenediamine
lb
0.73
lbperlbofTolueneDiisocyanate
Carbonmonoxide
lb
3.07
lbperlbofTolueneDiisocyanate
Oxygen
lb
0.18
lbperlbofTolueneDiisocyanate

TherequiredamountofTFEandNaIarefixedfortheentireprocesssincetheyarenot
consumed.AsmodeledbyASPEN,therespectiveamountofTFEandNaIneededare1,115,835
poundsand2,730poundsforatotalof314millionpoundsofTDIperyear.The5%excessofTDI
26

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

production works as a buffer considering possible polymeric formation throughout the

synthesis. In addition, the ratio of the carbon monoxide to oxygen in the vapor phase is
controlledto49:1toavoidexplosionrisk.
ToimprovetheoverallyieldofTDIproductionandinturnreducetheproductioncost,
twomajorreactorsystemoptionsareproposed.
Option1:
A single 3loop pass reactor is assembled to improve the overall TDI production yield
from64%(Fernandez,etal)to97.2%(Aspen).Theimprovedyieldisexpectedtobemaintained
astheoperationreachessteadystate.Theprocessflowsheetforthisscenarioispresentedin
Figure4.
Option2:
Two reactors are assembled such that the vapor product of the first reactor is mixed
withtherecyclestreamcomingfromtheseparationsystem.ThefocusistouseupasmuchTDA
and any intermediate products obtained from the first reactor. This process is presented in
Figure5.

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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

28

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Figure4:Option1Singlethreelooppassreactordetailedprocessflowsheet

29

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Figure5:Option2Tworeactorsystemdetailedprocessflowsheet

30

PhosgeneFreeRoutetoTolueneDiisocyanate

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Thechoiceofthereactorsystemismadebasedontwomainconsiderations:
1. PossiblecostsavingsofTFE
BasedonthediscussionwithShaunJulian,anAccountManagerinoils,greases,
waxesandchemicalsdepartmentatHalocarbonProductsCorporation,itisfoundthat
the required amount of TFE in this project accounts for approximately 25% of the
current TFE global demand of 5 million pounds. In addition, the current cost of TFE is
approximately $12 per kilogram or $5.45 per pound. Thus, the TDI manufacture is
enormouslysensitivetoTFErequirement.
ComparingtheamountofTFEofwhichthetwooptionswillconsumeusingthe
ASPEN flow sheet, option 1 will save 22,000 millions of TFE, which is equivalent to
$120,008.
2. Reactorsize
The reactor system in option 1 is a considerably more complex assembly than
thatinoption2whichonlyconsistsoftwoindividualpackedbedreactors.Thefollowing
isthefigureofreactorsystemconfigurationinoption1.

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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Holding
vessel
Fixedbedreactor

Pump
Cooler

Figure6:Threelooppassreactorsystem
AsshowninFigure6thereactorsysteminoption1consistsofaholdingvessel,a
packed bed reactor, a cooler, and a pump. In addition, there is a big tradeoff in
loweringthereactorsresidencetimesincethevolumerequiredisinverselyrelated.Size
optimization by changing the volumetric flow rate passing through the reactor also
involvesalargeuncertaintyintheeffectivenessoftheactualreactionstakeplace.Thisis
due to the unavailability of the reaction kinetics data. Furthermore, the net work
requiredbythepumpwillbeconsiderablyincreasedandthusincreasingtheelectricity
consumption.

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PhosgeneFreeRoutetoTolueneDiisocyanate

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Assuming a base case of per pass residence time of 20 minutes of halffull

reactor8,a3looppassreactorwillcost$55,109,461,withavesseldiameterandlength
of135ftand67ftrespectively.Ontheotherhand,thereactorsysteminoption2costs
$19,041,059.23 with the second reactor only onethird of the size of the first reactor.
Finally, there is no internal utility requirement involved. Appendix 1H contains the
detailedcalculationsonthereactorcosting.
Thesummaryoftheincrementalpossiblesavingofoption2istabulated.
Table2:Summaryofincrementalcostsavingofreactorsysteminoption2
TFEsaving
Reactorpricesaving
Utilityrequirement
Totalsaving

Option2
($120,008.15)
$36,068,401.73
None
$35,948,393.58
Considering the profitability of the two potential designs described, option 2 is
significantlybeneficialfrombusinessperspective.Furthermore,installingtwosmallerreactors
aremorefeasiblethanbuildingoneconsiderablybiggerreactor.
Separationprocessandheatintegration
FollowingtheproductionofTDI,itiscrucialtoisolatetheproductaspureaspossibleto
be accepted in the market. The competitive minimum purity requirement in the market is
99.5%. (ICIS) To achieve successful separation, 3 distillation columns are proposed. The
separationtrainswiththedetailsofisolatedcomponentsarepresentedinFigure7.

8TheUSpatentOneStepCatalyticProcessfortheSynthesisofIsocyanatesdescribesa
reactiontimerangesfrom3minutesto3hours.Duetothelackofrelevantreaction
kineticsdata,thereactiontimebasecaseassumptionisonehour.

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PhosgeneFreeRoutetoTolueneDiisocyanate

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O2,CO,TFE

H 2O

Productmix

TFE,TDI,H20,O2,
CO

TDI,H2O

TDA
TDCARB
NaI

TDI

Figure7:Distillationseparationcomplex

Finally,tominimizetheutilityrequirementandcost,andthusincreaseprofitability,heat
integrationprocesswouldalsobeconductedthoroughly.

34

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

ProcessFlowDiagramand
MaterialBalances

35

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

36

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

ProcessBlockDiagrams:

Recycle
D101TOPTORECYCLE

TDA

O2

Section1:

CO

Reactors

TFE

D101TOPTOR102

D100BOTTOMSTOR102

O2MAKEUP

R100LIQUIDTOSEPARATIONS

H2O

Section2:

TDI

Separations

SLUDGE

Figure8:ProcessBlockDiagram

37

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

38

PhosgeneFreeRoutetoTolueneDiisocyanate

Figure9:ProcessFlowDiagram

BouSaba,Dizon,Kasih,Stewart

Figure10:Reactorsystemsection

39

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Table3:StreaminformationfortheReactorsBlock

TemperatureF
Pressurepsia
VaporFrac
MoleFlow
lbmol/hr
MassFlow
lb/hr
MassFlow
lb/hr
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT

CO
248.00
652.67
1.00
456.91

O2
248.00
652.67
1.00
191.45

SOLVENT
248.00
652.67
0.00
0.95

TDA
248.00
652.67
0.00
228.88

O2MAKEUP
248.00
653.00
1.00
37.00

PSEUDLIQ
248.00
639.67
0.08
11964.12

PSEUDO
248.00
652.67
0.31
15267.13

PSEUDVAP
248.00
639.67
1.00
3303.01

S100
282.76
652.67
0.35
15901.80

S101
282.76
652.67
1.00
5622.44

S102
100.00
647.67
0.52
5622.44

S103
99.91
644.67
1.00
2951.70

S104
282.76
652.67
0.00
10279.36

12798.09

6126.27

95.34

27962.73

1183.96

1124680.62

1247481.61

122800.50

1294464.04

292971.02

292971.02

84460.84

1001493.02

0.00
0.00
12798.09
0.00
0.00
0.00
0.00

0.00
6126.27
0.00
0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00
0.00
0.00
95.34

27962.73
0.00
0.00
0.00
0.00
0.00
0.00

0.00
1183.96
0.00
0.00
0.00
0.00
0.00

927.29
450.12
29069.07
10279.58
1608.79
8567.39
1073778.38

927.51
1202.10
109097.65
10287.57
1661.71
8567.47
1115737.60

0.18
752.06
80028.69
7.49
52.92
0.00
41959.16

5200.24
1123.47
111032.73
39738.99
8648.41
17850.01
1110870.19

1.17
993.54
103246.65
34.13
417.05
0.01
188278.47

1.17
993.54
103246.65
34.13
417.05
0.01
188278.47

0.00
672.30
81428.69
0.00
0.23
0.00
2359.62

5199.07
129.93
7786.08
39704.85
8231.36
17850.01
922591.72

Table3(continued):StreaminformationfortheReactorsBlock

Temperature
F
Pressurepsia
VaporFrac
MoleFlow
lbmol/hr
MassFlow
lb/hr
MassFlow
lb/hr
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT

S120

S122

S123

S124

S125

S126

S127

S128

S129

S130

S131

S132

99.91
644.67
1.00

248.00
648.00
0.00

279.50
652.67
0.34

279.50
652.67
1.00

279.50
652.67
0.00

36.51
653.00
0.00

99.91
644.67
1.00

99.91
644.67
0.00

118.70
644.67
0.00

208.66
644.67
0.99

105.74
644.67
1.00

248.00
639.67
1.00

885.51

2750.53

3687.15

1236.83

2450.33

6843.05

2066.19

2670.74

11964.12

3303.01

922.51

922.51

25338.25

283360.47

309882.68

63677.91

246204.77

669965.68

59122.59

208510.18

1124680.62

122800.50

26522.21

26522.21

0.00
201.69
24428.61
0.00
0.07
0.00
707.88

5146.06
36.38
2180.10
0.70
0.05
17671.51
258325.68

926.29
316.78
24673.74
10252.94
1244.62
8567.39
263900.92

0.18
281.45
23028.61
7.49
52.76
0.00
40307.42

926.11
35.33
1645.13
10245.45
1191.86
8567.39
223593.50

0.00
93.55
5605.98
0.00
0.12
0.00
664266.03

0.00
470.61
57000.08
0.00
0.16
0.00
1651.73

1.17
321.23
21817.96
34.13
416.82
0.01
185918.85

927.29
450.12
29069.07
10279.58
1608.79
8567.39
1073778.38

0.18
752.06
80028.69
7.49
52.92
0.00
41959.16

0.00
1385.65
24428.61
0.00
0.07
0.00
707.88

0.00
1385.65
24428.61
0.00
0.07
0.00
707.88

40

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

41

PhosgeneFreeRoutetoTolueneDiisocyanate

Figure11:Section2SeparationProcess

BouSaba,Dizon,Kasih,Stewart

TemperatureF
Pressurepsia
VaporFrac
MoleFlowlbmol/hr
MassFlowlb/hr
MassFlowlb/hr
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT

S105
96.78
5.00
0.52
10279.36
1001493.02

5199.07
129.93
7786.08
39704.85
8231.36
17850.01
922591.72

S106
517.84
4.90
0.00
90.25
23048.75

5198.04
0.00
0.00
0.70
0.00
17850.01
0.00

S107
521.11
653.00
0.00
90.25
23048.75

5198.04
0.00
0.00
0.70
0.00
17850.01
0.00

S108
521.11
653.00
0.00
0.90
230.49

51.98
0.00
0.00
0.01
0.00
178.50
0.00

S109
34.98
2.00
0.00
10189.12
978444.27

1.03
129.93
7786.08
39704.15
8231.36
0.00
922591.72

S110
35.02
12.00
0.00
10189.12
978444.27

1.03
129.93
7786.08
39704.15
8231.36
0.00
922591.72

S111
120.00
7.00
0.89
10189.12
978444.27

1.03
129.93
7786.08
39704.15
8231.36
0.00
922591.72

S112
200.71
7.80
0.00
684.89
47936.39

1.03
0.00
0.00
39704.15
8231.20
0.00
0.01

S113
352.20
2.01
0.00
227.98
39662.81

1.03
0.00
0.00
39656.97
4.81
0.00
0.00

S114
352.25
7.01
0.00
227.98
39662.81

1.03
0.00
0.00
39656.97
4.81
0.00
0.00

S115
101.70
1.00
0.00
456.91
8273.58

0.00
0.00
0.00
47.18
8226.39
0.00
0.01

S116
521.11
653.00
0.00
89.35
22818.26

5146.06
0.00
0.00
0.70
0.00
17671.51
0.00

S117
34.09
5.00
0.00
9504.23
930507.88

0.00
129.93
7786.08
0.00
0.16
0.00
922591.71

Tab
le
4:
Stre
am
info
rma
tion
for
the
Sep

arationsBlock

Table4(continued):StreaminformationfortheSeparationsBlock

S118

S119

S121

SLUDGE

TDI

WASTEWTR

42

PhosgeneFreeRoutetoTolueneDiisocyanate

TemperatureF
Pressurepsia
VaporFrac
MoleFlowlbmol/hr
MassFlowlb/hr
MassFlowlb/hr
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT

36.51
653.00
0.00
9504.23
930507.88

0.00
129.93
7786.08
0.00
0.16
0.00
922591.71

36.51
653.00
0.00
2661.18
260542.21

0.00
36.38
2180.10
0.00
0.05
0.00
258325.68

74.96
653.00
0.00
2750.53
283360.47

5146.06
36.38
2180.10
0.70
0.05
17671.51
258325.68

140.00
648.00
0.00
0.90
230.49

51.98
0.00
0.00
0.01
0.00
178.50
0.00

BouSaba,Dizon,Kasih,Stewart
140.00
2.01
0.00
227.98
39662.81

1.03
0.00
0.00
39656.97
4.81
0.00
0.00

101.75
6.00
0.00
456.91
8273.58

0.00
0.00
0.00
47.18
8226.39
0.00
0.01

43

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

ProcessMaterialBalance:
Table5:ProcessMaterialBalance
InletStream
TDA
O2
CO
SOLVENT
O2MAKEUP

FlowRate(lb/hr)
27962.73
6126.27
12798.09
95.34
1183.96

Total

48166.40

OutletStream
WASTEWTR
TDI
SLUDGE

Flowrate(lb/hr)
8273.58
39662.81
230.49

48166.90

Table5clearlyshowsthatthemassconservationlawisupheldbyourprocess.Thefive
inlet streams (TDA, O2, CO, and SOLVENT fed to R100 & O2MAKEUP fed to R102) have a
combineflowrateof48,166.40poundsperhour.Thethreeoutletstreams(WASTEWTRand
TDI from D102 & SLUDGE from D100) have a combined flow rate of 48,166.90 pounds per
hourwhichisextremelyclosetotheinletflowrates.

44

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

ProcessDescription

45

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

ProcessDescription
BlockFlowDiagram

TDARecycle

TDA

O2

CO

Catalytic
oxycarbonylation
(Formationof
carbamate
intermediates)

Decompositionof
intermediatesto
TDI

Separation
process

TDI

CarbamatesRecycle

Figure12.BlockflowdiagramfortheTDIproduction
OverallProcessDescription
The block flow diagram given by Figure 12 illustrates the flows to and from the key
sections of the phosgenefree TDI production process. The conversion from TDA to TDI is
accomplished through a twostep catalytic reaction carried out between 120C and 180C
(248F356F)and5 100 bar(72.5psia1450psia).Therearetworeactorsintheprocess,
whichworktomaximizehourlyyield.Thereactorsinthisprocessareallowedtooperatenon
adiabatically with the feeds entering into the reactor at 120C (248F), the bottom of the
optimaltemperaturerange,andthereisatemperatureincreaseto139.3C(282.8F)inthefirst
reactorandatemperatureincreaseto137.5C(279.5F)inthesecondreactor.Thefirststepin
46

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

thereactioninvolvestheoxycarbonylationofTDA,whichproducesthecorrespondingisomeric
carbamates. The second step involves the decomposition of the carbamates into TDI. Both
stepsofthereactionoccurwithinonereactorandarefacilitatedbyaSchiffBaseTypeLigand
Catalyst that uses cobalt and is fixed to a silica bead solid support and a homogeneous
promoter,NaI,thatstayscompletelyinsolutionthroughouttheprocess.Itisimportanttonote
that the solvent used in this process 2,2,2trifluoroethanol (TFE) is consumed in the first
step and regenerated in the second step. In addition to serving as a necessary intermediate
reactant,asignificantamountofTFEisneededtomaintainstoichiometricamountsofO2and
COintheliquidphaseforreactionwhilekeepingtheO2levelsbelowthecombustionlimit.For
this reason, the mass fraction of TFE in the liquid feed to the reactor is very high. The other
components that comprise the liquid feed are NaI, TDA, recycled gases and recycled
carbamates. Fresh feed streams of gas phase O2 and CO are bubbled into the reactor to
saturatethesolution.
ThereactoreffluentstreamscontainingTDI,H2O,TFE,NaI,unreactedTDA,carbamates,
CO, and O2 are decompressed and either recycled back through one of the reactors or sent
throughatrainofthreelowpressuredistillationcolumnsforseparation.Inthefirstcolumn,the
unusedTDAandcarbamates,aswellastheNaI,aretakenoutasbottomsproductandsentto
thesecondreactor.Afterthenextseparationstep,thesolventandreactantgasesarerecycled
backtothereactorsystem,andtheheavierwastewaterandTDIaresenttothethirdandlast
distillationcolumnforseparation.

47

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

48

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

FlowSheetDiagram

Figure13DetailedASPENPlusflowsheetofTDIproduction

49

PhosgeneFreeRoutetoTolueneDiisocyanate

DetailedProcessDescription

BouSaba,Dizon,Kasih,Stewart

Figure13isamorecomprehensiveprocessflowsheetthatgivesadetailedviewofthe
equipmentandflowstreamsinvolvedintheTDIproductionprocess.Thereareeffectivelytwo
majorsectionsoftheprocessthereactionsectionandtheseparationsection.Throughoutthe
reaction section, all the streams and equipment are maintained at a high pressure,
approximately653psia(45bar).Theseparationprocesssectionismaintainedatlowpressure,
with a slight pressure drop gradient over the threecolumn distillation chain from 12psia to
9psia(0.83to0.62bar).Thestreamconnectingthereactionsectiontotheseparationsectionis
decompressedbyavalve,andthestreamsthatgetsrecycledbackfromtheseparationsection
tothereactionsectioniscompressedbyapump.Thevalvesafelyseparatesthehighpressure
halfoftheprocessfromthelowpressurehalfanditactsasasafeguardtomakesurethatif
somethinggoeswronginthehighpressurehalfitcanbeisolatedfromthelowpressurehalf.In
addition this allows all of the high pressure piping to be separated from the low pressure
piping.
TheflowsheetinFigure13showsanopenloopsystem,butismeanttomodelaclosed
loopsystem.Therearetworecyclestreamsleavingthesecondreactorsystemwhich,inreality
wouldcombinetoformthetotalrecycletothefirstreactor.Thesestreamsareseparatedinto
vapor (PSEUDVAP) and liquid (PSEUDLIQ). These streams consist of the combination of the
exits from the second reactor system and any reactant materials recovered from the
separationsprocessesandnotfedintothesecondreactor.Thoughitisnotexplicitlyillustrated
intheflowsheet,PSEUDOVAPismixedwiththeO2andCOstreamsandthenbubbledintoR
100.PSEUDOLIQwillbemixedwiththeTDAandSOLVENTstreamsbeforeenteringR100asa
50

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

singleliquidfeed.Thoughitisnotincludedintheprocesssimulation,thesystemwillalsobe
chargedwithafiniteamountofpromoter,NaI.TheadditionofNaIintothesystemflowwould
not affect the thermodynamics significantly because the amount of NaI needed is negligible
relativetototalflow. Thischemical,however,ishighlycorrosiveandwillrequiremostofthe
reactionsystemandthefirstcolumnoftheseparationsystemtobecoatedinHastelloyC276.
Since the salt is heavy, it should be completely contained within in the bottoms of the first
distillationcolumnandrecycledbacktothereactionsection.
AnothercaveattoFigue13isthattheflashvesselR101immediatelyfollowingR100is
notanactualpieceofequipmentintheproductionprocess,butmerelyameansofmodeling
thevaporandliquideffluentfromR100astwoseparatestreams.ThisisalsothecaseforR102
andR103.
TwoReactorSystem
Thisprocessrequiresbothaprimaryreactor(R100)thatprocessesthebulkoftheflow
through the system, with an inlet rate of 16145.3 lbmol/hr, and a secondary reactor (R102),
whichisfedatalowerflowrate,3673.04lbmol/hr,butatahigherconcentrationofcarbamates
and a comparable concentration of unreacted TDA. The vapor and liquid feeds into the first
reactorareheatedto120Candcompressedtoapressureof45bar.R100ismaintainedat45
bar(653psia)andreachesanonadiabatictemperatureofapproximately282.74F,whichisstill
withintheoptimaltemperaturerangeforthereactions;therefore,itisunnecessarytocoolthe
reactor.TherecyclestreamofTDA,NaIandcarbamates(S106)comingfromD100isfiltered
for sludge (S108/SLUDGE) and compressed to 45 bar (653psia). This stream (S116) is then

51

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

mixedwithapartofthecompressedsolventrecyclestream(S119),whichis28.0%ofthetotal
solventrecyclestream.Thiscombinedstream(S121)isheatedto248FandfedtoR102.The
othersplitfromstreamS118calledS126iscombinedwithtwootherreactorstreamstobe
recycledtoR100asPSEUDLIQ.Thegivensplitfractionsoftherecyclestreamswerecalculated
basedontheamountofTFEneededtodissolvetheO2andCOinthevaporeffluentandonthe
cost and yieldoptimal reactor size of the second reactor. The second reactor is also
maintained at 45 bar and increases to a temperature of 279.5F. Both the liquid and vapor
effluent streams (S124 and S125) from R102 are mixed with the recycle streams from
separationsthataresubsequentlyfedR100inthefollowingmanner.S125ismixedwithpart
oftheR100liquideffluent(S126)andeventuallyfedbacktoR100asPSEUDLIQ.PSEUDLIQ
willbemixedwiththeTDAandSOLVENTfeedliquidsandfedintothereactorasasingleliquid
feed. S124 is mixed with part of the R100 vapor effluent, S127, and refed to R100 as
PSEUDVAP. PSEUDVAP will be mixed with the O2 and CO gas feeds prior to being fed to the
reactorasasinglevaporfeedwhichwillbebubbledintothesystem.
Both reactors have an effective product yield of 64% (82% conversion from TDA to
carbamates, 78% conversion from carbamates to TDI). This particular reactor system design
was chosen over the number of considered alternatives because it is the most cost effective
withregardtoyieldandequipmentcost.Thestreamsfedintothefirstreactoraretabulatedfor
referenceinTable3.CO,O2,TDAandSOLVENTaresuppliedasfreshfeedsormakeupstreams
basedonconsumptionorlossofthereactantselsewhereintheprocess.
Withtheexceptionofthevaporphaseinthetworeactors,alloftheCOandO2inthe
systemmustbedissolvedintotheTFE,becauseinthegasphaseitisnecessarytomaintaina
52

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

19:1ratioofCOtoO2toremainoutsideoftheexplosionriskrange.Inordertomaintainsafe
gaseousconcentrations,thereactorsareinitiallychargedwithaCOandO2mixturesignificantly
greater than the prescribed 19:1 ratio. During regular operation, CO and O2 are bubbled into
thereactorsolutionatonlyalittleovera2:1ratio(2.39:1),therespectivestoichiometricratio
for the reaction. Because the gases are added just at or below their saturation point in the
solvent,theinitialcompositionofthegasphaseinthereactordoesnotdecreasesignificantly.
However, as a preventative measure, it is still necessary to include a control feedback
mechanismthatmonitorsthecomponentconcentrationsinthevaporphaseofthereactorand
controlstheCOandO2feedratesinresponse.
SeparationProcess

Wewillberunningasomewhattraditionalseparationsprocessbyusingdistillationto

separateourfinalproduct,TDI,fromthebyproductsandanyleftoverreactants.Toaccomplish
thedesiredseparations,theprocessrequired3distillationcolumns.Theonlystreamentering
theseparationsfromthereactorssectionisthebottomsliquidfromthefirstreactor.
The stream connecting the reaction to the separation section, S104, must be
decompressedfrom45barto0.345bar(653psiato5psia),sinceallthreedistillationcolumnsare
operatingatverylowpressures.D100separatestheTDA,carbamates,NaIandsludgeoutas
theheavycomponentsinthebottomsproduct(S106)atarateof90.2lbmol/hr.Thisstreamis
then recompressed to 653psia and a side stream is taken out to remove sludge before being
recycledbacktothereactionsection.Theflowsheetshowsasplitterwithanoutgoingsludge
stream at a split fraction of 1% to model the estimated sludge removal necessary to prevent

53

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

buildup.Asmentionedearlier,itisnecessaryforD100tobecoatedinHastelloyC276because
of the volume of NaI that will be flowing through it. The distillate (S109) from D100 is
compressedfrom2psiato12psiaandheatedfrom35Fto120FbeforeenteringD101forthe
next separation step. The D101 distillate (S117) contains almost all (99.99%) of the solvent
thatenterstheseparationsystem.Thisstreamiscompressedandrecycledbacktothereaction
system.Thebottoms(S112)arefedstraightintothethirddistillationcolumn,D102.S112is
almostpurelyTDIandwastewater.Wastewatercomesoutasdistillate(WASTEWTR)atabout
99.4% purity, with a negligible amount of TDI and trace amounts of TDA and solvent. This
wastewater stream will be stored and shipped to a treatment center to be disposed of as
outlinedinEPAregulationsdiscussedintheOtherConsiderationssectionofthisreport.The
bottomsproductofD102is99.9%pureTDIat352.2Fand2.01psia.Thisfinalproductiscooled
to140Fandsenttostorage.
Afinalnoteregardingtheseparationsofourprocessisablackboxdesign,notpictured
inthefigure,whichwillcontainawhitefilmevaporator.Thewhitefilmevaporatorwillbeused
todisposeoftheheavypolymericsludgematerialproducedinthefirstdistillationcolumnasa
resultofprocessingTDIatsuchhightemperatures.Weassumedalossofabout46%ofour
productduetothispolymericsludgewaste.Inresponse,webuiltina5%overproductionof
TDItoaccountforthisunavoidableloss.

54

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

EnergyBalanceandUtility
Requirements

55

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

EnergyBalance
Oneofthemajorconcernsinthisprocesswastheamountofheatingandcoolingwhich
isneeded,primarilyinthethreedistillationcolumns.Whileitisknownthatdistillationisboth
energyintensiveandanenergeticallyinefficientprocess,itwasstilldeemedthebestseparation
methodtoisolatethepureTDI.
One area where energy was managed to be saved was by operating the two reactors
nonadiabatically. Each reactor system was modeled in aspen, and the nonadiabatic
temperature rise was found for the entering composition of each reactor. According to the
patent, the reaction will occur between 212 F and 392 F, and it has an optimal temperature
rangebetween248Fand356F.Becausetheeffectofoperatinginanonoptimaltemperature
rangeisunknown,thefeedstreamstothereactorwerekeptat248F,andtheexittemperature
afteranonadiabaticreactionwasfoundtobe282.7Fforthefirstreactorand279.5Fforthe
secondreactor.Sincebothofthesetemperatureswerestillintheoptimaltemperaturerange
forthereaction,itwaschosentooperatethereactorsnonadiabaticallyandnotspendenergy
tomaintainaconstanttemperatureinthereactor.Thefirstreactorwouldhaverequiredthe
removalofover44MBtuperhourtomaintainitat248F,andthesecondreactorwouldhave
required the removal of over 8.8 MBtu per hour to maintain it at 248 F. This decision saved
roughly$150,000incoolingwater.
56

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

AsseeninTable6,therewerestill5streamsthatneededtobeheatedand3streams
thatneededtobecooled.Table7showsthateachofthethreedistillationcolumnshadbotha
condenser and a reboiler that require large amounts of energy. Stream S121 requires 20.6
MBtuperhourtoheatthestreamfrom75Fto248Ftopreheattheliquidstreamgoinginto
thesecondreactor.StreamS110requires173.4MBtuperhrtoheatthestreamfrom35Fto
120 F to preheat the liquid stream entering the second distillation column. Stream S129
requires 78.5 MBtu per hour to heat the stream from 119 F to 248 F to preheat the liquid
recyclestream.StreamS131requires1.0MBtuperhourtoheatthestreamfrom106Fto248
Table6:Streamsinreactorblockthatneedtobeheatedorcooled

Ftopreheatthevaporstreamenteringthesecondreactor.StreamS130requires1.9MBtuper
hourtoheatthestreamfrom209Fto248Ftopreheatthevaporrecyclestream.StreamS108
requirestheremovalof28,000Btuperhourtocoolthestreamfrom521Fto140Ftocoolthe
sludgestreamtobelowtheOSHAtemperaturelimitforpersonalprotection.Similarly,stream
S114requirestheremovalof3.2MBtuperhourtocoolthestreamfrom352Fto140Ftocool
the TDI stream to below the OSHA temperature limit for personal protection. Stream S101
requirestheremovalof49.5MBtuperhourtocoolthestreamfrom283Fto100Ftocoolthe
vaporstreamexitingthereactortoallowittobeflashedandseparatethevaporcomponentsin

57

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

thestream,whicharesenttothesecondreactor,fromtheliquidcomponentswhicharethen
recycledbacktothefirstreactor.
Thecondenseronthefirstdistillationcolumnrequirestheremovalof729.9MBtuper
houranditneedstocoolthestreamfrom203.1Fto35Faswellascondensethestream.The
reboileronthefirstdistillationcolumnrequires625.5MBtuperhouranditheatsthestream
Table7:Streamsinseparationblockthatneedtobeheatedorcooled

from465.8Fto517.8Fbeforevaporizingthestream.Thecondenserontheseconddistillation
columnrequirestheremovalof351.8MBtuperhourtocoolthestreamfrom93.2Fto34.1F
andthencondensethestream.Thereboilerontheseconddistillationcolumnrequires182.9
MBtuperhourtoheatthestreamfrom181.9Fto200.7Fandthenvaporizethestream.The
thirddistillationcolumnhasmuchmoremoderateenergyrequirementsbecauseithasamuch
lowerflowrate.Thecondenseronthecolumnonlyrequirestheremovalof8.6MBtuperhour
to cool the stream from 114.5 F to 101.7 F and then condense it. The reboiler on the third
distillationcolumnrequires10.2MBtuperhourtoheatthestreamfrom264.4Fto352.2Fand
thenvaporizethestream.Thiscomestoatotalheatingrequirementof1,094MBtuperhour
andatotalcoolingrequirementof1,143.1MBtuperhour.

Becausethisisanexcessivelyhighenergyrequirement,itisvitalthatcrossstreamheat

exchangebeusedasmuchaspossibletominimizetheutilitiesneedsoftheprocess.First,the
58

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

streamsthatmustbeheatedbutarehotterthananyofthestreamsthatneedtobecooledare
ruledoutforcrossstreamheatexchange.Bythisprocess,S106(thereboileroutstreamfrom
the first distillation column) was ruled out. Similarly, any streams that need cooling but are
colder than the streams that need heating cannot be used for cross stream heat exchange.
Initially there are no values that match this description. After pairing up the stream two
separateheatexchangernetworksweresetupasshownbyTable8.
Thefirstnetwork,HX1,involves5streams;thecondenserofthefirstdistillationcolumn
isthehotstreamforallfourheatexchangersinthenetwork,anditispairedwith4 streams
thatneedheating,S131,S129,S121,andS110.OriginallyS129wasplacedfirstintheorder,
becauseithasthehighestinitialtemperature,butthennoenergywasavailableforstreamS
131becausethehotstreamwouldleavethefirstheatexchangercoolerthanS131.Becauseof
this, S131 and S129 were changed in the order so that the most energy could be removed
from both streams. There is 661,000 Btu per hour exchanged over HX 1 1, 38.9 MBtu per
hourexchangedoverHX12,4.6MBtuperhourexchangedoverHX13,and34.4MBtuper
hour exchanged over HX 1 4. This means that 78.6 MBtu per hour is removed from the
condenser of the first distillation column. After the heat exchange, S131s temperature is
201F and it still needs
Table8:Energysavedperstream.
322,000Btuperhourtobe
reach 248 F. S129 is at
199Fanditstillneeds39.6
MBtu per hour to be
heatedto248F.S122isat
59

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

120Fandstillneeds16MBtuperhourtobeheatedto248F,andS110isat96Fandrequires
138.9MBtuperhourtobeheatedto120F.Thehotstreamwasloweredto37F,anditstill
required651.3MBtuperhourtoberemovedforittogetdownto35Fandthencondensethe
stream.
The second network, HX 2, involves three streams; the stream in the reboiler of the
seconddistillationcolumnisthecoldstreamforbothheatexchangers,anditispairedwithS
114andS101whicharebothhotstreamsthatneedcooling.S101isplacedfirstbecauseitis
notashotasS114.32.5MBtuperhourisexchangedoverHX21,and2.3MBtuperhour
over HX 2 2. This means that 34.8 MBtu per hour is put into the reboiler of the second
distillationcolumn.Aftertheheatexchangers,S101isat184Fanditstillneeds17MBtuper
hourtoberemovedforittogetto100F,andS114isat206Fanditstillneedstoremove0.9
MBtuperhourtogetto140F.Thecoldstreamisraisedto204Fwhichishigherthanitsfinal
temperatureshouldbe,butitstillneeds148.1MBtuperhourtovaporize.
Some streams, such as S108,
TotalHe at/Cool
Re q.(Btu/hr)
1,093,907,399
1,143,063,006

TotalHe at/Cool Savings

Savings(Btu/hr)
(% )
113,387,268
10.37%
113,387,268
9.92%

Table9:Totalenergysavingsand%energysaved

were left out of the heat exchanger

network because the energy that they
would contribute to the network is so

littlethatthetemperaturechangeduetopressuredropovertheexchangerwouldmorethan
offsetthecontributionofthestream.Theremainingstreamsthatwerenotincludedintothe
networkdidnothaveasuitablepartner.ThetotalenergysavingsshowninTable 9 of113.4
MBtuperhourinbothcoolingandheatingrepresents10.4%oftheheatingrequirementand

60

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

9.9%ofthecoolingrequirement.Thismeans$240,000issavedincoolingwaterand$3million
insteamcosts.
Other techniques to help lower the utility cost in the distillation columns are also
considered.Oneideaistousetwoparalleldistillationcolumnsinplaceofthefirstdistillation
column(becausethatisthecolumnwheremostoftheutilitycostis).Thisalternative,however,
does not save any energy. It is in fact increases the cooling duty by 75% and it increases the

CondenserHeat
Duty(Btu/hr)
D11
638,667,560
D12
1,277,335,120
D1
729,892,881
Difference
547,442,239
%Difference
175%

ReboilerHeat Column
Duty(Btu/hr) Diameter
586,347,970
9.97
1,172,695,940
9.97
625,253,709
9.57
547,442,231
188%

Reflux
Ratio
4.95
4.95
2.4

heatingdutyby88%.TheseresultscanbeseeninTable10.
Table10:Possibleheatdutysavingssummarybyusingtwoparalleldistillationcolumnsinplace
ofD100

61

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

UtilitiesRequirements
Coolingwater

Cooling water is required for all 6 streams that require cooling even after the heat

exchangersystemasseeninTable11.Thecondenseronthefirstdistillationcolumnrequires
morethan20,000,000,000gallonsofcoolingwaterperyear,whichcosts$1.65millionperyear.
Table11:Utilitycostofcoolingwater

Thecondenserontheseconddistillationcolumnrequires11.1billiongallonsofcoolingwater
peryear,whichcomesoutto$891,156peryear.Thecondenseronthethirddistillationcolumn
requires 273 million gallons of cooling water per year, which comes out to $21,858 per year.
The cooler C100 still requires 541 million gallons per year of cooling water which will cost
$43,259yearly.ThecoolerC102requires28.5milliongallonsperyearofcoolingwaterwhich
willcost$2,277yearly.Thelastcooler,C101,onlyrequires883,000gallonsperyearofcooling
waterwhichwillcost$71ayear.

62

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Steam

Thebottomofthefirstdistillationcolumnissohotthatsteamcannotbeusedtoheatit

up;insteadafiredreboilermustbeused.Forthisfiredreboiler,fueloilwasusedastheutility.
Theseconddistillationcolumnalsobenefitsifitusesafiredreboilerratherthansteam.Steam
isusedfortheheatersandthethirddistillationcolumnreboilerasseeninTable12.Thethird
distillationcolumncanthoughuseasteamreboiler,itwillrequire70.3millionpoundsoflow
pressure steam per year which will cost $224,799 every year. The heater H100 needs 1.11
billionpoundsoflowpressuresteamperyear,costing$3.5millionperyear.H101needs175
Table12:Utilitycostofsteam.

millionpoundsoflowpressuresteamperyearwhichwillcost$558,794ayear.H102needs
434million pounds oflowpressuresteamperyearwhichwillcost$1.4millionayear.H103
requires 3.53 million pounds of low pressure steam per year which will cost $11,279 a year.
Finally H104 requires 20.4 million pounds of low pressure steam per year which will cost
$65,356yearly.

63

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

FuelOilandSolidWaste

Table13:Utilitycostoffueloil.

The first distillation

columns fired reboiler will

use 2.81 billion gallons per
year of fuel oil which will
cost $4.5 million, and the
second distillation columns
fired reboiler will use 987
Table14:Utilitycostoflandfill.
Utilitytype
Materialhandled
Solidwaste
Amount(lb/hr)
Amount(lb/year)
Utilitycost
Unitprice:
Landfill($/drylb)
Adjustedlandfillcost(CEindexfor2010=532.7)
Costperyear($/year)

Landfill
Sludge

million gallons per year of

fuel oil which will cost $1.6

230
million.1.83millionpounds
1,825,465

ofsolidwasteareproduced
$0.10 each year by this process
$0.11
$194,558 whichmeansthattherewill

beayearlycostof$195,558todumpthewasteinalandfill.Thehandlingandtransportation
costisincludedasapercentageofthetotalfixedcost.ThesevaluesareshowninTable13and
Table14.
Electricity

64

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

Finally, we also need to supply electricity through the use of electric motors
accompanyingeverypumpwehaveplacedthroughouttheTDIproductionprocess.Thedetails
canbefoundinTable29inAppendix4.

EquipmentListandUnit
Descriptions

65

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

UnitDescriptions:
The following section is the description on what every unit does throughout the process.
Detailed sizing and costing calculations can be found in Appendix 1 and in the relevant unit
specificationsheets.
ReactorR100&R101:

R100andR101arecombinedtoformahorizontal,fixedbed,autoclavereactor.The

gases, CO and O2, are bubbled vigorously through the liquid from the bottom creating a
continuouslystirredtankreactorsystem.Thereactorworksatatemperatureof282.765Fand
apressureof652.67psi.ItlookslikeincertainplacesyouareusingEnglishunitsandincertain
placesSIunits(whenyoutalkedaboutthesuitabletempforreactions).Itwouldbebetterto
unifytheunits.ThefixedbediscomposedoftheCotBuSalencatalyst.Thereactorismade
outofcarbonsteelwithainchHastelloyCcoatingontheinsidetopreventcorrosionbythe
NaIpromoter.Thereactorhasadiameterof35.92ftandalengthof143.68ft.Itsbaremodule
costis$14,984,247.
ReactorR102&R103:
R102andR103arecombinedtoformahorizontal,fixedbed,autoclavereactor.The
gases, CO and O2, are bubbled vigorously through the liquid from the bottom creating a
continuouslystirredtankreactorsystem.Thereactorworksatatemperatureof282.765Fand
apressureof652.67psi.ThefixedbediscomposedoftheCotBuSalencatalyst.Thereactor
ismadeoutofcarbonsteelwithainchHastelloyCcoatingontheinsidetopreventcorrosion
66

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

bytheNaIpromoter.Thereactorisapproximatelythesizeofthefirstandhasadiameterof
21.85ftandalengthof87.39ft.Itsbaremodulecostis$4,056,812.
CoolerC100:
C100isafixedheadshellandtubecoolerusedtocoolthevaporfromthefirstreactor
system which will be fed to the flash drum. The main reason for this cooler is to lower the
temperature of the vapor from the first reactor so that the quantity of the product, TDI,
vaporizedinthereactorcanberecoveredandsenttoseparations.Thecoolerismadeoutof
carbonsteelshellwithainchHastelloyCcoatingtopreventcorrosionbytheNaIpromoter.
Thetubesare20ftinlength,andtheareaavailableforheattransferis3913.27ft2.Thehot
vapor stream enters at 184F and leaves at 100F. The cooling streaming enters at 90F and
leaves at 120F. The pressure drop through the cooler is 5 psi, and the cooler heat duty is
17,075,650.7Btu/hr.Thebaremodulecostofthiscooleris$88,092.
FlashdrumF100:
F100isaverticaltwophaseflashdrumwhichisusedtoseparatethesolventandgases
fromtherestofthematerialinthevaporstreamfromthefirstreactor.Thesolventandgases
aresenttobefurtherreactedinthesecondreactorsystemwhiletheliquidbottoms(TDA,TDI,
Water and remaining CO, O2, TDCARB, and SOVENT) are sent back to R100 as part of
PSEDUOUT.Theflashdrumismadeoutofcarbonsteel.Thevesselhasanestimatedresidence
time at half full of 5 minutes and a volume of 4957.21 ft3. The diameter is 14.67 ft and the
lengthis29.34ft.Thevesseloperatesatatemperatureof99.91Fandapressureof644.67psi.
Thebaremodulecostoftheflashdrumis$203,926.
67

PhosgeneFreeRoutetoTolueneDiisocyanate

SplitterSP100:

BouSaba,Dizon,Kasih,Stewart

SP100isasplitterusedtosplitS103into0.3S120whichwillbesenttoR102and0.7
S127whichwillsentbacktoR100aspartofPSEUDOUT.
StreamMixerM100:

M100 is used to model the combination of streams S116, S119, S120, O2MAKEUP,

andS121whichwillbesenttothesecondreactor.
HeaterH101:
H101isafixedheadshellandtubeheaterusedtoheatthefeedtoR102.Theheateris
madeoutofcarbonsteelshellwithainchHastelloyCcoatingtopreventcorrosionbytheNaI
promoter.Thetubesare20ftinlength,andtheareaavailableforheattransferis1329.88ft2.
Thepressuredropthroughthecooleris5psi,andtheheaterheatdutyis15,958,528.41Btu/hr.
Thebaremodulecostofthisheateris$135,554.
MixerM101:

M101isusedtomodelthecombinationofstreamsS124,S125,S126,S127,S128,

ANDS129whichwillbemixedtoformthePSEUDLIQstream.Thisstreamwouldbefedtothe
firstreactor.
HeaterH102:
H102isafixedheadshellandtubeheaterusedtoheatthePSEUDLIQstreamwhichwill
berecycledtoR100. TheheaterismadeoutofcarbonsteelshellwithainchHastelloyC

68

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

coatingtopreventcorrosionbytheNaIpromoter.Thetubesare20ftinlength,andthearea
availableforheattransferis3300.01ft2.Thepressuredropthroughthecooleris5psi,andthe
heaterheatdutyis39,600,089.7Btu/hr.Thebaremodulecostofthisheateris$214,773.
ValveV100:
V100 is a diaphragm valve which is used as a safety measure to separate the high
reaction and low separation pressures in the process. Steam S104, from the first reactor
system, enters the valve at 652.67 psia, and stream S105 leaves the valve at 5 psia. The
pressuredropacrossthevalveis647.67psi.Thebaremodulecostofthisheateris$301,962.
DistillationColumnD100:
D100 is a 20 stage carbon steel distillation column with a Hastelloy C coating to
prevent corrosion by the NaI promoter. The column has 19 Koch Flexitray trays with a tray
spacingof2ft,andithasaheightof52ft(assuminga10ftforthesumpand4ftforthespace
above the top tray). The column has a diameter of 9.7 ft. There is an estimated 0.15 psi
pressuredropperstage,andthetopstageisat11psi.Tohelpdecreasethenecessarysizeof
the column, it is packed from stage 219 with Koch Flexipac with a dimension of 500Y. The
columnhasarefluxratioof2.4.Thedistillateisremovedatatemperatureof34.98F,andthe
bottomsisremovedat465.75F.Thebaremodulecostofthiscolumnis$1,219,952.
PumpP100:
P100 is a centrifugal pump which is used to pump the bottoms from D100 to the
secondreactorsystem.ItismadeofcastironandhasainchHastelloyCcoatingtoprevent

69

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

corrosionbytheNaIpromoter.Thepumphasavolumetricflowrateof280.408cuft/hranda
pressurechangeof648.1psiwhilegeneratingaheadof13624.774inches.Thepumpmotoris
assumed to be explosionproof with a shaft rotation of 3600 rotations per minute. The
electricity requirement to run the pump is 12.3198 KW, and the pump efficiency is 0.8. This
pumphasabaremodulecostof$57,306.
SplitterSP101:
SP101isasplitterusedtosplitS107into0.99S116whichwillbesenttoR102and
0.01S108whichisthesludgefromD100whichwillbesenttostorage.
CoolerC101:
C101isafixedheadshellandtubecoolerusedtocoolthesludgebottomsfromD101
which will be sent to storage. The cooler is made out of carbon steel shell with a inch
HastelloyCcoating to prevent corrosion by the NaI promoter. The tubes are 20 ft in length,
and the area available for heat transfer is 6.61 ft2. The hot sludge stream, S108 enters at
521.1F and leaves at 140F. The cooling streaming enters at 90F and leaves at 120F. The
pressuredropthroughthecooleris5psi,andthecoolerheatdutyis27,856.499Btu/hr.The
baremodulecostofthiscooleris$53,159.
PumpP101:
P101isacentrifugalpumpwhichisusedtopumpthetopsfromD100tobefedtoD
101.ItismadeofcastironandhasainchHastelloyCcoatingtopreventcorrosionbytheNaI
promoter.Thepumphasavolumetricflowrateof9784.44cuft/hrandapressurechangeof10

70

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

psiwhilegeneratingaheadof172.8inches.Thepumpmotorisassumedtobeexplosionproof
withashaftrotationof3600rotationsperminute.Theelectricityrequirementtorunthepump
is6.63KW,andthepumpefficiencyis0.8.Thispumphasabaremodulecostof$57,774.
HeaterH100:
H100isafixedheadshellandtubeheaterusedtopreheatthetopliquidfromD100
whichwillbefedtoD101.Theheaterismadeoutofcarbonsteelshell.Thetubesare20ftin
length,andtheareaavailableforheattransferis11577.64ft2.Thepressuredropthroughthe
cooleris5psi,andtheheaterheatdutyis138,931,683.9Btu/hr.Thebaremodulecostofthis
heateris$517,879.
DistillationColumnD101:
D101isa20stagecarbonsteeldistillationcolumn.Thecolumnhas19KochFlexitray
trayswithatrayspacingof2ft,andithasaheightof52ft(assuminga10ftforthesumpand4
ft for the space above the top tray). The column has a diameter of 30.35 ft. There is an
estimated0.15psipressuredropperstage,andthetopstageisat10psi.Tohelpdecreasethe
necessarysizeofthecolumn,itispackedfromstage219withKochFlexipacwithadimension
of500Y.Thecolumnhasarefluxratioof1.05.Thedistillateisremovedatatemperatureof
34.09F, and the bottoms is removed at 200.71F. The bare module cost of this column is
$2,566,983.

71

PhosgeneFreeRoutetoTolueneDiisocyanate

PumpP104:

BouSaba,Dizon,Kasih,Stewart

P104 is a centrifugal pump which is used to pump the tops from D101 to be fed to
bothreactors.Itismadeofcastiron.Thepumphasavolumetricflowrateof9155.70cuft/hr
andapressurechangeof648psiwhilegeneratingaheadof11017.68inches.Thepumpmotor
is assumed to be explosionproof with a shaft rotation of 3600 rotations per minute. The
electricity requirement to run the pump is 402.196 KW, and the pump efficiency is 0.8. This
pumphasabaremodulecostof$251,744.
SplitterSP102:
SP102isasplitterusedtosplitS118into0.28S119whichwillbesenttoR102and
0.72S126whichwillsentbacktoR100aspartofPSEUDOUT.
DistillationColumnD102:
D100isa19stagecarbonsteeldistillation.Thecolumnhas11KochFlexitraytrayswith
atrayspacingof2ft,andithasaheightof36ft(assuminga10ftforthesumpand4ftforthe
spaceabovethetoptray).Thecolumnhasadiameterof4.19ft.Thereisanestimated0.15psi
pressuredropperstage,andthetopstageisat1psi.Tohelpdecreasethenecessarysizeof
thecolumn,itispackedfromstage27withKochFlexipacwithadimensionof2X.Thecolumn
has a reflux ratio of 3.2. The distillate is removed at a temperature of 101.71F, and the
bottomsisremovedat352.20F.Thebaremodulecostofthiscolumnis$385,015.

72

PhosgeneFreeRoutetoTolueneDiisocyanate

PumpP102:

BouSaba,Dizon,Kasih,Stewart

P102isacentrifugalpumpwhichisusedtopumptheTDIbottomsproductfromD102
tostorage.Itismadeofcastiron.Thepumphasavolumetricflowrateof604.575cuft/hrand
a pressure change of 5 psi while generating a head of 131.70 inches. The pump motor is
assumed to be explosionproof with a shaft rotation of 3600 rotations per minute. The
electricity requirement to run the pump is .32930 KW, and the pump efficiency is 0.5. This
pumphasabaremodulecostof$21,050.
CoolerC102:
C102isafixedheadshellandtubecoolerusedtocooltheTDIbottomsproductfromD
102whichwillbesenttostorage.Thecoolerismadeoutofcarbonsteelshell.Thetubesare
20ftinlength,andtheareaavailableforheattransferis135.39ft2.ThehotTDIstream,S113
entersat206Fandleavesat140F.Thecoolingstreamingentersat90Fandleavesat120F.
The pressure drop through the cooler is 5 psi, and the cooler heat duty is 898,760.8 Btu/hr.
Thebaremodulecostofthiscooleris$24,791.
PumpP103:
P103isacentrifugalpumpwhichisusedtopumpthewastewatertopproductfromD
102tostorage.Itismadeofcastiron.Thepumphasavolumetricflowrateof135.091cuft/hr
andapressurechangeof5psiwhilegeneratingaheadof141.07inches.Thepumpmotoris
assumed to be explosionproof with a shaft rotation of 3600 rotations per minute. The
electricity requirement to run the pump is .12390 KW, and the pump efficiency is 0.3. This
pumphasabaremodulecostof$25,404.
73

PhosgeneFreeRoutetoTolueneDiisocyanate

TDAStorageTankST100:

BouSaba,Dizon,Kasih,Stewart

ST100isacarbonsteelstoragetankusedtoholdtheTDAstartingmaterial.Thistank

holds 1weeks worth of TDA at a temperature of 248F and a pressure of 652.67 psia. The
volumeofthevesselis73,017cuft,andithasapurchasecostof$243,316.
TFEMakeupStorageTankST101:
ST101isacarbonsteelstoragetankusedtoholdtheSOLVENTmakeup.Thistankholds
1weeks worth of SOLVENT makeup at a temperature of 248F and a pressure of 652.67 psia.
Thevolumeofthevesselis199cuft,andithasapurchasecostof$3,462.
CarbonMonoxideStorageTankST102:
ST102isacarbonsteelstoragetankusedtoholdtheCOstartingmaterial.Thistank
holds 1weeks worth of CO at a temperature of 248F and a pressure of 652.67 psia. The
volumeofthevesselis896,650cuft,andithasapurchasecostof$2,731,981.
OxygenStorageTankST103:

ST103 is a carbon steel storage tank used to hold the O2 starting material. This tank

holds1weeksworthofO2atatemperatureof248Fandapressureof653psia.Thevolumeof
thevesselis444,514cuft,andithasapurchasecostof$2,020,415.

74

PhosgeneFreeRoutetoTolueneDiisocyanate

TFEStorageTankST104:

BouSaba,Dizon,Kasih,Stewart

ST104 is a carbon steel storage tank used to hold the TFE solvent. This tank holds 3

hoursworthofTFEatatemperatureof248Fandapressureof639.67psia.Thevolumeofthe
vesselis54,571cuft,andithasapurchasecostof$197,296.
WasteWaterStorageTankST105:
ST105isacarbonsteelstoragetankusedtoholdtheWASTEWATER.Thistankholds
1weeks worth of WASTE WATER at a temperature of 101.7F and a pressure of 6 psia. The
volumeofthevesselis22,696cuft,andithasapurchasecostof$104,902.
Sludge/SolidWasteStorageTankST106:
ST106isacarbonsteelrailstoragetankusedtoholdtheSLUDGEfromthebottomsof
D100.Thistankholds1weeksworthofSLUDGEatatemperatureof168Fandapressureof
648psia.Thevolumeofthevesselis395cuft,andithasapurchasecostof$5,679.
TDIProductStorageTankST107:
ST107isacarbonsteelrailcarstorageusedtoholdtheTDIproduct.Thistankholds
1weeks worth of TDI product at a temperature of 140F and a pressure of 2.01 psia. The
volumeofthevesselis90,520cuft,andithasapurchasecostof$284,026.

75

PhosgeneFreeRoutetoTolueneDiisocyanate

RecycleStreamIntermediateStorageTankST108:

BouSaba,Dizon,Kasih,Stewart

ST108isacarbonsteelstoragetankusedtoholdthePSEUDOUTtoberecycledtoR
100.Thistankholds1hoursworthofPSEUDOUTatatemperatureof248Fandapressureof
639.67psia.Thevolumeofthevesselis66,654cuft,andithasapurchasecostof$227,854.
HeaterH103:
H103isafixedheadshellandtubeheaterusedtopreheatthetopliquidfromD100
whichwillbefedtoD101.Theheaterismadeoutofcarbonsteelshell.Thetubesare20ftin
length, and the area available for heat transfer is 26.84 ft2. The pressure drop through the
cooler is 5 psi, and the heater heat duty is 322,132.4 Btu/hr. The bare module cost of this
heateris$134,065.
HeaterH104:
H104isafixedheadshellandtubeheaterusedtopreheatthetopliquidfromD100
whichwillbefedtoD101.Theheaterismadeoutofcarbonsteelshell.Thetubesare20ftin
length, and the area available for heat transfer is 155.54 ft2. The pressure drop through the
cooler is 5 psi, and the heater heat duty is 1,866,485 Btu/hr. The bare module cost of this
heateris$134,583.
M102:

M102isusedtomodelthecombinationofS127,partoftheflashdrumvaporstream,

andS124,thevaporstreamcomingoffthetopofthesecondreactor.Thestreamscombineto
formS130whichwillbefedbacktothefirstreactorasthePSEUDVAPstream.
76

PhosgeneFreeRoutetoTolueneDiisocyanate

M103:

BouSaba,Dizon,Kasih,Stewart

M103 is used to model the combination of O2MAKEUP, the the oxygen makeup

necessarytobefedintothesecondreactor,andS120,parofthevaporstreamcomingoffthe
topoftheflashdrum.ThestreamscombinetoformS131whichwillbethegasfeedbackto
thesecondreactorsystem.
HeatExchangerHX100:

HX100 models the heat exchanger that transfers energy from the hot stream, S109,

goingintothecondenserofcolumn1,D100,tothecoldstream,S131,thatisthevaporfeed
going into the second reactor, R101. The hot stream temperature in is 203F and the hot
streamtemperatureoutis202F.Thecoldstreamtemperatureinis106Fandthecoldstream
temperatureoutis201F.Theheatdutyis660,603Btu/hr.
HeatExchangerHX101:

HX101 models the heat exchanger that transfers energy from the hot stream, S109,

goingintothecondenserofcolumn1,D100,tothecoldstream,S129,thatistheliquidrecycle
streamgoingbackintothefirstreactor,R100.Thehotstreamtemperatureinis202Fandthe
hot stream temperature out is 122F. The cold stream temperature in is 119F and the cold
streamtemperatureoutis199F.Theheatdutyis38,886,131Btu/hr.
HeatExchangerHX102:

HX102 models the heat exchanger that transfers energy from the hot stream, S109,

goingintothecondenserofcolumn1,D100,tothecoldstream,S121,thatistheliquidfeed
77

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

going into the second reactor, R101. The hot stream temperature in is 122F and the hot
streamtemperatureoutis112F.Thecoldstreamtemperatureinis75Fandthecoldstream
temperatureoutis120F.Theheatdutyis4,649,530Btu/hr.
HeatExchangerHX103:

HX103 models the heat exchanger that transfers energy from the hot stream, S109,

going into the condenser of column 1, D100, to the cold stream, S110, that is the stream
enteringtheseconddistillationcolumn,D101.Thehotstreamtemperatureinis112Fandthe
hot stream temperature out is 37F. The cold stream temperature in is 35F and the cold
streamtemperatureoutis96F.Theheatdutyis34,428,316Btu/hr.
HeatExchangerHX104:

HX104 models the heat exchanger that transfers energy from the hot stream, S101,

the vapor stream leaving the first reactor, R100, that is cooled before entering the flash
vaporization vessel, F100, to the cold stream, S112, that is going into the reboiler of
distillation column 2, D101. The hot stream temperature in is 283F and the hot stream
temperature out is 184F. The cold stream temperature in is 182F and the cold stream
temperatureoutis204F.Theheatdutyis32,467,349Btu/hr.
HeatExchangerHX105:

HX105 models the heat exchanger that transfers energy from the hot stream, S114,

theTDIexitstreamwhichmustbecooledtobestored,tothecoldstream,S112,thatisgoing
intothereboilerofdistillationcolumn2,D101.Thehotstreamtemperatureinis352Fandthe

78

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

hot stream temperature out is 206F. The cold stream temperature in is 204F and the cold
streamtemperatureoutis204F.Theheatdutyis2,295,339Btu/hr.
HeatExchanger(HotOilSystem)HX106:

HX106modelsthefiredreboilerthatreplacesthetraditionalsteamreboilerofthefirst

distillationcolumn,D100,becausethetemperatureatthebottomofthatcolumnistoohotfor
steamtobeused.Thestreamisheatedto518Fandthenvaporizedusing625,534,000Btu/hr.
HeatExchanger(HotOilSystem)HX107:

HX107 models the fired reboiler that replaces the traditional steam reboiler of the

seconddistillationcolumn,D101.Thestreamisvaporizedusing148,120,312Btu/hr.

79

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

UnitSpecificationSheets

80

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

81

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Cooler
Identification:Item HEATER
ItemNo.
C100
No.Required
1
Function: TocoolthetopvaporfromR101tobefedtoF100
OperationContinuous
Materialshandled:
InletStream
StreamID:
S101
Quantity(lb/hr):
2.9297+05
Composition:
TDA
1.1713
O2
993.5
CO
1.0325+05
TDI
34.1342
WATER
417.0485
TDCARB
7.687003
SOLVENT
1.8828+05

Date: 4/4/2010

OutletStream
S102
2.9297+05
1.1713
993.5
1.0325+05
34.1342
417.0485
7.687003
1.8828+05

100
Temperature( F):
Pressure(psi):
647.67
DesignData:
MaterialofConstruction:
PressureDrop
HeatDuty
U
Area

CarbonSteelwithHastelloycoating
5
psi
()1707565Btu
150
Btu/hrft^2F
3913.271 ft^2

Comment ThepurposeofthiscooleristocoolthevaporofthefirstreactorsothatanyTDI
thatwasvaporizedduringthereactioncanberecoveredandsenttoseparations.

82

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Cooler
Identification:Item HEATER
ItemNo.
C101
No.Required
1
Function: TocooltheSLUDGEstreamfromD100forstorage
OperationContinuous
Materialshandled:
InletStream
StreamID:
S108
Quantity(lb/hr):
230.4875
Composition:
TDA
51.9804
O2
0.0
CO
0.0
TDI
7.022003
WATER
2.273624
TDCARB
178.5001
SOLVENT
7.820020

Date: 4/4/2010

OutletStream
SLUDGE
230.4875
51.9804
0.0
0.0
7.022003
2.273624
178.5001
7.820020

140
Temperature( F):
Pressure(psi):
648
DesignData:
MaterialofConstruction:
PressureDrop
HeatDuty
U
Area

CarbonSteelwithHastelloycoating
5
psi
()27856.499
Btu/hr
25
Btu/hrft^2F
6.608
ft^2

Comments:

83

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Cooler
Identification:Item HEATER
Date: 4/4/2010
ItemNo.
C102
No.Required
1
Function: TocooltheTDIproductstreamfromthebottomofD102forstorage
OperationContinuous
Materialshandled:
InletStream
OutletStream
StreamID:
S114
TDI
Quantity(lb/hr):
3.9663+04
3.9663+04
Composition:
TDA
1.0299
1.0299
O2
0.0
0.0
CO
0.0
0.0
TDI
3.9657+04
3.9657+04
WATER
4.8083
4.8083
TDCARB
0.0
0.0
SOLVENT
6.568112
6.568112

140
Temperature( F):
Pressure(psi):
2.077
DesignData:
MaterialofConstruction:
PressureDrop
HeatDuty
U
Area

CarbonSteelwithHastelloycoating
5
psi
()898760.8
Btu
100
Btu/hrft^2F
135.39
ft^2

Comment ThepointofthiscooleristocooltheTDIproductto140Fwhich
istheOSHArequirementforstoragewithouttheneedofspecialheatsafegear.

84

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo. D100REBOILERPUMP
No.Requi
1
Function: TopumpthebottomsofD100toberefedunderneaththebottomtray
OperationContinuous
Materialshandled:
STREAM
StreamID:
S106
Quantity(lb/hr):
23048.75
Composition:
TDA
5198.0
O2
0.0
CO
0.0
TDI
0.702195
WATER
2.27E22
TDCARB
17850.0
SOLVENT
7.82E18

517.84
Temperature( F):
Pressure(psi):
4.9
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
280.398420924574cuft/hr
0.15psi
6.63296kW
0.386078

Comments:

85

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo. D100REFLUXPUMP
No.Requi
1
Function: TopumpthetopsofD100toberefedabovethetoptray
OperationContinuous
Materialshandled:
STREAM
StreamID:
S109
Quantity(lb/hr):
978444.3
Composition:
TDA
1.029994
O2
129.9303
CO
7786.079
TDI
39704.15
WATER
8231.36
TDCARB
3.647230
SOLVENT
922591.7

34.981
Temperature( F):
Pressure(psi):
2
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
33267.66752232cuft/hr
0.0922660000000004psi
6.63296KW
0.85249

Comments:

86

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Distillationcolumn
Identification:Item RADFRACDistillationColumn
Date: 4/4/2010
ItemNo.
D100
No.Required
1
Function: Toseparateheavies(TDAandTDCARB)fromSOLVENT(TFE),O2,CO,Water,&TDI
OperationContinuous
Materialshandled:
InletFeed
TopOut BottomOut
StreamID:
S105
S109
S106
Quantity(LB/HR):
1001493
978444.3 23048.75
Composition:
TDA
5199.073
1.029994 5198.043
O2
129.9303
129.9303 1.47E46
CO
7786.079
7786.079 3.62E47
TDI
39704.85
39704.15 0.702195
WATER
8231.36
8231.36 2.27E22
TDCARB
17850.01
3.65E30 17850.01
SOLVENT
922591.7
922591.7 7.82E18

Temperature( F):

Top=34.98,Bot.=517.84

DesignData:
Material:
Stages:
Pressure:
Pressuredropperstage:
Diameter:
Height:
TraySpacing:
TrayType:

CarbonSteelwitha1/4inchHastelloyCoating
20
11psi
0.15psi
9.57ft
52ft
2ft
KochFlexitray

Comments:

87

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

RefluxAccumulator
Identification:Item HorizontalRefluxAccumulatorTank
Date:
4/4/2010
ItemNo.
D100ACCUMULATOR
No.Required
1
Function: ToaccumulateexcesstopsfromD100tobefedtofedtorefluxpump
Operation: Continuous
Materialshandled:
Reflux
Stream
StreamID:
S109
Quantity(lb/hr):
978444.3
Composition:
TDA
1.029994
O2
129.9303
CO
7786.079
TDI
39704.15
WATER
8231.36
TDCARB
3.647230
SOLVENT
922591.7

34.981
Temperature( F):
Pressure(psi):
2psi
DesignData:
Material:
Pressure:
MolarRefluxRatio:
Height:
VaporFraction:
HoldupTime:

CarbonSteel
2psi
2.4
12.0848262248967ft
0
5min

Comments:

88

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Condenser
Identification:Item Condenser
ItemNo.
D100CONDENSER
No.Required
1
Function: TocondensethetopsofD100
Operation: Continuous
Materialshandled:
D100Condenser
StreamID:
S109
Quantity(lb/hr):
978444.3
Composition:
TDA
1.029994
O2
129.9303
CO
7786.079
TDI
39704.15
WATER
8231.36
TDCARB
3.647230
SOLVENT
922591.7

Inlettemperatur(inF):
OutletTemperature(inF):
DesignData:
MaterialofConstruction:
HeatDuty:
Utilities:
Type:

Date:

4/4/2010

StainlessSteel
651472422.5btu/hr
CoolingWater
Total

Comments:

89

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Reboiler
Identification:Item DistillationReboiler
Date: 4/4/2010
ItemNo.
D100REBOILER
No.Required
1
Function: Toreheatthebottomsofthecolumnwhichwillbereintroducedtothecolumnasvapor
Operation: Continuous
Materialshandled:
D100REBOILER
StreamID:
S106
Quantity(lb/hr):
23048.75
Composition:
TDA
5198.043
O2
1.47E46
CO
3.62E47
TDI
0.702195
WATER
2.27E22
TDCARB
17850.01
SOLVENT
7.82E18

InletTemperature(F)
OutletTemperature(
DesignData:

465.75
517.842

MaterialofConstruction: CarbonSteelwith1/4inchHastelloycoating
HeatDuty:
625534412Btu/hr
Utilities:
13.9psiSteam
Type:
Kettle
Comments:

90

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo.
D101REBOILERPUMP
No.Required
1
Function: TopumpthebottomsofD101toberefedunderneaththebottomtray
OperationContinuous
Materialshandled:
STREAM
StreamID:
S112
Quantity(lb/hr):
47936.39
Composition:
TDA
1.029994
O2
8.18E26
CO
1.06E26
TDI
39704.15
WATER
8.23E+03
TDCARB
0
SOLVENT
9.78E03

200.71
Temperature( F):
Pressure(psi):
7.8
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
709.85324300311cuft/hr
0.15psi
6.63296KW
0.519631

Comments:

91

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo. D101REFLUXPUMP
No.Requi
1
Function: TopumpthetopsofD101toberefedabovethetoptray
OperationContinuous
Materialshandled:
STREAM
StreamID:
S117
Quantity(lb/hr):
930507.9
Composition:
TDA
6.64E44
O2
129.9303
CO
7786.079
TDI
1.45E30
WATER
0.162563
TDCARB
0.0
SOLVENT
922591.7

34.092
Temperature( F):
Pressure(psi):
5
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
18768.5864395356cuft/hr
0.0922660000000004psi
6.63296KW
0.825443

Comments:

92

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Distillationcolumn
Identification:Item RADFRACDistillationColumn
Date:
ItemNo.
D101
No.Required
1
Function: ToseparateSOLVENT(TFE),CO,andO2fromWaterandTDI
Operation: Continuous
Materialshandled:
InletFeed
TopOut
StreamID:
S111
S117
Quantity(LB/HR):
978444.3
930507.882
Composition:
TDA
1.029994
0.0
O2
129.9303
129.930304
CO
7786.079
7786.07937
TDI
39704.15
1.45E30
WATER
8231.36
0.1625633
TDCARB
3.65E30
0.0
SOLVENT
922591.7
922591.709

Temperature( F):

4/4/2010

BottomOut
S112
47936.3895
1.02999379
8.18E26
1.06E26
39704.152
8231.1978
0.0
0.00977767

Top=34.09,Bot.=200.71

DesignData:
Material:
Stages:
Pressure:
Pressuredropperstage:
Diameter:
Height:
TraySpacing:
TrayType:

CarbonSteel
20
10psi
.15psi
30.35ft
52ft
2ft
KochFlexitray

Comments:

93

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

RefluxAccumulator
Identification:Item HorizontalRefluxAccumulatorTank
Date:
4/4/2010
ItemNo.
D101ACCUMULATOR
No.Required
1
Function: ToaccumulateexcesstopsfromD101tobefedtofedtorefluxpump
Operation: Continuous
Materialshandled:
Reflux
Stream
StreamID:
S117
Quantity(lb/hr):
930507.9
Composition:
TDA
6.64E44
O2
129.9303
CO
7786.079
TDI
1.45E30
WATER
0.162563
TDCARB
0.0
SOLVENT
922591.7

34.092
Temperature( F):
Pressure(psi):
5psi
DesignData:
Material:
Pressure:
MolarRefluxRatio:
Height:
VaporFraction:
HoldupTime:

CarbonSteel
5psi
1.05
9.98566090073922ft
0
5min

Comments:

94

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Condenser
Identification:Item Condenser
ItemNo.
D101CONDENSER
No.Required
1
Function: TocondensethetopsofD101
OperationContinuous
Materialshandled:
D101Condenser
StreamID:
S117
Quantity(lb/hr):
930507.9
Composition:
TDA
6.64E44
O2
129.9303
CO
7786.079
TDI
1.45E30
WATER
0.162563
TDCARB
0.0
SOLVENT
922591.7

Inlettemperatur(F)
34.092
OutletTemperature
34.1
DesignData:
MaterialofConstruction:
HeatDuty:
Utilities:
Type:

Date: 4/4/2010

StainlessSteel
351768841btu/hr
CoolingWater
Total

Comments:

95

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Reboiler
Identification:Item DistillationReboiler
Date: 4/4/2010
ItemNo.
D101REBOILER
No.Required
1
Function: Toreheatthebottomsofthecolumnwhichwillbereintroducedtothecolumnasvapor
Operation: Continuous
Materialshandled:
D101REBOILER
StreamID:
S112
Quantity(lb/hr):
47936.39
Composition:
TDA
1.029994
O2
8.18E26
CO
1.06E26
TDI
39704.15
WATER
8.23E+03
TDCARB
0
SOLVENT
9.78E03

InletTemperature(F)
OutletTemperature(
DesignData:

181.88
200.71

MaterialofConstruction: CarbonSteel
HeatDuty:
148120311.5Btu/hr
Utilities:
13.9psiSteam
Type:
Kettle
Comments:

96

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo. D102REBOILERPUMP
No.Requi
1
Function: TopumpthebottomsofD102toberefedunderneaththebottomtray
OperationContinuous
Materialshandled:
STREAM
StreamID:
S113
Quantity(lb/hr):
39662.81
Composition:
TDA
1.029915
O2
0
CO
0
TDI
39656.97
WATER
4.808312
TDCARB
0
SOLVENT
6.57E12

Temperature( F):
352.2
Pressure(psi):
2.0077
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
604.616027439024cuft/hr
0.092266psi
6.63296KW
0.498037

Comments:

97

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo. D102REFLUXPUMP
No.Requi
1
Function: TopumpthetopsofD102toberefedabovethetoptray
OperationContinuous
Materialshandled:
STREAM
StreamID:
S115
Quantity(lb/hr):
8273.578
Composition:
TDA
7.90E05
O2
0.0
CO
0.0
TDI
4.72E+01
WATER
8226.389
TDCARB
0.0
SOLVENT
0.009778

Temperature( F):
101.7
Pressure(psi):
1
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
136.06256363243cuft/hr
0.0922660000000004psi
6.63296KW
0.267787

Comments:

98

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Distillationcolumn
Identification:Item RADFRACDistillationColumn
ItemNo.
D102
No.Required
1
Function: ToseparateWaterandTDI
Operation: Continuous
Materialshandled:
InletFeed
StreamID:
S112
Quantity(LB/HR):
47936.39
Composition:
TDA
1.029994
O2
8.18E26
CO
1.06E26
TDI
39704.15
WATER
8231.198
TDCARB
0.0
SOLVENT
0.009778

Temperature( F):

Date:

4/4/2010

TopOut
BottomOut
S115
S113
8273.57811 39662.8114
0.0
0.0
0.0
47.1787663
8226.38949
0.0
0.00977767

1.02991481
0
0
39656.9732
4.80831193
0.0
6.57E12

Top=101.71,Bot.=352.20

DesignData:
Material:
Stages:
Pressure:
Pressuredropperstage:
Diameter:
Height:
TraySpacing:
TrayType:

CarbonSteel
12
1psia
.15psi
4.19ft
36ft
2ft
KochFlexitray

Comments:

99

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

RefluxAccumulator
Identification:Item HorizontalRefluxAccumulatorTank
Date:
4/4/2010
ItemNo.
D102ACCUMULATOR
No.Required
1
Function: ToaccumulateexcesstopsfromD102tobefedtofedtorefluxpump
Operation: Continuous
Materialshandled:
Reflux
Stream
StreamID:
S115
Quantity(lb/hr):
8273.578
Composition:
TDA
7.90E05
O2
0.0
CO
0.0
TDI
4.72E+01
WATER
8226.389
TDCARB
0.0
SOLVENT
0.009778

101.7
Temperature( F):
Pressure(psi):
1psi
DesignData:
Material:
Pressure:
MolarRefluxRatio:
Height:
VaporFraction:
HoldupTime:

CarbonSteel
1psi
0.007
1.93261720784302ft
0
5min

Comments:

100

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Condenser
Identification:Item Condenser
ItemNo.
D102CONDENSER
No.Required
1
Function: TocondensethetopsofD102
Operation: Continuous
Materialshandled:
D102Condenser
StreamID:
S115
Quantity(lb/hr):
8273.578
Composition:
TDA
7.90E05
O2
0.0
CO
0.0
TDI
4.72E+01
WATER
8226.389
TDCARB
0.0
SOLVENT
0.009778

Inlettemperatur(inF):
OutletTemperature(inF):
DesignData:
MaterialofConstruction:
HeatDuty:
Utilities:
Type:

Date:

4/4/2010

StainlessSteel
8628054.3btu/hr
CoolingWater
Total

Comments:

101

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Reboiler
Identification:Item DistillationReboiler
Date: 4/4/2010
ItemNo.
D102REBOILER
No.Required
1
Function: Toreheatthebottomsofthecolumnwhichwillbereintroducedtothecolumnasvapor
Operation: Continuous
Materialshandled:
D102REBOILER
StreamID:
S113
Quantity(lb/hr):
39662.81
Composition:
TDA
1.029915
O2
0.00E+00
CO
0.00E+00
TDI
39656.97
WATER
4.81E+00
TDCARB
0
SOLVENT
6.57E12

InletTemperature(F)
OutletTemperature(
DesignData:

264.38
352.2

MaterialofConstruction: CarbonSteel
HeatDuty:
8628054.3Btu/hr
Utilities:
13.9psiSteam
Type:
Kettle
Comments:

102

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

FlashDrum
Identification:Item VerticalFlashDrum
Date: [Date]
ItemNo.
F100
No.Required
1
Function: ToseparatethegasesandsolventtobesenttoR102andliquidbottomstobesentbacktoR100
Operation: Continuous
Materialshandled:
InletStream
TopStream
BottomStream
StreamID:
S102
S103
S128
Quantity(lb/hr):
292971.018
84460.84
208510.2
Composition:
TDA 1.17130117
5.19E08
1.171301
O2 993.537324
672.3039
321.2334
CO 103246.652
81428.69
21817.96
TDI 34.1342455
0.000107
34.13414
WATER 417.048468
0.228977
416.8195
TDCARB 0.00768696
7.69E13
0.007687
SOLVENT 188278.467
2359.616
185918.9

Temperature( F):
Pressure(psi):
DesignData:

99.91
644.67
Material:
VaporFraction:
HalfFullResidenceTime:
Diameter:
Length:
ShellThickness:

CarbonSteelwith1/4"HastelloyCoating
0.525
5min
14.67ft
29.34ft
0.75in

Comments:

103

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Heater
Identification:Item HEATER
ItemNo.
H100
No.Required
1
Function: TopreheatthetopliquidofD100tobefedtoD101
Operation: Continuous
Materialshandled:
InletStream
StreamID:
S110
Quantity(lb/hr):
9.7844+05
Composition:
TDA
1.03
O2
129.9303
CO
7786.079
TDI
3.9704+04
WATER
8231.36
TDCARB
3.647230
SOLVENT
9.2259+05

Date: 4/4/2010

OutletStream
S111
9.7844+05
1.03
129.9303
7786.079
3.9704+04
8231.36
3.647230
9.2259+05

120
Temperature( F):
Pressure(psi):
7
DesignData:
Type
MaterialofConstruction:
PressureDrop
HeatDuty
UtilityFluid
UtilityRequred
Comments:

KettleVaporizer
CarbonSteel
5
psi
138931683.9
Btu/hr
LowPressureSteam
140077
lb/hr

Toavoidboiling,assumeheatfluxof12000Btu/hr^2ft^2

104

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Heater
Identification:Item HEATER
ItemNo. H101
No.Requi
1
Function: ToheattheliquidfeedtoR102
OperationContinuous
Materialshandled:
InletStream
StreamID:
S121
Quantity(lb/hr):
3.0988+05
Composition:
TDA
5146.062
O2
1422.207
CO
2.6609+04
TDI
0.6952
WATER
0.1142
TDCARB
1.7672+04
SOLVENT
2.5903+05

Date: 4/4/2010

OutletStream
S122
3.0988+05
5146.062
1422.207
2.6609+04
0.6952
0.1142
1.7672+04
2.5903+05

Temperature( F):
248
Pressure(psi):
639.67
DesignData:
Type
MaterialofConstruction:
PressureDrop
HeatDuty
Area
UtilityRequired
Comments:

KettleVaporizer
CarbonSteelwithHastelloycoating
5
psi
15958528.41
Btu/hr
1329.9
ft^2
22066.27
lb/hr

Toavoidboiling,assumeheatfluxof12000Btu/hr^2ft^2

105

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Heater
Identification:Item HEATER
ItemNo.
H102
No.Required
1
Function: TopreheattheliquidstreamtoberecycledtoR100
Operation: Continuous
Materialshandled:
InletStream
StreamID:
S129
Quantity(lb/hr):
1.2475+06
Composition:
TDA
927.4625
O2
1202.179
CO
1.0910+05
TDI
1.0287+04
WATER
1661.714
TDCARB
8567.397
SOLVENT
1.1157+06

Date: 4/4/2010

OutletStream
PSEUDOUT
1.2475+06
927.4625
1202.179
1.0910+05
1.0287+04
1661.714
8567.397
1.1157+06

248
Temperature( F):
Pressure(psi):
639.67
DesignData:
Type
MaterialofConstruction:
PressureDrop
HeatDuty
Area
UtilityRequired
Comments:

KettleReboiler
CarbonSteelwithHastelloycoating
5
psi
39600089.7
Btu/hr
3300
ft^2
54756.08
lb/hr

Toavoidboiling,assumeheatfluxof12000Btu/hr^2ft^2

106

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Heater
Identification:Item HEATER
ItemNo.
H103
No.Required
1
Function: ToheatthegasstreamtobefedtoR102
Operation: Continuous
Materialshandled:
InletStream
StreamID:
S129
Quantity(lb/hr):
1.2475+06
Composition:
TDA
927.4625
O2
1202.179
CO
1.0910+05
TDI
1.0287+04
WATER
1661.714
TDCARB
8567.397
SOLVENT
1.1157+06

Date: 4/4/2010

OutletStream
PSEUDOUT
1.2475+06
927.4625
1202.179
1.0910+05
1.0287+04
1661.714
8567.397
1.1157+06

248
Temperature( F):
Pressure(psi):
639.67
DesignData:
Type
MaterialofConstruction:
PressureDrop
HeatDuty
Area
UtilityRequired
Comments:

KettleReboiler
CarbonSteel
5
322132.4
26.8
445.4209

psi
Btu/hr
ft^2
lb/hr

Toavoidboiling,assumeheatfluxof12000Btu/hr^2ft^2

107

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Heater
Identification:Item HEATER
ItemNo. H104
No.Requi
1
Function: ToheatgasrecyclestreamtobefedtoR100
OperationContinuous
Materialshandled:
InletStream
StreamID:
S129
Quantity(lb/hr):
1.2475+06
Composition:
TDA
927.4625
O2
1202.179
CO
1.0910+05
TDI
1.0287+04
WATER
1661.714
TDCARB
8567.397
SOLVENT
1.1157+06

Date: 4/4/2010

OutletStream
PSEUDOUT
1.2475+06
927.4625
1202.179
1.0910+05
1.0287+04
1661.714
8567.397
1.1157+06

Temperature( F):
248
Pressure(psi):
639.67
DesignData:
Type
MaterialofConstruction:
PressureDrop
HeatDuty
Area
UtilityRequired
Comments:

KettleReboiler
CarbonSteel
5
1866484.52
155.5
2580.837

psi
ft^2
Btu/hr^2ft^2

Toavoidboiling,assumeheatfluxof12000Btu/hr^2ft^2

108

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

HeatExchanger
Identification:Item HeatExchanger
Date:
ItemNo.
HX100
No.Required
1
Function: Toexchangeenergybetweenhotandcoldstreams
OperationContinuous
Materialshandled:
Coldin
Hotin
HotOut
StreamID:
S131
S109
S109
Quantity(lb/hr):
26522.2 2006412 2006412
Composition:
TDA
0
0
0
O2
43.303
0.006
0.006
CO
872.126
0.578
0.578
TDI
0
0
0
WATER
0.004
0.001
0.001
TDCARB
0
0
0
SOLVENT
7.076
0.415
0.415

Temperature( F):
Pressure(psi):
DesignData:
Type
MaterialofConstruction:
HeatDuty:
ShellDiameter
HeatTransferCoefficient:
HeatTransferArea
Comments:

106
645

203
2

4/4/2010

ColdOut
S132
26522.2
0
43.303
872.126
0
0.004
0
7.076

202
2

201
640

ShellandTubeHeatExchanger
CarbonSteel
660603
Btu/hr
15.25
in
149.69
Btu/hrft^2F
180.63
ft^2

109

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

HeatExchanger
Identification:Item HeatExchanger
Date: 4/4/2010
ItemNo.
HX101
1
No.Required
Function: Toexchangeenergybetweenhotandcoldstreams
OperationContinuous
Materialshandled:
Coldin
Hotin
HotOut ColdOut
StreamID:
S129
S109
S109
PSEUDLIQ
Quantity(lb/hr):
1124680.65 2006412 2006412 1124681
Composition:
TDA
7.59
0
0
7.59
O2
14.067
0.006
0.006
14.067
CO
1037.796
0.578
0.578 1037.796
TDI
59.024
0
0
59.024
WATER
89.302
0.001
0.001
89.302
TDCARB
22.893
0
0
22.893
SOLVENT
10733.445
0.415
0.415 10733.45

Temperature( F):
Pressure(psi):
DesignData:
Type
MaterialofConstruction:
HeatDuty:
ShellDiameter:
HeatTransferCoefficient:
HeatTransferArea:
Comments:

119
645

202
2

122
2

199
640

ShellandTubeHeatExchanger
CarbonSteel
Btu/hr
4649530
15.25
in
149.69
Btu/hrft^2F
87906.291
ft^2

110

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

HeatExchanger
Identification:Item HeatExchanger
Date: 4/4/2010
HX102
ItemNo.
1
No.Required
Function: Toexchangeenergybetweenhotandcoldstreams
Operation: Continuous
Materialshandled:
Coldin
Hotin
HotOut ColdOut
StreamID:
S121
S109
S109
S122
Quantity(lb/hr):
283361 2006412 2006412
283361
Composition:
TDA
42.122
0
0
42.122
O2
1.137
0.006
0.006
1.137
CO
77.832
0.578
0.578
77.832
TDI
0.004
0
0
0.004
WATER
0.003
0.001
0.001
0.003
TDCARB
47.22
0
0
47.22
SOLVENT
2582.213
0.415
0.415 2582.213

Temperature( F):
Pressure(psi):
DesignData:
Type:
MaterialofConstruction:
HeatDuty:
Shelldiameter:
Heattransfercoefficient:
Heattransferarea:
Comments:

75
653

122
2

112
2

120
648

ShellandTubeHeatExchanger
CarbonSteelwith1/4"HastelloyonTubeSide
4649530
Btu/hr
15.25
in
149.69
Btu/hrft^2F
2629.09
ft^2

111

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

HeatExchanger
Identification:Item HeatExchanger
Date: 4/4/2010
ItemNo. HX103
No.Requi
1
Function: Toexchangeenergybetweenhotandcoldstreams
OperationContinuous
Materialshandled:
Coldin
Hotin
HotOut ColdOut
StreamID:
S110
S109
S109
S111
Quantity(lb/hr):
978444 2006412 2006412
978444
Composition:
TDA
0.008
0
0
0.008
O2
4.06
0.006
0.006
4.06
CO
277.971
0.578
0.578 277.971
TDI
227.977
0
0 227.977
WATER
456.91
0.001
0.001
456.91
TDCARB
0
0
0
0
SOLVENT
9222.19
0.415
0.415 9222.19

Temperature( F):
Pressure(psi):
DesignData:
Tyoe:
MaterialofConstruction:
HeatDuty:
Shelldiameter:
Heattransfercoefficient:
Heattransferarea:
Comments:

35
12

112
2

37
2

96
7

ShellandTubeHeatExchanger
CarbonSteelwith1/4"HastelloyonTubeSide
34428316
Btu/hr
15.25
in
149.69
Btu/hrft^2F
190932.4
ft^2

112

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

HeatExchanger
Identification:Item HeatExchanger
ItemNo. HX104
No.Requi
1
Function: Toexchangeenergybetweenhotandcoldstreams
OperationContinuous
Materialshandled:
Coldin
Hotin
StreamID:
S112
S101
Quantity(lb/hr):
708099
292971
Composition:
TDA
0
0.01
O2
0
31.049
CO
0 3686.011
TDI
0.333
0.196
WATER
0.667
23.15
TDCARB
0
0
SOLVENT
0 1882.024

Temperature( F):
Pressure(psi):
DesignData:
Type:
MaterialofConstruction:
HeatDuty:
Shelldiameter:
Heattransfercoefficient:
Heattransferarea:
Comments:

182
8

283
626

Date: 4/4/2010

HotOut ColdOut
S102
S112
292971
708099
0.01
31.049
3686.011
0.196
23.15
0
1882.024

0
0
0
0.333
0.667
0
0

184
621

204
8

ShellandTubeHeatExchanger
CarbonSteel
32467349
15.25
in
149.69
Btu/hrft^2F
20138.73
ft^2

113

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

HeatExchanger
Identification:Item HeatExchanger
Date: 4/4/2010
ItemNo. HX105
No.Requi
1
Function: Toexchangeenergybetweenhotandcoldstreams
OperationContinuous
Materialshandled:
Coldin
Hotin
HotOut ColdOut
StreamID:
S112
S114
TDI
S112
Quantity(lb/hr):
708099
39663
39663
708099
Composition:
TDA
0
0.008
0.008
0
O2
0
0
0
0
CO
0
0
0
0
TDI
0.333 227.706 227.706
0.333
WATER
0.667
0.267
0.267
0.667
TDCARB
0
0
0
0
SOLVENT
0
0
0
0

Temperature( F):
Pressure(psi):
DesignData:
Type:
MaterialofConstruction:
HeatDuty:
Shelldiameter:
Heattransfercoefficient:
Heattransferarea:
Comments:

204
8

352
626

206
621

204
8

ShellandTubeHeatExchanger
CarbonSteel
Btu/hr
2295339
15.25
in
149.69
Btu/hrft^2F
462.55
ft^2

114

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
ItemNo.
P100
No.Required
1
Function: TopumpthebottomsofD100tobefedtoR102
OperationContinuous
Materialshandled:
InletStream
StreamID:
S106
Quantity(lb/hr):
2.3049+04
Composition:
TDA
5198.043
O2
0.0
CO
0.0
TDI
0.7022
WATER
2.273622
TDCARB
1.7850+04
SOLVENT
7.820018

Date: 4/4/2010

OutletStream
S107
2.3049+04
5198.043
0.0
0.0
0.7022
2.273622
1.7850+04
7.820018

521.1076
Temperature( F):
Pressure(psi):
653
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
280.408cuft/hr
648.1psi
28.672kW
0.78

Comments:

115

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
ItemNo.
P101
No.Required
1
Function: TopumpthetopsofD100tobefedtoD101
Operation: Continuous
Materialshandled:
InletStream
StreamID:
S109
Quantity(lb/hr):
978444.271
Composition:
TDA
1.0
O2
129.9
CO
7786.1
TDI
39704.152
WATER
8231.36036
TDCARB
0.0
SOLVENT
922591.719

Date: 4/4/2010

OutletStream
S110
978444.3
1.0
129.9
7786.1
39704.15
8231.36
0.0
922591.7

35.0177
Temperature( F):
Pressure(psi):
12
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
9784.44365cuft/hr
10psi
7.8426kW
0.8

Comments:

116

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo.
P102
No.Required
1
Function: TopumptheTDIbottomproductfromD102tostorage
OperationContinuous
Materialshandled:
InletStream
OutletStream
StreamID:
S113
S114
Quantity(lb/hr):
3.9663+04
3.9663+04
Composition:
TDA
1.0299
1.0299
O2
0.0
0.0
CO
0.0
0.0
TDI
3.9657+04
3.9657+04
WATER
4.8083
4.8083
TDCARB
0.0
0.0
SOLVENT
6.568112
6.568112

35.0177
Temperature( F):
Pressure(psi):
12
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
604.575cuft/hr
5psi
0.4258kW
0.498

Comments:

117

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo.
P103
No.Required
1
Function: TopumpthewastewaterfromthetopofD102tostorage
OperationContinuous
Materialshandled:
InletStream
OutletStream
StreamID:
S115
WASTEWTR
Quantity(lb/hr):
8273.578
8273.578
Composition:
TDA
7.898705
7.898705
O2
0.0
0.0
CO
0.0
0.0
TDI
47.1788
47.1788
WATER
8226.39
8226.39
TDCARB
0.0
0.0
SOLVENT
9.7777.03
9.7777.03

101.7455
Temperature( F):
Pressure(psi):
6
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
135.091cuft/hr
5psi
0.1854kW
0.2666

Comments:

118

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Pump&Motor
Identification:Item Pump
Date: 4/4/2010
ItemNo.
P104
No.Required
1
Function: TopumpthetopsofD101tobefedtoR100&R102
OperationContinuous
Materialshandled:
InletStream
OutletStream
StreamID:
S117
S118
Quantity(lb/hr):
9.3051+05
9.3051+05
Composition:
TDA
0.0
0.0
O2
129.9
129.9
CO
7786.1
7786.1
TDI
1.450630
1.450630
WATER
0.1626
0.1626
TDCARB
0.0
0.0
SOLVENT
9.2259+05
9.2259+05

36.513
Temperature( F):
Pressure(psi):
653
DesignData:
Type:
VolumetricFlowRate:
PressureChange:
ElectricityRequired:
Efficiency:

Centrifugal
9155.70cuft/hr
648psi
443.683kW
0.8

Comments:

119

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Reactor
Identification:Item HorizontalReactor
Date:
ItemNo.
R100&R101
No.Required
1
Function: Toreactthethestartingmaterialstocreatetheproducts
Operation: Continuous
Materialshandled:
CombinesInletStream
StreamID:
TDA,O2,CO,SOLVENT,&PSUEDO
Quantity(lb/hr):
1.2945+06
Composition:
TDA
28890.5137
O2
7328.4448
CO
121898
TDI
10287
WATER
1661.7135
TDCARB
8567.4708
SOLVENT
1115795.34

4/4/2010

OutletStream
RX1MID
1.2945+06
5200.244
1123.468
1.1103+05
3.9739+04
8648.409
1.7850+04
9.2259+05

282.765
Temperature( F):
Pressure(psi):
652.67
DesignData:
ResidenceTimeatHalfFull:
60min
MaterialofConstruction:
CarbonSteelwithHastelloycoating
Type:
FixedBedAutoclaveReactor
RXN1HeatofReaction:
()150773.43btu/lbmol
RXN2HeatofReaction:
()12384.795btu/lbmol
145609.0ft^3
Volume:
Comments:
Thegaseswillbebubbledupthroughtheliquidcausingthoroughmixing.
AlthoughASPENshowsR100&R101astwoseparatevessels,theywillbe
onesinglevessel.

120

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Reactor
Identification:Item HorizontalReactor
Date: 4/4/2010
ItemNo. R102&R103
No.Requi
1
Function: Toreactthethestartingmaterialstocreatetheproducts
Operation: Continuous
Materialshandled:
InletStream
OutletStream
StreamID:
B4RX2
RX2MID
Quantity(lb/hr):
309882.677
309882.7
Composition:
TDA
5146.0623
926.2912
O2
1422.02726
316.7826
CO
26608.7099
24673.74
TDI
0.69520548
10252.94
WATER
0.11421085
1244.617
TDCARB
17671.5052
8567.389
SOLVENT
259033.563
263900.9

Temperature( F):
Pressure(psi):
DesignData:

282.765
652.67

MaterialofConstruction:
Type:

CarbonSteelwithhastelloycoating
FixedBedAutoclaveReactor

Comments:
Thegaseswillbebubbledupthroughtheliquidcausingthoroughmixing.
AlthoughASPENshowsR102&R103astwoseparatevessels,theywillbe
onesinglevessel.

121

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo.
ST100
No.Required
1
Function: TostoreTDA
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
27962.73
Composition:
TDA
27962.73

Date: 4/4/2010

248
Temperature( F):
Pressure(psi):
652.67
DesignData:
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type
Comments:

CarbonSteel
1week
146035ft^3
103.714ft
17.286ft
336hrs
Open

122

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo.
ST101
No.Required
1
Function: TostoreSOLVENTmakeup
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
95.339
Composition:
SOLVENT
95.339

Date: 4/4/2010

248
Temperature( F):
Pressure(psi):
652.67
DesignData:
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type
Comments:

CarbonSteel
1week
199ft^3
11.493ft
1.9156ft
168hrs
Open

123

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo.
ST102
No.Required
1
Function: TostoreCO
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
12798.09
Composition:
CO
12798.09

Date: 4/4/2010

248
Temperature( F):
Pressure(psi):
652.67
DesignData:
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type
Comments:

CarbonSteel
1week
896650ft^3
189.916ft
31.653ft
168hours
Open

124

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo.
ST103
No.Required
1
Function: TostoreO2
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
7310.222
Composition:
O2
7310.222

Temperature( F):
Pressure(psi):
DesignData:

Date: 4/4/2010

248
653
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type

CarbonSteel
1week
444514ft^3
150.308ft
25.051ft
168hours
Open

Comments:

125

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo. ST104
No.Requi
1
Function: TostoreTFEsolvent
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
1.12E+06
Composition:
TFEsolvent
1.12E+06

Date: 4/4/2010

248
Temperature( F):
Pressure(psi):
639.67
DesignData:
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type
Comments:

CarbonSteel
1week
54571ft^3
74.704ft
12.451ft
3hrs
Open

126

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo.
ST105
No.Required
1
Function: TostoreWASTEWATER
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
8273.578
Composition:
WASTEWATER
8273.578

Date: 4/4/2010

101.7
Temperature( F):
Pressure(psi):
6
DesignData:
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type
Comments:

CarbonSteel
1week
22696ft^3
55.762ft
9.294ft
168hrs
Open

127

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BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo.
ST106
No.Required
1
Function: TostoreSLUDGE
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
230.488
Composition:
SLUDGE
230.488

Date: 4/4/2010

140
Temperature( F):
Pressure(psi):
648
DesignData:
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type
Comments:

CarbonSteel
1week
395.0ft^3
14.454ft
2.409ft
168hrs
Open

128

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

StorageTank
Identification:Item VerticalStorageTank
ItemNo.
ST107
No.Required
1
Function: TostoreTDI
OperationContinuous
Materialshandled:
Flow
StreamID:
Quantity(lb/hr):
39662.81
Composition:
TDI
39662.81

Date: 4/4/2010

140
Temperature( F):
Pressure(psi):
2.01
DesignData:
Material:
HoldingAmount:
Volume:
Diameter:
Length:
TimePeriod:
Type
Comments:

CarbonSteel
1week
90520ft^3
88.43ft
14.738ft
168hrs
Open

129

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Valve
Identification:Item ProcessSafetyValve
ItemNo.
V100
No.Required
1
Function: Toseparatethehighpressureandlowpressureprocesses
Operation: Continuous
Materialshandled:
Streams
StreamID:
RX1LIQ>TOSEP1
Quantity(lb/hr):
1001493
Composition:
TDA
5199.073
O2
129.9303
CO
7786.079
TDI
39704.85
WATER
8231.36
TDCARB
17850.01
SOLVENT
922591.7

DesignData:
PressureDrop:
Type:

Date:

4/4/2010

647.67psi
Diaphragm

Comments: Thisvalveisasafetymeasuretoseparatethehighandlow
pressurereactorandseparationsprocesses.

130

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

EquipmentCostSummary

131

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

Table 15 on the following page shows all the equipment to be used in the TDI
production process. The first column shows the unit numbers, as referenced on the detailed
visioProcessFlowDiagrams,followedbythepurchasecost,whichisadjustedfor2010CEIndex
of532.79,baremodulefactorandthebaremodulecostofeachunit.

The process machinery amounted to a bare module cost of $67,616,401, with an

additionalamountofpipingcost,calculatedas5%ofthetotalequipmentcost,of$4,335,982,
andestimatedshippingcost10,basedonindustrialconsultantssuggestion,of$9,105,563.The
totalbaremodulecost,thus,amountsto$81,057,946.

9http://www.che.com/pci/
10Shippingcostsincludethosepertainingtoprocessmachineries,fabricatedequipments,rawmaterials,TDI

product,solidwasteandwastewaterdisposals.

132

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

133

PhosgeneFreeRoutetoTolueneDiisocyanate

Table15:Equipmentcostsummary
ItemNo.
R100&R101
R102&R103
D100
D100Condenser
HX106
D100ReboilerPump
D100Accumulator
D100RefluxPump
D101
D101Condenser
HX107
D101ReboilerPump
D101Accumulator
D101RefluxPump
D102
D102Condenser
D102Reboiler
D102ReboilerPump
D102Accumulator
D102RefluxPump
HX100
HX101
HX102
HX103
HX104
HX105
P101
P102
P103
P100
P104
H100
H101
H102
H103
H104
C100
C102
C101
F100
ST104
ST105
ST106
ST107
ST100
ST101
ST102
ST103

Name
Reactor1
Reactor2
Distillation1column
Col1condenser
Col1hotoilsystem
Col1reboilerpumpandmotor
Col1refluxaccumulator
Col1refluxpumpandmotor
Distillation2column
Col2condenser
Col2hotoilsystem
Col2reboilerpumpandmotor
Col2refluxaccumulator
Col2refluxpumpandmotor
Distillation3column
Col3condenser
Col3reboiler
Col3reboilerpumpandmotor
Col3refluxaccumulator
Col3refluxpumpandmotor
Heatexchanger1
Heatexchanger2
Heatexchanger3
Heatexchanger4
Heatexchanger5
Heatexchanger6
Pumpandmotor1
Pumpandmotor2
Pumpandmotor3
Pumpandmotor4
Pumpandmotor5
Heater1
Heater2
Heater3
Heater4
Heater5
Cooler1
Cooler2
Cooler3
Flashdrum
Storagetank1
Storagetank2
Storagetank3
Storagetank4
Storagetank5
Storagetank6
Storagetank7
Storagetank8
Piping,mixer,splitter
Shipping
Total

BouSaba,Dizon,Kasih,Stewart

Type
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment

PurchaseCost
$3,601,982
$975,195
$358,784
$732,226

BareModuleFactor
4.16
4.16
4.16
3.17

BareModuleCost
$14,984,247
$4,056,812
$1,492,542
$2,321,158

FabricatedEquipment
ProcessMachinery
FabricatedEquipment
ProcessMachinery
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
ProcessMachinery
FabricatedEquipment
ProcessMachinery
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
ProcessMachinery
FabricatedEquipment
ProcessMachinery
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
ProcessMachinery
ProcessMachinery
ProcessMachinery
ProcessMachinery
ProcessMachinery
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
FabricatedEquipment
Storage
Storage
Storage
Storage
Storage
Storage
Storage
Storage
Spares
OtherEquipment

$121,330
$20,873
$42,323
$604,915
$2,081,824
$664,903
$18,467
$8,417
$27,045
$361,561
$105,262
$200,000
$34,077
$10,040
$16,220
$15,303
$15,022
$705,720
$34,099
$1,859,691
$178,472
$17,307
$6,959
$4,883
$5,844
$14,048
$72,557
$163,369
$42,762
$67,752
$32,150
$26,031
$27,789
$7,820
$16,770
$49,837
$210,278
$111,805
$6,053
$302,715
$427,157
$3,689
$2,911,746
$2,153,358

3.17
3.30
3.05
3.30
4.16
3.17
3.17
3.30
3.05
3.30
4.16
1.00
3.17
3.30
3.05
3.30
3.17
3.17
3.17
3.17
3.17
3.17
3.30
3.30
3.30
3.30
3.30
3.17
3.17
3.17
4.17
5.17
3.17
3.17
3
4
3
3.0
3
3
3.0
3
3
3.0

$384,618
$68,881
$129,086
$1,996,220
$8,660,388
$2,107,742
$58,540
$27,777
$82,487
$1,193,151
$437,889
$200,000
$108,024
$33,131
$49,472
$50,500
$47,618
$2,237,132
$108,095
$5,895,221
$565,756
$54,864
$22,964
$16,115
$19,287
$46,358
$239,439
$517,879
$135,554
$214,773
$134,064
$134,583
$88,092
$24,791
$53,159
$207,321
$630,833
$335,414
$18,159
$938,416
$1,281,471
$11,068
$8,735,237
$6,460,075
$4,335,982
$9,105,563
$81,057,946

134

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

FixedCapitalInvestment
Summary

135

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

FixedCapitalInvestmentSummary

ThefixedcostsfortheTDIproductionprocessmainlyincludeequipmentandshipcosts,

whichhavebeendiscussedearlierintheprevioussection.Therearealsoothercostswhichare
assumed to be driven by the total bare module costs, direct permanent investment and
depreciable capital. Table 16 below shows the total permanent investment assumptions and
thefixedcapitalinvestmentsummaryoftheproject.
Table16:Totalpermanentinvestmentinputassumptions
CostofSitePreparations:
CostofServiceFacilities:
AllocatedCostsforutilityplantsandrelated
facilities:
CostofContingenciesandContractorFees:
CostofLand:
CostofRoyalties:
CostofPlantStartUp:

5.00% ofTotalBareModuleCosts
5.00% ofTotalBareModuleCosts
$0
10.00% ofDirectPermanent
Investment
2.00% ofTotalDepreciableCapital
$0
4.00% ofTotalDepreciableCapital

Thecostofsitepreparationsisassumedtobe5%ofthetotalbaremodulecosts.Since

theprojectwillbecarriedoutattheGulfCoastarea,webelievethatthesitealreadyhasan
existing integrated complex. That is, it is relatively unnecessary to undertake land surveys,
surface clearing, excavating and landscaping. Therefore, the 5% cost allocation would be
reasonableforthisparticularproject.

The cost of service facilities includes utility lines, control rooms, laboratories for feed

and product testing, maintenance shops, and other buildings. According to Seider, et al, the
costallocationof5%wouldbeadequateandrelativelyconservative.Furthermore,wedidnot
allocateanycostforutilityplantsandrelatedfacilitiessincetheutilitieswillbepurchasedfrom
vendors.

136

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

Moreover,weallocate7%ofdirectpermanentinvestmenttothecostofcontingencies
sincetheTDIproductionisaverytypicalindustrialprocess.Itdoes notinvolve tremendously
hazardousmaterialsandwaste.Thus,wedonotexpectahighprobabilityofcontingencyinthe
project. The other 3% cost allocation goes to the contractor fees, as suggested by Guthrie
(1969)11.Thecostoflandisalsopredictedas2%oftotaldepreciablecapital.Finally,thecostof
plant startup should not be too expensive since our process does not involve highly novel
technology, such that the process and equipment are well known to skilled operators.
AccordingtoSeider,etal,thestartupcostmaybeaslowas2%,buttoremainconservative
withourassumptions,wechose4%instead.

With all these assumptions, the calculated total fixedcost investments to be incurred

duringthefirstyearaftertheprojectstartdatearetabulatedinTable17.Itisshownthatthe
totalcapitalinvestmentamountsto$105,569,294.

11Seider,Seader,Lewin,Widagdo;ProductandProcessDesignPrinciples

137

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Table17:Fixedcapitalinvestmentsummary
InvestmentSummary

BareModuleCosts

FabricatedEquipment

$45,491,906

ProcessMachinery

$3,713,822

Spares

$4,335,982

Storage

$558,300

OtherEquipment

$13,662,014

Catalysts

$14,546,797

Computers,Software,Etc.

$82,308,821
TotalBareModuleCosts:

DirectPermanentInvestment

CostofSitePreparations:

$4,115,441

CostofServiceFacilities:

$4,115,441

AllocatedCostsforutilityplantsandrelatedfacilities: $

$90,539,703
DirectPermanentInvestment

TotalDepreciableCapital

CostofContingencies&ContractorFees
$9,053,970

$99,593,673
TotalDepreciableCapital

TotalPermanentInvestment

CostofLand:

$1,991,873

CostofRoyalties:

$

CostofPlantStartUp:

$3,983,747

TotalPermanentInvestmentUnadjusted

$105,569,294
SiteFactor

1.00

$105,569,294
TotalPermanentInvestment

138

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

OperatingCostand
EconomicAnalysis

139

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

EconomicAssumptionsandProjectOperations
Oureconomicanalysesarebasedonthefollowingtabulatedassumptionsandproject
chronology.TheprojectwillalsoyieldTDIasitssoleproduct.
Table18:Projectassumptionsandoperationssummary
GeneralInformation

ProcessTitle:

Product:

PlantSiteLocation:

SiteFactor:

OperatingHoursperYear:

OperatingDaysPerYear:

OperatingFactor:

ProductInformation
ThisProcesswillYield

Price

Chronology

Year
Action
2010 Design
2011 Construction
2012 Production
2013 Production
2014 Production
2015 Production
2016 Production
2017 Production
2018 Production
2019 Production
2020 Production
2021 Production
2022 Production
2023 Production
2024 Production
2025 Production
2026 Production

PhosgeneFreeRoutetoIsocyanate

TolueneDiisocyanate(TDI)

GulfCoast

1.00

7920

330

0.9041

39,663 lbofTolueneDiisocyanateperhour

951,907 lbofTolueneDiisocyanateperday

314,129,466 lbofTolueneDiisocyanateperyear

12
$1.50 /lb

Distributionof
Production Depreciation
PermanentInvestment
Capacity
5yearMACRS

0.0%

100%
0.0%

0%
45.0%
20.00%
0%
67.5%
32.00%
0%
90.0%
19.20%

90.0%
11.52%

90.0%
11.52%

90.0%
5.76%

90.0%

90.0%

90.0%

90.0%

90.0%

90.0%

90.0%

90.0%

90.0%

ProductPrice

$1.50
$1.52
$1.55
$1.57
$1.59
$1.62
$1.64
$1.66
$1.69
$1.72
$1.74
$1.77
$1.79
$1.82
$1.85

12Givenintheproblemstatement

140

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

OperatingCostSummary
Variablecosts

The main components for our variable costs include the raw materials, utility costs,

catalyst and promoter costs, and general expenses. The raw materials include TDA, oxygen,
carbon monoxide, and TFE makeup. The prices of the first three materials are given in the
problemstatement.Anestimateof$12perkilogramforthepriceofTFEwassuggestedbyone
ofitssuppliers,Halocarbon.Sincewewillbeconsumingapproximately1millionpoundsofTFE,
which makes up 20% of the current global TFE demand, we assumed a bulk price of $9 per
kilogramor$4.08perpoundofTFE.
TheutilitypricesaretakenfromSeider,etal,database,adjustedfor 2010$.Thecost
breakdownforutilitiesisprovidedinAppendix4.
The prices of the CotBuSalen catalyst and the NaI promoter are relatively harder to
obtain. One of the project consultants, Mr. Gary Sawyer of Lyondell Chemical Company,
suggestedthatthecatalystpriceismainlydependsontheligandused.Mr.Sawyerreferredus
toacomparablecatalystligand,AcetylAcetone(AcAc)ofwhichthepricerangesfrom$500to
$6,000perkilogramor$227to$2,727perpound.Thus,wemadeabasecaseassumptionof
$3,000perkilogramor$1,364perpoundforthepriceofCotBuSalencatalyst.Thepriceofthe
NaI promoter is estimated from Mandev Enterprises, a wholesaler company from India.13
Finally,tobemoreconservative,wealsotookaccountforthepossibilitiesthatthecatalystand

13Chatha,SodiumIodide

141

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

theNaIbeingwornoutandthereforeneedtobereplaced.Weassumedthatthecatalystand
theNaIhavetobereplacedevery9monthsand6monthsrespectivelyasabasecase.
The general expenses comprise of selling and transfer expenses, research expenses,
administrative expenses and management compensation. In an industry where technology
advancementisverycrucial,itisreasonabletoassumethatthedirectandallocatedresearch
expensesshouldmakeupmostofthecosts.Inourcase,itmakesup41.6%ofthetotalgeneral
expenses.
Below is the tabulated summary of the annual variable costs which will be incurred
shouldweundertaketheproject.
Table19:Summaryofannualvariablecosts
VariableCostSummary
VariableCostsat100%Capacity:

GeneralExpenses

Selling/TransferExpenses:

DirectResearch:

AllocatedResearch:

AdministrativeExpense:

ManagementIncentiveCompensation:

TotalGeneralExpenses

RawMaterials

Byproducts

Utilities

TotalVariableCosts

$1.051077 perlbofToluene
Diisocyanate

$0.000000 perlbofToluene
Diisocyanate

$0.048050 perlbofToluene
Diisocyanate

$
14,135,826
$
22,617,322
$2,355,971
$9,423,884
$5,889,927

$
54,422,930

$330,174,135

$0

$15,093,772

$
399,690,837

142

PhosgeneFreeRoutetoTolueneDiisocyanate
BouSaba,Dizon,Kasih,Stewart

From Table 19 and based on the amount of TDI produced per year, it is found that $1.27
variablecostswillbeincurredforeverypoundofTDIsold.GiventhepriceofTDIof$1.50per
pound,theprojectwillhaveaprofitmarginof$0.23perpoundofTDIsold.
Thebreakdownofthetotalvariablecostscanbeseeninthefollowingfigure.

Figure14.BreakdownofannualvariablecostsofTDIproduction
Thebreakdownshowsthattherawmaterialsmakeupmostofthevariablecosts,followedby
thegeneralexpenses,andutilities.

143

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

FixedCosts

FixedcostsareindependentoftheamountofTDIproducedannually.Table20shows

thesummaryoftheannualfixedcostswillbeincurredforthisproject.
Table20:Summaryofannualfixedcosts
FixedCostSummary

Operations

DirectWagesandBenefits

DirectSalariesandBenefits

OperatingSuppliesandServices

TechnicalAssistancetoManufacturing

ControlLaboratory

TotalOperations

Maintenance

WagesandBenefits

SalariesandBenefits

MaterialsandServices

MaintenanceOverhead

TotalMaintenance

OperatingOverhead

GeneralPlantOverhead:

MechanicalDepartmentServices:

EmployeeRelationsDepartment:

BusinessServices:

TotalOperatingOverhead

PropertyTaxesandInsurance

PropertyTaxesandInsurance:

OtherAnnualExpenses

RentalFees(OfficeandLaboratorySpace):

LicensingFees:

Miscellaneous:

TotalOtherAnnualExpenses

$936,000
$140,400
$56,160
$900,000
$975,000

$3,007,560

$3,485,779
$871,445
$3,485,779
$174,289

$8,017,291

$385,787
$130,407
$320,584
$402,088

$1,238,866

$1,991,873

$20,000
$
$10,000

$30,000

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TotalFixedCosts

BouSaba,Dizon,Kasih,Stewart

$14,285,590

Comparing the fixed costs to the total variable costs, they are relatively low and
thereforenotamajorfactorintheprofitabilityoftheproject.

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CashFlowandProfitabilityAnalysis
ProjectEconomics

ThefeasibilityandtheprofitabilityoftheTDIproductionprocessareanalyzedbasedon
several metrics, namely the net present value (NPV), internal rate of return (IRR), return on
investment(ROI),andpaybackperiod.Adiscountrateof15%isusedtocalculatetheNPV,as
recommendedbySeider,etal.Theeconomicanalysissummarybasedonassumptionsonthe
base,best,andworstcasescenariosaretabulatedbelow.
Table21:Economicanalysissummary
Worst
Rawmaterials
TDIprice($/lb)
TFEprice($/lb)
Catalystprice($/lb)
NaIprice($/lb)
Process
Reactorresidencetime(min)
Catalystlifespan(month)
NaIlifespan(month)

ProfitabilityMeasures
NetPresentValue
ROI
IRR
Paybackperiod(years)

Base

Best

$1.20
$5.45
$2,272.73
$1.00

$1.50
$4.09
$1,363.64
$0.45

$1.90
$3.60
$681.82
$0.35

180
4
4

60
8
8

20
12
12

($435,917,600) $20,658,400 $392,139,600

43.15%
12.03%
76.69%

18.05%
66.55%

3
0

Basedontheresultsabove,itissatisfyingtoseethatonthebasecaseassumption,the

TDIproductionprocessisfeasibleandalsoprofitable.Inaddition,theassumptionsmadeinthe
base case scenario are conservative. The raw materials prices have been discussed in the
earliersection.Withregardstothereactorresidencetime,ourassumptionsaresolelybasedon
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theknowledgefromthepatentcontributedbyFernandez,etal(2008),whichmentionsthatthe
reaction time ranges from 3 minutes to 3 hours. Due to the limited readily available kinetics
data on our particular reaction processes, the information from the patent is deemed
reasonable.ThesameargumentappliestotheusablelivesofourcatalystandNaIpromoter.
Thus,roughassumptionsweremadeaftergettingapprovalfromtheprojectconsultants.

Table22summarizesthebasecasecashflowoftheTDIproductionprocess.

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Table22:TDIproductionbasecasecashflowsummary

CashFlowSummary
Year
2010
2011
2012
2013
2014
2015
2016
2017
2018
2019
2020
2021
2022
2023
2024
2025
2026

Sales

212,037,400

322,826,900

436,892,400

443,445,800

450,097,500

456,849,000

463,701,700

470,657,200

477,717,100

484,882,900

492,156,100

499,538,400

507,031,500

514,637,000

522,356,500

CapitalCosts

(105,569,300)

WorkingCapital

VarCosts
FixedCosts



(10,623,700)

(5,311,800) (202,121,557) (14,285,590)

(5,311,800) (294,972,516) (14,428,446)

(389,660,281) (14,572,731)

(393,556,884) (14,718,458)

(397,492,453) (14,865,643)

(401,467,377) (15,014,299)

(405,482,051) (15,164,442)

(409,536,872) (15,316,086)

(413,632,240) (15,469,247)

(417,768,563) (15,623,940)

(421,946,248) (15,780,179)

(426,165,711) (15,937,981)

(430,427,368) (16,097,361)

(434,731,642) (16,258,334)

21,247,300 (439,078,958) (16,420,918)

Depreciation
Taxes
NetEarnings
CashFlow

(116,193,000)

(19,918,735)
8,986,700 (15,301,800)
(694,900)

(31,869,975)
6,824,300 (11,619,700)
14,938,400

(19,121,985)
(5,008,900)
8,528,600
27,650,600

(11,473,191)
(8,768,000)
14,929,300
26,402,500

(11,473,191)
(9,718,500)
16,547,700
28,020,900

(5,736,596) (12,813,400)
21,817,300
27,553,900

(15,930,400)
27,124,800
27,124,800

(16,947,600)
28,856,700
28,856,700

(17,987,800)
30,627,800
30,627,800

(19,051,400)
32,438,900
32,438,900

(20,139,000)
34,290,700
34,290,700

(21,250,900)
36,183,900
36,183,900

(22,387,500)
38,119,300
38,119,300

(23,549,400)
40,097,600
40,097,600

(24,737,000)
42,119,700
63,367,000

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SensitivityAnalysis

Astherangeoftheprofitabilityhasbeendetermined,moredetailedeconomicanalyses

arecarriedouttoensurethereliabilityofourrecommendation.Aftercarefulanalysesonthe
keydriversoftheTDIproductionprocess,thereareseveralitemsthroughwhichour
recommendeddecisionontheprojectmayormaynotchange,namely:
TDIproductprice
CotBuSalencatalystpriceandlifespan
Reactorresidencetime
SensitivityofNPVtowardsTDIProductPriceandProductInflationRate

Product Price

Table23:SensitivityanalysisonNPVtowardsTDIpriceanditsinflationrate

Product Price Inflation Rate

1.0%
1.5%

###

0.0%

0.5%

2.0%

2.5%

3.0%

$0.75

($510,959,000)

($579,394,700)

($563,175,500)

($546,378,700)

($528,981,200)

($510,959,000)

($492,287,000)

$0.90

($390,467,600)

($472,590,500)

($453,127,400)

($432,971,300)

($412,094,300)

($390,467,600)

($368,061,200)

$1.05

($269,976,300)

($365,786,300)

($343,079,400)

($319,563,800)

($295,207,400)

($269,976,300)

($243,835,500)

$1.20

($149,484,900)

($258,982,100)

($233,031,300)

($206,156,400)

($178,320,500)

($149,484,900)

($119,609,700)

$1.35

($28,993,600)

($152,177,900)

($122,983,300)

($92,749,000)

($61,433,500)

($28,993,600)

$4,616,000

$1.50

$91,497,800

($45,373,700)

($12,935,200)

$20,658,400

$55,453,400

$91,497,800

$128,841,800

$1.65

$211,989,100

$61,430,500

$97,112,900

$134,065,800

$172,340,300

$211,989,100

$253,067,500

$1.80

$332,480,500

$168,234,700

$207,160,900

$247,473,300

$289,227,200

$332,480,500

$377,293,300

$1.95

$452,971,800

$275,038,900

$317,209,000

$360,880,700

$406,114,100

$452,971,800

$501,519,000

$2.10

$573,463,200

$381,843,100

$427,257,000

$474,288,100

$523,001,000

$573,463,200

$625,744,800

$2.25

$693,954,600

$488,647,300

$537,305,100

$587,695,500

$639,887,900

$693,954,600

$749,970,500

ThetableaboveshowsthatthepositiveNPVwehavecurrentlyisverysensitivetowards

thefutureproductinflationrateandtheTDIcompetitiveprice.IftheglobalTDIdemandisnot
sustainableorkeepsindecreasingtrend,itisnaturalthattheTDIproductpricemaybecome
cheaper.Inaddition,theriskofdeflationmayalsobecomemoreimportant.Ifthisisthecase,
thentheprojectmaynotlookattractivesinceNPVstartsbecomingnegativerightaway.

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However, it is expected that the current decreasing trend in global TDI demand will

rebound soon after the economy recovers. In addition, TDI is one of the most important
materials in automotive and transport industries. These industries are growing really fast
especiallyindevelopingcountries.Forexample,itsdemandinthegianteconomicdriver,China,
has been showing promising trend. Even in the more developed countries like the US,
transportationandautomotiveindustriesareamongstthemostsustainable.Thus,itisunlikely
thattheTDIpricewilldropinthefuture,nottomentionanygreatpossibilityofdeflation.
SensitivityofNPVtowardsCatalystPriceanditsLifespan

Co-tBu-Salen Price per lb

Table24:SensitivityanalysisonNPVtowardsCotBuSalencatalystpriceandlifespan

#####
$600
$650
$850
$1,050
$1,250
$1,364
$1,450
$1,650
$1,850
$2,050
$2,250

2
($23,848,900)
($35,602,800)
($82,618,600)
($129,634,400)
($176,650,300)
($176,650,300)
($223,666,100)
($270,681,900)
($317,697,700)
($364,713,500)
($411,729,300)

4
$41,862,900
$35,584,900
$10,473,100
($14,638,800)
($39,750,700)
($39,750,700)
($64,862,500)
($89,974,400)
($115,086,300)
($140,198,100)
($165,310,000)

Co-tBu-Salen Replacement Period (month)

6
8
10
$63,766,800
$74,718,800
$81,290,000
$59,314,200
$71,178,800
$78,297,600
$41,503,600
$57,018,900
$66,328,100
$23,693,100
$42,859,000
$54,358,600
$5,882,500
$28,699,100
$42,389,100
$5,882,500
$28,699,100
$42,389,100
($11,928,000)
$14,539,200
$30,419,600
($29,738,600)
$379,300
$18,450,100
($47,549,100)
($13,780,600)
$6,480,600
($65,359,700)
($27,940,500)
($5,489,000)
($83,170,300)
($42,100,400)
($17,458,500)

12
$85,670,800
$83,043,500
$72,534,200
$62,025,000
$51,515,700
$51,515,700
$41,006,500
$30,497,200
$19,988,000
$9,478,700
($1,030,500)

14
$88,799,900
$86,433,400
$76,967,200
$67,501,000
$58,034,800
$58,034,800
$48,568,600
$39,102,300
$29,636,100
$20,169,900
$10,703,700

Thesensitivitytableaboveshowsaverywiderangeofthepossiblecatalystpricesand

its lifespan. However, we are more interested in observing the data around our base case,
which are highlighted in blue. In this region, there is only one negative NPV data point, i.e.
whenthecatalystlifespanis2monthsshorterthanthatinourbasecaseandthepriceisabout
$100higher.Althoughwebelievethatourassumptionsarefairlyconservative,wewouldstill
be uncertain since theprofitabilityreally depends on the specific properties of this particular
catalyst. As per current understanding, the project is recommended only if the catalysts
lifespanisatleast6monthswithapriceoflessthan$1,450perlb.FurtherresearchonCotBu
Salenisstronglyrecommendedinordertocomeupwithsolidprojectrecommendation.
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SensitivityofNPVtowardsReactorResidenceTime

NPV

Table25:SensitivityanalysisonNPVtowardsreactorresidencetime

20
$38,155,300

40
$29,295,700

60
$20,653,700

Reactor residence time (min)

80
100
120
$12,122,000
$3,660,000
($4,752,900)

140
160
180
($13,128,600) ($21,475,100) ($29,797,600)

Same as the previous section, it is rather difficult to decide whether the assumptions

madearevalidwhenthekineticsanddetailedreactiondataarenotavailable.However,from
the current knowledge that we have, the project is still profitable and thus should be
undertakenaslongasthereactiontimedoesnotreachtwohours.Again,furtherresearchon
thereactionkineticsneedstobecarriedoutthoroughly.

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OtherEconomicUncertainties

Therearequiteanumberofeconomicuncertaintiesthatneedtobeconsideredinthis

project.
RawMaterialsandTDIProduct
As mentioned before, the price of the CotBuSalen catalyst and any information
pertainingitskinetics,lifespan,andeffectivenessinsupportingtheTDIformationreactionare
not readily available. In addition, the global TDI demand is currently fluctuating in various
regions. Thus, further economic research has to be done before deciding whether it is truly
worthwhiletostartproducingTDIthroughthephosgenefreeroute.
ProductionProcess

There are also some uncertainties that need to be account for during the production

process. Firstly, it is assumed that there are no polymeric materials formed during the TDI
production process even when the process machineries operate at high pressure. The
polymericmaterialsformationwillreducethetotalamountofTDIproduced.Therefore,there
arepossibilitiesthatweneedtoaccountfortheequipmenttoremovepolymericmaterials,i.e.
the whitefilm evaporator. Although we already have a 5% buffer on the amount of the TDI
produced per year, the uncertainties still exist and we do not have 100% confidence in how
muchpolymericmaterialmaybeformed.

In addition, we also assumed that any solid waste and wastewater produced in the

process are within the regulatory limits. This implies that we may need to account for waste
managementcoststhatmightpossiblycomeup.
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OtherEconomicUncertainties
Major economic uncertainties include changes in macroeconomic growth, changes in
raw material and product prices, government regulations, and supply and demand sides
technologicaladvancesrelatedtoTDIproductionprocess

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OtherIssuesand
Considerations

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OtherIssuesandConsiderations
EnvironmentalConcerns:

In keeping up with EPA guidelines, the wastewater produced as a byproduct in the

reactionwillbedistilledtoashighapurityaspossibletopreventenvironmentalcontamination.
The EPA has produced guidelines for the treatment, storage, and transportation of industrial
wastewater. The federal government regulates the dumping of hazardous industrial
wastewater by requiring companies to apply for dumping permits. These permits are only
issued if the company wishing to dump can prove that their wastewater meets federal
standardsofcompositionandthattheirwastewillnotcontaminatethedrinkingwatersupply
or surfacewater in which there isa high risk for human contact. The EPA also regulates the
storage of wastewater. Wastewater storage tanks must be placed on special platforms or in
speciallydesignatedstoragefacilities.Theymustalsobemonitoredcontinuouslyforcracking
andleaks.Thetransportationofwastewatertooffsitewatertreatment/waterdisposalsitesis
alsohighlyregulatedbyfederallaw14.Inall,theseprecautionsareallimportantinpreventing
accidentalrunofforleakageofindustrialwasteintotheenvironmentatlarge.Thecollection
andremovaloftheheavysludgefromthefirstdistillationcolumnaresimilarlyregulated.
As one of our main project goals, an environmentally friendly process is highly
importanttoplantsustainability.Inthisregard,weplantofollowallfederalandregionalwaste

14EPA,EMSHandbookforWastewaterUtilities

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storage and removal guidelines (EPA, OSHA, etc.) to prevent any of our hazardous materials
fromenteringandmaliciouslyimpactingtheenvironment.
PlantSafetyConcerns:
Aprimaryconcerninthedesignofthisprocessisplantsafety.Althoughphosgeneisby
farthemosthazardouscomponentofalternativeTDIproductionprocessdesigns,therearestill
safety hazards in this design that need to be carefully monitored. The safety risk of greatest
concern is the ratio gaseous O2 to CO where both coexist in a gas phase. The areas of the
process to which this is relevant include the vapor phase in the two reactors and within the
pipingthatconnectsthevaporeffluentstreamstoandfromthesereactors.Theexplosionrisk
concentrationrangeofCOinO2at392Fand14.7psigoesfrom14.2%to95.3%.Itistherefore
necessary to keep a high ratio of CO:O2 in the gas phase; a ratio of at least 19:1 is
recommended.Theprocessisdesignednottocomeneartheexplosiveriskrange,howeverit
cannot be determined that all of the equipment will consistently operate to maintain the
concentrationsatanygiventime.Thatis,althoughtheaveragesteadystatemaybewellwithin
safetystandards,deviationsinoperabilitymayposeathreat.Toaccountforthis,thereisone
controlsystemforeachreactorsetinplacetomaintainthisoperationcondition.Thefeedback
controlleradjuststheCOandO2feedvalvesinresponsetotherelativeconcentrationsofCO
andO2inthereactorvapors.Itisimportanttonoteherethatafullscalecontrolanalysisfor
thisprocessisnotinthescopeofthisproject.

Thehighpressurereactionsystemposesanothersafetyhazard.Pressurebuildupsand

leaks within the reactors and piping can lead to serious problems. Control valves should be
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installed as necessary at various stages throughout the process to monitor and manage
unexpectedpressurerelatedissues.Controlmechanismsmeasuringtheoxygenconcentration
inside the columns are extremely necessary because they operate at pressures lower than
atmosphericpressure.Thismeansthatifthereisaleakinacolumn,aircouldenterthevessel
increasing the oxygen concentration in the vapor phase which could bring the vapor
composition into the explosion envelope. Obviously, this scenario could be extremely
dangerous.

As mentioned previously, the reaction section and first distillation column must be

coated in Hastelloy to prevent equipment corrosion. The reaction promoter, NaI, is highly
corrosiveandcancausesubstantialdamagetotheequipmentandpipingwithoutthecoatof
highlycorrosionresistantalloy.TheHastelloycoatsignificantlyincreasestheequipmentcosts
but is absolutely necessary to prevent more costly damage. At this time, there is not enough
information about the role and properties of NaI within this process to develop control
measures to ensure that all of the NaI is contained within the designated equipment loops;
howeverthatisanecessarycourseofinvestigationinthelaterstagesofprocessdevelopment.

Asfaraschemicalhandling,themainmaterialsthatwillbepresentintheprocesspose

moderatehealthrisks.TFEisharmfulifinhaled,absorbedthroughtheskin,incontactwiththe
eyesoringested(TFEMSDS).WorkersmusttakecaretoavoidinhalingTFEfumesasthishas
been proven to cause serious health problems over prolonged exposure. Most of the TFE
handlingwillbeduringtheinitialchargeandrechargesafterdowntime,sincethesolventisnot
consumedandispreservedtoahighdegreeduringseparations.

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TDAishighlypoisonousandmaybefatalifswallowed,inhaledorabsorbedthroughthe
skin (TDA MSDS). As with TFE, direct contact with TDA should be minimal as its only contact
pointtothesystemistypicallyasteadyfeed.TheamountofTDAusedinourprocessmustbe
reportedtotheEPAbecauseitexceedsthe10lbreportablequantitylimit15.Thehandlingand
disposalofquantitiesexceedingthislimitfallsunderaregulationcalledResourceConservation
and Recovery Act (RCRA). Based on RCRA criteria, materials contaminated with TDA are
considered hazardous waste upon disposal. For this reason we will need to follow certain
storage,handlinganddisposalrestrictionsasoutlinedintheRCRA(TDAMSDS).
TDIishazardousifingested.TDIisalsoclassifiedasaneyeandskinirritantwithariskof
deathifsevereexposureoccurs.AnothersafetyconcernarisesinthestorageofTDI.TDiisa
highly flammable substance at high temperature, and it must be stored in locations far away
fromheatandanyareainwhichitcanbeignited(TDIMSDS).TheamountofTDIproducedin
our process must be reported to the EPA because it exceeds the 100lb reportable quantity
limit. Finally, a monitoring system must be put in place to test whether TDI stays below the
OSHAmaximumof0.02ppminair15.
NaI,whichshouldbepresentinmuchlowerconcentrationsthantheothercomponents,
is an irritant and can cause complications if ingested, inhaled or absorbed by the skin (NaI
MSDS).However,thischemicalwillalsobealmostentirelycontainedwithinthesystematall
times.
Oxygengasismosthazardousduetocombustionrisk.

15Barbalace,EnvironmentalChemistry

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Carbonmonoxideishighlytoxicandparticularlydangerousbecauseitishardtodetect.
Monitorswillbeinstalledtopreventunknownexposure.Forsafetyreasons,itisaprioritythat
bothofthesegasesbehandledverycarefully.
Startup
Theamountofsolventrequiredtochargethereactorwillneedtobesuppliedinvery
highvolume.Infact,theamountofTFErequiredforthisprocesswillconsumeapproximately
1520% of the current worlds supply. Because this requires such high volume of chemical
purchase, transport, and storage, the predicted costs for TFE supply are only approximate
estimateswhicharesubjecttochangebasedonthemethodoftransport,theequipmentthat
may be necessary for delivery of the solvent to the system and potential price shifts
correspondingtothesignificantincreaseinglobaldemand.
AnotherexceptionduringstartupistheinitialchargeofCOandO2gasesinthereactor.
Theinitialchargemustbeconductedverycarefully,sincetheexplosionriskisactivewhilethe
system tries to equilibrate. To avoid this, the system will be initially charged to nearly full
pressurewithCO,followedbytheTFEandNaIchargeandasmallstreamofO2willbebubbled
upthroughthesolutionuntilthemoleratioofCOtoO2isabout120:1(closetothesteadystate
ratioof(118.7:1).Whenoperationbegins,theCOandO2freshfeedswillenterthereactorat
about a 2:1 ratio, and should be maintained safely since almost all of the fresh gas will be
dissolvedintothesolvent.

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Conclusionsand
Recommendations

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ConclusionsandRecommendations

BasedonthepatenttitledOneStepCatalyticProcessfortheSynthesisofIsocyanates

contributedbyFernandez,etalin2008,andseveralassumptionsonrelevantreactionkinetics,
aneconomicallyviableandtechnicallyfeasiblephosgenefreeTDIproductionprocesshasbeen
designed.Thedesignrequirestworeactorsinordertoconsumeasmuchreactantsaspossible
ineachproductioncycle.Thisisparticularlyimportantespeciallybecauseoftheveryexpensive
TFEsolventofwhichcurrentlyweneedaboutofthetotalworlddemand.AstheTDIhasbeen
formed,theproductmixispassedthroughthedistillationseparationtrains.Themainfocusin
the first distillation column is to isolate the NaI promoter since it is corrosive and requires
expensive hastelloy coating on every pipe and process units it flows through. The second
distillationcolumnseparatesalltheisocyanatesatthebottomofthestage.Thelastdistillation
columnthenisolatesthewastewater.Unreactedmaterials,includingthesolvent,thecatalyst
andtheNaIpromoterarerecycledbacktothereactorscontinuously.

Looking at the base case scenario results, it is apparent that our project results in a

positive NPV of $20,653,700, with an ROI of 12.03% and an IRR of 18.05%. The result is
satisfying remembering that the assumptions we made are conservative. However, the
feasibility also strongly depends on several moving parts like future economic outlook, which
willaffectglobalTDIdemandandthusitsprice,andotherrawmaterialscosts
Aside from the inherent economic risks like the health of our company, which is
assumed to be perfectly operational with no debt maturing in visibility projection, the actual
reactionprocesskineticsareverycrucialpieceofinformation.Theamountoftimerequiredfor
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thereactiontocompletewilldeterminethesizeofourreactorandthustheinvestmentcosts.
Thesameappliestotheimportantknowledgeweneedregardingthelifespanofthecatalyst,
whichwillaffectthevariablecostseveryyear.

Other risks are related to government regulatory limits on the atmospheric

concentrationsofourchemicalsthroughouttheproductionprocess.Basedonthecalculations
wegetfromtheAspensimulationmodel,thechemicalsinvolvedintheTDIproductionprocess
are not too hazardous and they do not exceed the amounts described in the government
regulations.However,wearestillneedtobereadyshouldanyunexpectedcircumstancesarise.

SincetheNPVofthebasecasescenarioispositiveandrememberingtheconservative

assumptions we made along with a reasonable payback period of 3 years, we recommend

undertakingthisproject.Notonlytheprojectlookspromising,thefactthatitisanovelprocess
thatisphosgenefreemakesitevenmoreattractive.

Evenso,westillstronglyrecommendfurtherdetailedresearchonthereactionkinetics,

thecatalystandthepromotercharacteristics,aswellasglobaleconomicresearchonTDI.
Further research needs to be conducted on the kinetics of the process, the exact role of the
catalystandthepromoterinthereactionsandtheireffectsontheTDIyield,andofcoursethe
life span of the three components. The information would enable us to look for comparable
catalysts,solventsandpromotersofsimilarrolesasthosewearecurrentlyusing,andthusfind
cheaperalternativestodrivedowninvestmentandvariablecostseachyear.

In addition, it would be worthwhile to do more research on various other ways to

produceTDIinthecurrentmarket.Itwouldbegreatifwecanreducethenumberofdistillation
we use. One way to do this may be by having a solid support to hold the NaI in one place
162

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togetherwiththecatalystbeds.Therefore,wewouldnotneedtoisolateNaIandtransferitto
the recycle stream back to the reactors, driving down hastelloy coating cost and more
importantlytakingawayoneofthedistillationcolumnsusedtoisolateNaI.Inaddition,further
researchneedstobedoneonothermeansofseparationprocesswhichiscrucialinthisproject.

Thus,untilweareclearaboutalltheuncertaintiesandtheunderlyingassumptionsthat

we made, it is very difficult be properly confident about the feasibility of the TDI production
through a free phosgeneroute. Although we are still positive that TDI production process
described in this report is viable, looking at the nature of complexity of the project, which is
actuallyrelativelyconventionalandnotsodifficulttosetupbyexperiencedcontractorsatthe
GulfCoast.

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Acknowledgments

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Acknowledgments:

Throughout the design process we have been provided with an abundant amount of

help from our faculty advisor, professors, industrial consultants, and industrial contacts.
Without their time, energy, and effort, this report would not have been. For this reason we
wouldliketothankDr.DaeyeonLee,ProfessorLeonardFabiano,Dr.WarrenSeider,Mr.Bruce
Vrana,Mr.SteveTieri,Dr.E.RobertBecker,andMr.GarySawyerfortheirhelpinouroverall
process design, ASPEN modeling, and for help estimating prices for our exotic materials.
ProfessorFabiano,withampleexperienceinreallifeTDIproductionprocesses,wasespecially
helpfulinhelpingusmodify,optimize,andtroubleshootourASPENflowsheetsothatthespecs
metthepatentandrealworldstandardsascloselyaspossible.Hespentseveralhoursofhis
own time with us in weekly meeting and at home in an effort to help us reach our goal of
creating an environmentallyfriendly process. Additionally, as the creator of the problem
statement, Mr. Bruce Vrana, DuPont, was extremely helpful in guiding us through the
intricacies of the phosgenefree process for creating TDI from TDA. He also helped us to
develop adequate assumptions for process parameters and price estimates which were
paramountinthecompletionofthisreport.

In addition to our professors and consultants, we would like to thank the sales

representatives at for their price estimates and availability for industrial scale TFE which was
used as the basis for pricing the highly expensive solvent used in the process. The

165

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representatives also provided us with estimates of the prices of competitive solvents which
ultimatelyledtoourselectionofTFEasoursolvent.

ListofFiguresandTables

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ListofFiguresandTables

Figure1:InnovationMap
Figure2:MajorproducersTDIproductioncapacity
Figure3:ModeratelyincreasingTDIdemandinUSA
Figure4:Option1singlethreelooppassreactordetailedprocessflowsheet
Figure5:Option2Tworeactorsystemdetailedprocessflowsheet
Figure6:Threelooppassreactorsystem
Figure7:Distillationseparationcomplex
Figure8:ProcessBlockDiagram
Figure9:ProcessFlowDiagram
Figure10:Reactorsystemsection
Figure11:Section2SeparationProcess
Figure12:BlockflowdiagramfortheTDIproduction
Figure13:DetailedASPENPlusflowsheetofTDIproduction
Figure14:BreakdownofannualvariablecostsofTDIproduction

Table1:TherequiredratioofrawmaterialsperpoundofTDIproduced
Table2:Summaryofincrementalcostsavingofreactorsysteminoption2
Table3:StreaminformationfortheReactorsBlock
Table4:StreaminformationfortheSeparationsBlock
Table5:ProcessMaterialBalance
Table6:Streamsthatneedtobeheatedorcooled
Table7:Streamsinseparationblockthatneedtobeheatedorcooled
Table8:Energysavedperstream
Table9:Totalenergysavingsand%energy
Table10:PossibleheatdutysavingssummarybyusingtwoparalleldistillationcolumnsinplaceofD100
Table11:Utilitycostofcoolingwater
Table12:Utilitycostofsteam
Table13:Utilitycostoffueloil
Table14:Utilitycostoflandfill
Table15:Equipmentcostsummary
Table16:Totalpermanentinvestmentinputassumptions
Table17:Fixedcapitalinvestmentsummary
Table18:Projectassumptionsandoperationssummary
Table19:Summaryofannualvariablecosts
Table20:Summaryofannualfixedcosts
Table21:Economicanalysissummary
Table22:TDIproductionbasecasecashflowsummary
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Table23:SensitivityanalysisonNPVtowardsTDIpriceanditsinflationrate
Table24:SensitivityanalysisonNPVtowardsCotBuSalencatalystpriceandlifespan
Table25:SensitivityanalysisonNPVtowardsreactorresidencetime
Table26:2010ChemicalEngineeringCostIndices
Table27:Catalystpricingcalculations
Table28:Solvent(TFE)andpromoter(NaI)costcalculations
Table29:Utilitycostsforrelevantprocessunits

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Bibliography

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PhosgeneFreeRoutetoTolueneDiisocyanate

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http://EnvironmentalChemistry.com/yogi/chemicals/cn/Toluene%A0diisocyanate.html
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"CDCNIOSHPocketGuidetoChemicalHazardsPhosgene."NIOSHPocketGuidetoChemical
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Chatha,Devindersingh."SodiumIodide."Alibaba.com.Web.20Mar.2010.
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HealthHazardAssessment.Dec.2000.Web.2Feb.2010.
DevelopmentsinTolueneDiisocyanate(TDI)ProcessTechnology.Rep.Nexant,Inc.,Oct.2008.Web.
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Hassan,Abbas,EbrahimBagherzadeh,RayfordG.Anthony,GregoryBorsinger,andAzizHassan.
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Harrison,Karl."Phosgene@3DChem.com."Phosgene,WhatIsPhosgene?AboutItsScience,
ChemistryandStructure.3DChem.com,Sept.2007.Web.28Jan.2010
MSDSobtainedfromanInternetsearch
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TheBenefitsofChlorineChemistryinPolyurethanes.Rep.GlobalInsight,Dec.2006.Web.22Mar.
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TolueneDiisocyanate:HandlingGuide.Rep.PerstorpWinningFormulas.Web.20Apr.2010.
"TolueneDiisocyanate(TDI)PricesandPricingInformation."ChemicalIndustryNews&Intelligence
|ICIS.com.Web.13Mar.2010.<http://www.icis.com/V2/Chemicals/9076540/toluene
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CryoGas).Web.06Apr.2010.<http://www.uigi.com/MSDS_gaseous_O2.html>.
Zhiyang,Hou."StablePriceofTDIin2009.(Organics)Entrepreneur.com."Entrepreneur.16Apr.
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Appendix

174

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BouSaba,Dizon,Kasih,Stewart

Appendix1:Equipment
SizingandCostingSample
Calculations

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Appendix1A:SampleCalculationforDistillationColumnSize
andPrice
Modeledasverticalvessel;Example:DistillationcolumnD100
Columnsizing
FromtheAspenstreamreport:

Distillaterate,D(lb/hr):978460.81;

AverageMW:96.03;Refluxratio,R:2.4

Liquidrate,L(lb/hr)=DxR=2348305.94

Vaporrate,V(lb/hr)=DxL=3326766.75

Assumingidealgas:

R(ft^3.psi/R.lbmol):10.73159;

T(R):662.72;

Pressure(psi):2.2

Floodingvelocity,Uf(ft/s):

;Assume:Fst=1(RecommendedbySeider,etal)
Ff=1;nonfoamingsystem
FHA=1;sievetrayswithAh/AA=0.1

Platespacing=11in,Csb=0.28(From19.4p.505)

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Columnsize:

FromAspenreport:

Columndiameter,Dt=9.57;Numberoftrays,Nt=20

Columnheight,H(ft)=4+2(Nt1)+10=52

ColumnPurchasePrice

Cv(Costofverticaltower):
Weightoftheshell:

Material:CarbonsteelwithincoatingofHastelloy

Corrosionallowance(in)=0.25(recommendedbySeideretal)

Minimumwallthickness(in)=0.5(recommendedbySeideretal)

Fm:Fm,carbonsteel=1;Fm,hastelloy=2.95

Densityofmaterial:carbonsteel=490lb/ft3;hastelloy=554.98lb/ft3

ts(in)=0.25+0.5=0.75

Fm,weighted=0.75Fm,carbonsteel+0.25Fm,hastelloy=1.4875

material=0.75m,carbonsteel+0.25m,hastelloy=506.25lb/ft3

Cpl(Costofplatformsandladders):

Ct(Costoftrays):

20)

Typesievetrays;Typefactor,FTT=1;FTM=1.4875;Numberfactor,FNT=1(fortrays

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PhosgeneFreeRoutetoTolueneDiisocyanate

;Adjusted

BouSaba,Dizon,Kasih,Stewart

Baremodulefactor(Fm)=4.16,

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Appendix1B:SampleCalculationforCoolerandCondenser
Modeledasshell&tubeheatexchanger(fixedhead);Carbonsteelshell;20ftlong
Example:DistillationcondenserD100
Condensersizing:
Heatduty,Q(Btu/hr)=651,276,420
Hotstreamtempin(F)
Hotstreamtempout(F)
Coldstreamtempin(F)
Coldstreamtempout(F)

36.8
34.98
90
120

U(Btu/hrft2F)=100

Purchasecostofcondenser:

CB(Basecost;fixedhead):

Fm=1Carbonsteel
Fl=1;tubelengthcorrectionforL=20ft
;Adjusted

Baremodulefactor(Fm)=4.16,
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Appendix1C:SampleCalculationforHeaterandReboiler
Modeledasshell&tubeheatexchanger(fixedhead);Carbonsteelshell;20ftlong
Example:DistillationcondenserD100
Reboilersizing:
Toavoidboiling,heatflux=12000Btu/hrft2
FromAspen,

Heatduty,Q(Btu/hr)=625,534,412

Purchasecostofreboiler:
Assume:kettlevaporizercarbonsteel

CB(Basecost;kettlevaporizer):

Fm=1Carbonsteel
Fl=1;tubelengthcorrectionforL=20ft
;Adjusted

Baremodulefactor(Fm)=4.16,

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Appendix1D:Samplecalculationforpumpandelectricmotor
Modeltype:centrifugalpump;Example:D100Reboilerpump
Pumpsizing:
FromAspen:

Densityofliquid(lb/ft3)=82.2

Volumetricflowrate(ft3/hr)=280.40;conversionfactortogpm=8.02064269

Volumetricflowrate(gpm)=34.96

Pressureincrease(psi)=0.15

Purchasecostofpump:

Pumpdetails:

No.ofstage=1;material=CarbonSteelandHastelloy(Fm=1.4875);
Shaftrotation=3600rpm;Ft=1;

(AdjustedbyCE2010=532.9)
Motorsizing:
Motordetails:

Explosionproofmotor;Shaftrotation=3600rpm;Ft=1.8

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Purchasecostofmotor:
;(AdjustedbyCE2010=532.9)
Purchasecostofpumpandmotor:
;(AdjustedbyCE2010=532.9)
Fbm=3.05,

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Appendix1E:SampleCalculationforFlashDrumandReflux
Accumulator
Model:Verticalpressurevesselofappropriatecapacity;
Material:carbonsteelandhastelloy;
Example:F100FlashDrum
Flashdrumsizing:
FromAspen:
Volumetricflowrate(ft3/hr)=29743.25
Designspecifications:

Residencetimeathalffull(min)=5

Aspectratio(length/diameter)=2

Purchasecostofflashdrum:

Cv(Costofverticalvessel):

Corrosionallowance(in)=0.25

Minimumwallthickness(in)=0.50

ts(in)=0.25+0.50=0.75

Fm=1.4875;densityofmaterial=506.25lb/ft3(fromprevioussample)

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Baremodulefactor,Fm=4.16,

ForRefluxAccumulator,itwasassumedthatthevesselishorizontal.Thus,weusedthe
followingcorrelationtofindtheCvofthehorizontalvessel:

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Appendix1F:SampleCalculationforStorageTanks
Example:ST100
Material:carbonsteel;Type:Opentank;Periodofstorage:2weeks
Storagetanksizing:
FromAspen:

Temperature(F)=248;pressure(psia)=652.67

Volumetricrate(ft3/hr)=434.63

Volume(gal)=(volrate)(336hours)(7.480519gal/ft3)=1,092,415
Designspecifications:

Aspectratio(Length/diameter)=0.167

Purchasecostofstoragetanks:
Thecorrelationforopentank:
;

Fm=3.0

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Appendix1G:SampleCalculationforHeatExchangers
Heatexchangersizing
Shell&tubeheatexchanger;floatinghead;carbonsteel(Fm=1)
Example:HX100Heatexchanger
Assumptions:

Tubelength(ft)=20(Fl=1);Tubeinsidediameter(in)=1

Designspecifications:

Shellinsidediameter=15.25in(Seider,etal)

Squarepitch

FromAspen:

Hotstreamtempin(F)
Hotstreamtempout(F)
Coldstreamtempin(F)
Coldstreamtempout(F)
Hotstreamflowrate(lb/hr)
Coldstreamflowrate(lb/hr)
coldstreamdensity(lb/ft^3)
Heattransfercoefficient,Ui,(Btu/ft^2hrF)
Heatduty,Q,(Btu/hr)

203
202
106
201
2.01E+06
2.65E+04
28.75
149.693657
660602.923

Foulingfactor,Ft(R,S)

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Estimatevelocityinsidethetube(ft/s)=5

FromAspen:
Heattransferarea(tubeoutsidearea),AtNt,(ft2)=180.63
=1

Estimatebafflespacing,b(in)=10(BasedonSeider,etal)
FromAspen:

Hotside(shellside)pressure(psig)=2

Designdatasummary:
Heatduty(MMBtu/hr)
Shelldiameter(in)
Heattransfercoefficient(Btu/hr
ft^2F)
Heattransferarea(ft^2)
Tubelength(ft)
Shelllength(ft)

0.660602923
15.25
149.693657

180.634765
20
22

PurchasecostofHeatexchanger:
Purchasecost,

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Fm=1;Fl=1

Purchasecost,Cp=$14,094.12;Adjustedpurchasecost,Cp=$14,094.12x532.7/500
=$15,022
Fbm=3.17,
Baremodulecost,Cbm=FbmCp=$47,618.21

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Appendix1H:SampleCalculationsforReactorSystem
VF=MF/L
72804.5=1294464/17.78
V=VF*tR/60*2
145609=72804.5*60/60*2
Di=((4*V)/(A*))1/3
35.9=((4*145609)/(4*))1/3
L=A*Di
143.7=35.9*4
tM=Di*0.0313+0.125
1.375~35.9*.0313+0.125(thematerialonlycomesin0.125inintervals)
tS=tC+tM
1.625=1.375+0.25
W=(Di+tS/12)(L+0.8Di)tS/12*M
28456.3=(36.2+1.375/12)(143.7+.8*35.9)*1.375/12*490
CV=exp[7.0132+0.18255{ln(W)}+0.02297{ln(W)}2]
80953.19=exp[7.0132+0.18255{ln(28456.3)}+0.02297{ln(28456.3)}2]
CPL=361.8(Di)0.7396(L)0.70684
171294.52=361.8*(35.9)0.7396(143.7)0.70684
CP=FMCV+CPL+VCPK+CDR
3379604.46=30000.48*2.95+80953.19*1+171.294+20*145609+126675.35
CBM=FBMCP
14984246.90=4.16*3601982.43

VF=VolumetricFlowRate(ft3/hr)
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MF=FeedMassFlowRate(lb/hr)
L=LiquidDensity(lb/ft3)
tR=ResidenceTimeathalffull(min)
V=Volume(ft3)
Di=Diameter(ft)
L=Length(ft)
A=AspectRatio(L/D)
tM=minimumwallthickness(in)
tC=corrosionallowance(in)
tS=shellthickness(in)
M=metaldensity(lb/ft3)
W=weightoftheshell(lb)
CV=Costofverticalvessel($)
CPL=Costofplatformsandladders($)
FM=Materialsofconstructionfactors
CPK=CostofPacking($/ft3)
CDR=Costofhighperformanceliquiddistributorsandredistributors($)
CP=Purchasecostofcolumnwithtrays($)
FBM=baremodulefactor
CBM=baremodulecost($)

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Appendix1i:SampleCalculationsforUtilities
Coolingwater:
Example:D100Condenser
FromAspen:

Heatduty,Q(btu/hr)=651,276,420

Physicalproperties:

Specificheatofwater(Btu/lbF)=1

Densityofwater(lb/gal)=8.33

Designspecifications:

Inletwatertemp(F)=90

Outletwatertemp(F)=120

Twater(F)=30

Costofwater($/1000gal)=$0.08;Adjustedcoolingwaterprice=
$0.08*(532.9/500)=$1,649,914
Steam,FueloilandLandfilldisposal
Example:D103Reboiler;Lowpressuresteam
FromAspen:

Heatduty,Q(btu/hr)=8,628,054

Operatingpressure(psi)=13.9

Hvap(btu/hr)=971.9

Steamrequired(lb/hr)=(Q/d)=8877.09;
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BouSaba,Dizon,Kasih,Stewart

Steamflowrate(lb/year)=(steamflowrate)(330days)(24hrs)=70,306,570.58
Lowpressuresteamunitprice($/1000lb)=$3.00;Adjusted(steamunitprice)=$3.20;

Electricity
Example:P3Pump
Assumptions:

Plantoperationsperyear=7128hours

FromAspen:

Brakehorsepower(Bhp)=9.06

Motorefficiency=0.86

Unitprice=$0.06;Adjustedunitprice=$0.08

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Appendix2:Chemical
EngineeringCostIndices

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Table26:2010ChemicalEngineeringCostIndices
ChemicalEngineeringPlantCostIndex

CEINDEX
Equipment
HeatExchangesandTanks
ProcessMachinery
Pipe,valvesandfittings
ProcessInstruments
PumpsandCompressions
Electricalequipment
Structuralsupports
ConstructionLabor
Buildings
EngineeringSupervision

Jan'10Prelim.
532.9
631.8
572
601.9
794.5
419.7
903
469.2
640.2
330.8
494.7
342.4

Dec'09Final
524.2
618.4
554.2
597.9
776.3
417.5
895.2
467.2
620
331.2
494.6
343.2

Jan'09Final
539.6
642.4
603.4
620
781.8
389.6
902.1
457.9
671.5
324.5
500
350.3

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Appendix3:Catalyst,
Solvent,andPromoter
CostCalculations

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Appendix3:Catalyst,Solvent,andPromoterCostCalculations

Catalystpricingcalculations
REAC1

Patent
Example

Volume[cu.
Ft.]
145608.9989

Catalystper
Catalyst
Volume
Type
Reactor[g/L]
7.6 CotBu
Salen/Silica
1.05714 CotBu
Salen(No
Silica)
0.5714 Cobaltfree
Silica

Catalystper
Patent
Catalyst
REAC2

Volume
Example
Type
Reactor[g/L]
Volume[cu.

5
7.6 CotBu
Ft.]
Salen/Silica
16378.58351
6
1.05714 CotBu
Salen(No
Silica)

7
0.5714 Cobaltfree
Silica
TotalCostforCatalystforBoth
$
Reactors:
14,546,797.33
Table27:Catalystpricingcalculations

Estimated
TotalCostfor
Cost
Reactor
[$/kg]
3000
$
94,005,868.60
3000
$
13,075,968.94
3000

$
7,067,757.02

Estimated
TotalCostfor
Cost
Reactor
[$/kg]
3000
$
10,574,092.13
3000
$
1,470,828.39
3000

$
795,004.77

Table28:Solvent(TFE)andpromoter(NaI)costcalculations
Amountrequired(lb)16
Unitcost($/lb)17
Totalcost($)
TFE
1,115,835
$4.08 $4,555,209.57
NaI
2,730
$0.45 $1,240.97

16FromAspenmodel

17TFEcostisassumedtobe$9/kgor$4.08/lbbasedonsuggestionfromHalocarbonsconsultant;NaIcostis

basedoncurrentmarketprice.

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Appendix4:UtilityCost
Summary

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Table29:Utilitycostsforrelevantprocessunits
Utility
Unit#
UtilityRequirement Unitprice(adjusted)
Coolingwater
(gal/yr)
($/1000gal)

D100
20,640,693,266
$0.08

D102

11,148,501,321

$0.08

D103
273,446,002
$0.08

C100
541,173,083
$0.08

C102

28,484,136

$0.08

C101
882,847
$0.08

Total

Lowpressuresteam
(lb/yr)
($/1000lb)

Fueloil

70,306,571
1,109,409,468
174,764,895
433,668,152
3,527,733
20,440,229

HX106
HX107

Sludge

Landfill

Electricity

D103
H100
H101
H102
H103
H104

P101

P102

P103

P100

P104

D100ReboilerPump

D101ReboilerPump
D102ReboilerPump
D100RefluxPump
D101RefluxPump
D102RefluxPump

(gal/year)
2,814,484,991
986,804,228

(lb/yr)
1,825,465

(kWhr/yr)
55,902
3,035
1,322
204,374
3,162,570
70
125
72
1,040,830
528,583
1,815

$3.20
$3.20
$3.20
$3.20
$3.20
$3.20
Total

Annualcost
$1,649,913.82
$891,155.45
$21,857.91
$43,258.67
$2,276.88
$70.57
$2,608,533.30

$224,798.23
$3,547,225.83
$558,793.28
$1,386,610.55
$11,279.58
$65,355.59
$5,794,063.05

($/1000gal)
$1.60
$1.60
Total

$4,499,517.15
$1,577,603.92
$6,077,121.07

$0.11
Total

$194,558.06
$194,558.06

($/kWhr)
$0.08
$0.08
$0.08
$0.08
$0.08
$0.08
$0.08
$0.08
$0.08
$0.08
$0.08
Total

$4,691.36
$254.74
$110.92
$17,151.33
$265,406.82
$5.86
$10.49
$6.01
$87,347.77
$44,359.31
$152.28
$419,496.89

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Totalutilitycost $15,093,772.37

Appendix5:Problem
Statement

200

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BouSaba,Dizon,Kasih,Stewart

201

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BouSaba,Dizon,Kasih,Stewart

202

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BouSaba,Dizon,Kasih,Stewart

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Appendix6:USPatent
7423171OneStep
CatalyticProcessforthe
SynthesisofIsocyanates

204

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BouSaba,Dizon,Kasih,Stewart

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USPatent7423171Onestepcatalyticprocessforthesynthesisof
isocyanates
USPatentIssuedonSeptember9,2008
EstimatedPatentExpirationDate:June20,2027
Abstract
Aonepotprocessforthesynthesisofisocyanates,polyisocyanatesormixturesthereofwhich
includesthestepsof:i.preparingamixturecomprisinganamine,analcohol,anoxygen
containinggas,carbonmonoxide,ametalcomplexcatalystselectedfromthegroupconsistingof
macrocycliccomplexcatalystsandcobaltShiffbasecatalysts;andasolventselectedfromthe
groupconsistingofaliphaticoraromatichalocarbons,perhalogenatedalcohols,halogenated
ethers,halogenatedketones,perfluorinatedhydrocarbons,polymersofchlorotrifluoroethylene
havingtheformula(CF2CFCl)nwhereinnisbetween2and10,andmixturesthereof;ii.
subjectingtheresultingmixturetoafirstheatingunderpressure;iii.coolinganddepressurizing
themixtureresultingfromthepreviousstep;andiv.subjectingthemixtureofthepreviousstep
toasecondheatingtoseparateouttheisocyanateproductfromthemixture.
Claims
Whatisclaimedis:

1.Aonepotprocessforthesynthesisofisocyanates,polyisocyanatesormixturesthereof,
whichcomprisesthestepsof:i.preparingamixturecomprisinganamine,analcohol,an
oxygencontaininggas,carbonmonoxide,ametalcomplexcatalystselectedfromthegroup
consistingofmacrocycliccomplexcatalystsandcobaltShiffbasecatalysts;andasolvent
selectedfromthegroupconsistingofaliphaticoraromatichalocarbons,perhalogenated
alcohols,halogenatedethers,halogenatedketones,perfluorinatedhydrocarbons,polymersof
chlorotrifluoroethylenehavingtheformula(CF2CFCl)nwhereinnisbetween2and10,and
mixturesthereof;ii.subjectingtheresultingmixturetoafirstheatingunderpressure;iii.
coolinganddepressurizingthemixtureresultingfromthepreviousstep;andiv.subjectingthe
mixtureoftheprevioussteptoasecondheatingtoseparateoutanisocyanateproductfromthe
mixture.

2.Theprocessaccordingtoclaim1,whereinsaidsolventisselectedfromthegroupconsisting
of2,2,2trifluoroethanol,2,2,3,3tetrafluoro1propanol,1,1,1,3,3,3hexafluoropropan2ol,
perfluoronhexane,perfluoronheptane,perfluoronnonane,perfluorodecaline,nonafluoro
tertbutanol,andmixturesthereof.

3.Theprocessaccordingtoclaim2,whereinthesolventis2,2,2trifluoroethanol.

4.Theprocessaccordingtoclaim1,whereinthealcoholispresentinmorethanstoichiometric
amountssoastoactasboth(co)solventandreactant.
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BouSaba,Dizon,Kasih,Stewart

5.Theprocessaccordingtoclaim1,whereinthetemperatureinsaidfirstheatingisinarange
offrom100to200C.,andthepressureisinarangeoffrom5to100bar.

6.Theprocessaccordingtoclaim5,whereinthetemperatureinsaidfirstheatingisinarange
offrom120to180C.,andthepressureisinarangeoffrom20to70bar.

7.Theprocessaccordingtoclaim1,whereinthetemperatureinsaidsecondheatingisina
rangeoffrom50to240C.

8.Theprocessaccordingtoclaim1,whereinacosolventisaddedpriortosaidsecondheating.

9.Theprocessaccordingtoclaim1,whereinstepiv.comprisesatleastonedistillationto
removesolventsandatleastonedistillationtoseparatetheisocyanateproduct.

10.Theprocessaccordingtoclaim9,whereinsaiddistillationsareindependentlyselectedfrom
distillationsunderpressure,distillationsundervacuumanddistillationsatatmospheric
pressure.

11.Theprocessaccordingtoclaim9,whereinsaidfirstdistillationiscarriedoutata
temperatureinarangeoffrom50to180C.andunderapressureinarangeoffrom0.1to10
bar,andsaidseconddistillationiscarriedoutatatemperatureinarangeoffrom140and240
C.andunderapressureinarangeoffrom1to900mbar.

12.Theprocessaccordingtoclaim9,characterisedinthatthedistilledsolventsarerecycledfor
furtherreactions.

13.Theprocessaccordingtoclaim1,comprisingacontinuousprocess.

14.Theprocessaccordingtoclaim13,whereinthespacevelocityisinarangeoffrom20to
40.000h1.

15.Theprocessaccordingtoclaim13,whereinthedistilledsolventisrecycledintothereaction.

16.Theprocessaccordingtoclaim1,whereinthemetalofthemetalcomplexcatalystis
selectedfrommetalsofGroupVIII.

17.Theprocessofclaim1,whereinthemetalcomplexcatalystisselectedfromthegroup
consistingofcobaltporphyrinsofformulaI##STR00004##whereinR1andR2areeach
independentlyselectedfromhydrogen,cyano,substitutedorunsubstitutedalkyl,substitutedor
unsubstitutedcycloalkyl,substitutedorunsubstitutedalkenyl,substitutedorunsubstituted
alkynyl,substitutedorunsubstitutedaryl,substitutedorunsubstitutedheterocyclyl;orR1and
R2togetherformasubstitutedorunsubstitutedcycloalkyl,substitutedorunsubstituted
cycloalkenyl,substitutedorunsubstitutedcycloalkinyl,substitutedorunsubstitutedaryl,
207

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

substitutedorunsubstitutedheterocyclyl;R3isselectedfromhydrogen,cyano,substitutedor
unsubstitutedalkyl,substitutedorunsubstitutedcycloalkyl,substitutedorunsubstituted
alkenyl,substitutedorunsubstitutedalkynyl,substitutedorunsubstitutedaryl,substitutedor
unsubstitutedheterocyclyl;acobaltphthalocyanineofformulaII##STR00005##whereinR1and
R2havethesamemeaningasinformulaI;andacobaltShiffbasecatalystofformulaIII
##STR00006##whereinR1andR2havethesamemeaningasinformulaI;R4,R5,R6andR7are
eachindependentlyselectedfromamonghydrogen,cyano,substitutedorunsubstitutedlinear
alkyl,substitutedorunsubstitutedbranchedalkyl,substitutedorunsubstitutedalkoxy,OSi
R10,whereinR10isasubstitutedorunsubstitutedalkyl,substitutedorunsubstitutedcycloalkyl,
substitutedorunsubstitutedalkenyl,substitutedorunsubstitutedalkynyl,substitutedor
unsubstitutedaryl,substitutedorunsubstitutedheterocyclyl;R9andR8areeachindependently
selectedfromhydrogen,cyano,substitutedorunsubstitutedalkyl,substitutedorunsubstituted
cycloalkyl,substitutedorunsubstitutedalkenyl,substitutedorunsubstitutedalkynyl,
substitutedorunsubstitutedaryl,substitutedorunsubstitutedheterocyclyl;andmixtures
thereof.

18.Theprocessaccordingtoclaim17,whereinR4,R5,R6andR7areeachindependently
selectedfromasubstitutedorunsubstitutedbranchedalkylgroup.

19.Theprocessaccordingtoclaim17,whereinR5andR7areeachindependentlyselectedfrom
aC1C.sub.4alkoxygroup.

20.Theprocessaccordingtoclaim1,whereinthecatalystcomprisesasolidsupportselected
fromthegroupconsistingofsilica,inorganicrefractorymetaloxides,zeolites,carbonand
polymersormixturesthereof.

21.Theprocessaccordingtoclaim1,whereintheamineisselectedfromthegroupconsisting
ofsubstitutedorunsubstitutedarylamines,substitutedorunsubstitutedaryldiamines,
polyaminopolyphenylmethanesandmixturesthereof.

22.Theprocessaccordingtoclaim21,whereintheamineisselectedfromthegroupconsisting
oftoluenediamines,diaminodiphenylmethanesandmixturesthereof.

23.Theprocessaccordingtoclaim1,whereinahalidepromoterselectedfromthegroup
consistingofalkalimetalhalides,alkalineearthmetalhalides,oniumhalides,compounds
capableofformingoniumhalidesatcontactingconditions,oxoacidsofhalogenatomsandtheir
salts,organichalidesandhalogenmoleculesandmixturesthereof,isaddedpriortothefirst
heatingunderpressure.
Description
CROSSREFERENCETORELATEDAPPLICATION

ThepriorityofEuropeanPatentApplicationNo.EP06380178.1filedJun.20,2006ishereby
208

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

claimedundertheprovisionsof35USC119.ThedisclosureofsaidEuropeanPatentApplication
No.EP06380178.1isherebyincorporatedhereinbyreferenceinitsentirety,forallpurposes.

FIELDOFTHEINVENTION

Thepresentinventionisrelatedtothedirectconversionofaminesintoisocyanates,andtoa
catalyticchemicalprocessforeffectingsuchconversiontoproduceisocyanates.

BACKGROUNDOFTHEINVENTION

Isocyanatesareimportantchemicals.Forexample,theworldproductionofisocyanatesexceeded
5megatonsin2001.Traditionally,isocyanatesaremanufacturedonacommercialscaleby
reactionofphosgenewithaminesoraminesalts.Thereaction,however,hasseveralserious
drawbacks.PhosgeneisanextremelytoxicreagentandastoichiometricamountofHClis
producedasabyproduct.Furthermore,HClcausesseriouscorrosion,andastoichiometric
amountofNaOHisrequiredtoneutralizetheHCl,wherethesameamountofNaClisformed.As
restrictionsupontheuseofverytoxicmaterialssuchasphosgenewithinthechemicalindustry
havebecomemorerigorouslyenforced,therehasbeenincreasinginterestin
developingalternativemethodstophosgeneinthesynthesisofisocyanate.

Asanalternative,theuseofdimethylcarbonateordimethylsulfateasphosgenesubstitutes
arerelativelyexpensiveforcommercialapplications(seeM.Selvaet.al.,TetrahedronLetters.
2002,43(7),12171219;JP20044262835;WO98/56758;WO99/47493).

Manyothersstrategiesfornonphosgeneroutes,includingreductivecarbonylationand
oxidativecarbonylationbyusingCOascarbonylsource,havebeenreported.Onepromising
alternativeapproachthathasbeenthesubjectofresearchinrecentyearsinvolvestheoxidative
carbonylationofaminestocarbamatesinthepresenceofanalcohol,usuallymethanol,
followedbycatalyticdecompositionofthecarbamatestoisocyanates.

AlperandHartstock(J.Chem.Soc.,Chem.Commun.1141,1985)disclosecatalyticsystems
includingpalladiumchloride,copperchlorideandhydrochloricacidtoproducecarbamatesfrom
amines.ThisWackertypecatalyticsystem,consistingofPdCl2CuCl.sub.2HCl,isdisclosedasbeing
effectiveatmildconditions(1atmandroomtemperature)intheoxidativecarbonylationof
aminestoproducehighyieldsofcarbamate.Inthissystemcarbonmonoxide(CO)andoxygen
(O2)arebubbledthroughanalcoholtowhichisaddedPdCl2and,finally,theamine.Themixture
isstirredovernight,atroomtemperatureandpressure,andfiltered.Thefiltrateissubjectto
rotaryevaporation.Theresultingoilistreatedwitheitherdiethyletheroracetoneandfiltered,
andconcentrationofthefiltrateyieldsthecarbamateester.Furtherpurificationiscarriedout
bythinlayerorcolumnchromatography(silicagel).

GupteandChaudhari,JournalofCatalysis,114,246258,1988,studiedtheoxidative
carbonylationofaminesusingaPd/CNaIcatalyticsystem.Althougheffectiveatproducing
carbamates,thiscatalyticsystemusesaCO/O2molarratioof5/1,whichisinsidethe
209

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

flammabilityenvelope.

US2002/0183541employaGroupVIIImetalcatalystand/orcopperbasedcatalystwithhalide
promoterstoproducecarbamateestersthroughheterogeneousoxidativecarbonylationina
gassolidcarbonylationprocess.Thecarbamateproducedremainsonthecatalystsurfaceand
mustberecoveredthroughexpensiveextractionanddistillationsteps.

T.W.Leung,J.Chem.Soc.Chem.Comm.,3,1992,2056andU.S.Pat.No.5,194,660describesa
processforproducingcarbamates,usingahomogeneouscatalystthatcomprisescontactinga
firstreactantselectedfromprimaryaminecomponents,secondaryaminecomponents,urea
componentsandmixturesthereof;carbonmonoxide;atleastoneoxygencontainingoxidizing
agent,inthepresenceofcatalystcompositioncomprisingatleastonemetalmacrocyclic
complex,preferablyinthefurtherpresenceofoneiodinecomponent.Themacrocycliccomplex
isselectedfromthegroupconsistingofmetalporphyrinormetalphthalocyanineincludinga
metalselectedfromthemetalsofgroupIIIatoVaandgroupVIIIofthePeriodicTableandat
leastoneiodinecomponentispresentinanamounteffectivetofacilitatetheformationofthe
carbamate.

A.Bassolietal.,J.Mol.Catal.1990,60,41teachestheformationofureasingoodyields,with
smallamountsofcarbamatesandazoderivativesviatheN,N
bis(salicylidene)ethylenediaminocobalt(II)catalyzedoxidativecarbonylationofaromaticprimary
aminesinmethanol.

E.Bolzacchinietal.,J.Mol.Catal.A:Chemical,111,1996,281287,describestheN,N
bis(salicylidene)ethylenediaminocobalt(II)catalyzedoxidativecarbonylationofsubstituted
aromaticprimaryaminesinmethanoltogiveblendsofureas,isocyanates,carbamatesand
azoderivatives.Suchblendsareunsuitableforthesynthesisofcommercialisocyanates.Further,
thelongreactiontimesrequired(48hours)precludesthepracticalindustrialapplicationofthis
approach.

USPatentApplicationPublication2003/0162995describesaonepotsynthesisofisocyanates
byreactionofamineswithdimethylcarbonateandsubsequentheatingtoobtainthe
isocyanate.Duetoreactionconditions,theseparationoftheisocyanateproductinvolvesa
complicatedseparationprocesswhichcompriseswateraddition,furtherheating,filtrationand
anumberofdistillationsinordertoobtaintheisocyanate,inimpureform,whichthenmustbe
furtherpurified.

Therefore,thereisanextensiveliteratureregardingtheproductionofisocyanatesand
polyisocyanates.Themostcommonlyusedprocedureinvolvesthetransformationofanamine
intothecorrespondingcarbamateinafirststep,followedbythethermaldecompositionofthe
carbamatetoobtainthedesiredisocyanateorpolyisocyanate.Alargenumberofprior
publicationsrefertooneofthesetwosteps.

Forexample,asmentionedabove,U.S.Pat.No.5,194,660disclosesamethodforthe
210

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

preparationofcarbamates.However,thesynthesisofthecorrespondingisocyanatesisonly
suggestedandonlyfromthecorrespondingcarbamatesafterisolation.Further,accordingto
U.S.Pat.No.5,194,660itisnecessarytoisolatethecarbamateintermediatepriortoits
conversionintothedesiredisocyanate.

Onlyafewreferencesmentionorsuggestthepossibilityofdirecttransformationofaminesinto
thecorrespondingisocyanates.However,asinUSPatentApplicationPublication
2003/0162995,theyusuallyrequirecomplicatedseparationsteps.

Inviewofalloftheabove,thereisanexistingneedtoprovideanalternativecosteffectiveand
efficientmethodforthedirectsynthesisofisocyanatesandpolyisocyanates.

SUMMARYOFTHEINVENTION

Anefficient,safeandcosteffectiveonepotprocessforthesynthesisofisocyanateproducts
hasnowbeensurprisinglyfound.

Theonepotcatalyticprocessdisclosedhereinsatisfiestheneedintheartforanindustrially
viableoxidativecarbonylationprocesscapableofproducingisocyanateproducts,whichatthe
sametimedoesnotrequiretheisolationofintermediatecarbamates.

Further,theprocessaccordingtothepresentinventiondoesnotinvolvecomplicated
separationsteps.Theisocyanateproductsareseparatedbymeansofdistillationofthereaction
mixtureand,usually,theisocyanateproductisobtainedinessentiallypureform.

Further,thepresentinventionovercomestoalargeextentthehazardsassociatedwiththe
directreactionofcarbonmonoxideandoxygeninthepresenceoforganiccompoundsby
dissolvingthereactantgasesinareactionsolvent(e.g.halocarbonsand/oroxygenated
fluorinatedhydrocarbons).

Therefore,anaspectofthepresentinventionisaonepotprocessforthesynthesisof
isocyanates,polyisocyanatesormixturesthereof,whichcomprisesthestepsof:ipreparinga
mixturecomprisinganamine,analcohol,anoxygencontaininggas,carbonmonoxide,ametal
complexcatalystselectedfromthegroupconsistingofmacrocycliccomplexcatalystsand
cobaltShiffbasecatalystsandasolvent,selectedfromthegroupconsistingofaliphaticor
aromatichalocarbons,perhalogenatedalcohols,halogenatedethers,halogenatedketones,
perfluorinatedhydrocarbons,polymersofchlorotrifluoroethylenehavingtheformula(CF2
CFCl)nwhereinnisbetween2and10,andmixturesthereof;iisubjectingtheresultingmixtureto
afirstheatingunderpressure;iiicoolinganddepressurizingthemixtureresultingfromthe
previousstep;andivsubjectingthemixtureoftheprevioussteptoasecondheatingto
separateouttheisocyanateproductfromthemixture.

Additionalfeatures,aspectsandembodimentsoftheinventionwillbemorefullyapparent
fromtheensuingdisclosureandappendedclaims.
211

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BouSaba,Dizon,Kasih,Stewart

DETAILEDDESCRIPTIONOFTHEINVENTION

Itisknownthatexplosiveconcentrationofcarbonmonoxideinoxygenat200C.and
atmosphericpressureisbetween14.295.3%,thus,therangeisextremelybroad.Itisalso
knownthatdilutionofthegaseousmixturewithaninertgaslikenitrogenscarcelychangesthe
lowerlimitconcentration.Further,variationofpressurebetween1200atmospheresand
temperaturesbetween0200C.haveamodesteffectontheexplosiverange.Furthermore,
evenwhenthesereactantsarebroughttogetherinaratiothat,inhomogeneousconditions,
wouldbeoutsidetheflammabilityenvelope,theestablishmentofhomogeneityfrompure
componentsinvolvesatleastatemporarypassagethroughtheflammabilityenvelope.For
thesereasons,theexplosionrisksassociatedwiththedirectcontactofcarbonmonoxideand
oxygenarenoteasilymitigated.Furthermore,unfortunately,carbonmonoxideandoxygenare
onlyslightlysolubleinthealcoholsusedassolventsandreactantsinthepriorart,whichlimits
theconcentrationofthesetwocomponentsinthereactionmixtureandthusresultsinalower
speedofreaction.

Inthepresentinventionthesolventisselectedfromthegroupofaliphaticoraromatic
halocarbons,perhalogenatedalcohols,halogenatedethers,halogenatedketones,
perfluorinatedhydrocarbons,polymersofchlorotrifluoroethylenehavingtheformula(CF2
CFCl)nwhereinnisbetween2and10,andmixturesthereof.Thesesolventspossesshighoxygen
solubilityandallowforahigherconcentrationofoxygeninreactionmixtureatagivenoxygen
partialpressure.Therefore,byusingthesolventsoftheinvention,itispossibletoreducethe
partialpressureofoxygenandstillmaintainanacceptableconcentrationofoxygeninthe
reactionmixturesothatagoodspeedofreactioncanbeobtainedand,atthesametime,
thesafetyoftheprocessisimprovedbyworkingwelloutsidetheflammabilityenvelopeandin
conditionsoflowertemperaturesandpressuresthanthoseusedinthepriorart.

Halocarbonsarepreferablyarylhalocarbonssuchaschlorobenzene,dichlorobenzeneand
trichlorobenzene,fluorocarbons,chlorofluorocarbons,andhydrochlorofluorocarbons.
PreferredreactionsolventsarethecompletelyfluorinesubstitutedC5C.sub.10hydrocarbonssuch
asperfluoronhexane,perfluoronheptane,perfluoronnonane,perfluorodecalineor
nonafluorotertbutanol.Theseliquidsareavailableundervarioustradenames,suchas3M
PerformanceFluids(Minneapolis,Minn.).Polymersofchlorotrifluoroethylenearealso
commerciallyavailable,suchasthegrade0.8ofHalocarbonProductCorporationofUSA.Those
halocarbonscanbeaddedtothereactionmixtureorattheoutletofthereactortofacilitatethe
workupofthemixtureortofacilitateitscooling.

Thehalocarbonsandparticularlyfluorinatedhydrocarbonsareespeciallyinertversusstrong
oxidizingagents,includingoxygen,anddissolvegasesreadily.Forexample,itisknownthat
solubilityofoxygeninperfluoroalkanesisextremelyhigh(ClarkL.C.etal.PureAppl.Chem.,
1982,54,23832406andMarrucho,I.M.,FluidPhaseEquilibria,222223,2004,325330).This
isthereasonwhythepresentprocesscanuselowerpressurestoachievethesame
concentrationsofthereactivegasesintheliquidmediumofreactioncomparedwiththeprior
212

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

artprocessesthatproducecarbamates,andeasilyavoidsgaseousenvironmentcontainingany
explosivemixtureofreactantsabovetheliquidreactionsystem.

Accordingtoapreferredembodiment,solventsareoxygenatedfluorinatedhydrocarbons(e.g.
fluorinatedalcoholsanditsblendswithfluorinatedethersand/orketones),whereatleastone
alkylhydrogenofthehomologousoxygenateissubstitutedforfluorine.Preferredoxygenated
fluorinatedhydrocarbonsinclude,withoutlimitation,2,2,2trifluoroethanol,2,2,3,3
tetrafluoro1propanol,1,1,1,3,3,3hexafluoropropan2ol,fluorophenolsandmixturesthereof,
preferably2,2,2trifluoroethanol.Onepreferredfluorinatedetherisnonafluorobutylmethyl
ether.Onepreferredfluorinatedketoneishexafluoroacetone.

Accordingtoamostpreferredembodiment,thepreferredsolventscanbedefinedonthebasis
oftheiroxygensolubilitymeasuredinmolarfractionofoxygeninthesolvent.Thus,preferred
solventsarethosefallingwithintheoxygensolubilityrangeof105to101(limitsoftherange
includedinthisandinthenextcases);morepreferredsolventsarethosefallingwithinthe
range5105to5101;evenmorepreferredsolventsarethosefallingwithintherange104to510
2
;finally,themostpreferredsolventsarethosefallingwithintherange4104to7103as,for
example,perfluoronhexane,perfluoronheptane,perfluoronnonane,perfluorodecaline,
1,1,1,3,3,3hexafluoropropan2oland2,2,2trifluoroetanol.

Inordertocarryouttheoxidativecarbonylation,thepresenceofanalcoholisnecessarysinceit
actsasareagentintheprocessoftheinvention.Accordingtoonepreferredembodiment,such
alcoholisaperhalogenatedalcohol.Asmentionedabove,perhalogenatedalcoholsaregood
oxygensolvents.Therefore,perhalogenatedalcoholscanbepresentinthemixtureofstepi.in
morethanstoichiometricamount,andatthesametimeactasboth,asreactantandas
(co)solvent.

Thefeedandoxidizingagentcanbedissolvedinthereactionsolventinanyorderorfed
simultaneouslyinseparatestreamstothereactionsolvent.Forexample,itispossibleto
dissolveoxygeninthereactionsolventtosaturationandsubsequentlycontacttheresulting
oxygensaturatedreactionsolventwiththearomaticamine,thecatalystandcarbonmonoxide
inatubularmixer.Usingthereactionsolventsdescribedabove,thecarbonmonoxidesolubility
isgenerallyaffectedtoonlyaminorextentbythepresenceofoxygeninthereactionsolvent.

Inafurtherembodiment,riskofgasphasecontactingofreactantsmayalsobeeliminatedby
independentlydissolvingoxygeninthereactionsolventandcarbonmonoxideinthearomatic
amineorpolyamine.Inthiscase,thedissolutionstepsmaybecarriedout,forexample,in
separatedstirredtanksbeforemixingallthereagents.Thus,itisnotnecessarytodissolveall
thereagentsinthesamereactionvesseloratthesametime.Itiscertainlypossiblethatthe
reactionsolventcontainingpreviouslydissolvedreactantscanbepassedthroughafixedbedof
catalystorreactedinaslurryreactor.Inthelattercase,mechanicalagitation(e.g.stirring,
shaking,vibrating,etc.)canbeusedtoeffectthecontactingbetweenthecatalystandthe
reactants.Itisalsopossibletousealiquidfluidizedbedofcatalyst,usingaflowofgaseous
carbonmonoxideasdescribedin"Perry'sChemicalEngineers'Handbook,Sixthedition",1984
213

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

pages425,426,203and2058to2075.

Accordingtooneembodiment,thetemperatureduringthefirstheatingisinarangeoffrom
100to200C.,preferablyfrom120to180C.,andpressureisinarangeoffrom5to100bar,
preferablyfrom20to70bar.Theseconditionsassureaneffectiveoxidativecarbonylation.The
reactiontimecanvarydependingonthereactionsystememployed,catalystandotherreaction
conditionschosen.Atypicalreactiontimeisintherangeoffromaboutoneminutetoabout
3hours.

Accordingtoafurtherembodiment,afterthereactionmixtureiscooled,thetemperature
duringthesecondheatingisinarangeoffrom50to240inordertoseparatethesolventby
distillationandrecovertheisocyanateproduct.Betweenstepiiiandivanadditionalstep
comprisingseparatingthecatalystfromthereactionmixturemaybeoptionallyperformed.

Accordingtoafurtherembodiment,theseparationofthesolvent(stepiv.)canbedone
throughone,twoormore,preferablytwo,consecutivedistillationprocesses.Dependingonthe
relativeboilingpointsandnatureoftheisocyanateproductandthesolventsused,itispossible
todirectlyobtaintheisocyanateproductbyheatingandsubsequentdistillation(s).Oncethe
isocyanateproducthasbeenseparated,withoutfurthertreatment,thesolventmaybe
recoveredbyasecondsubsequentdistillation(s)ofthemixtureresultingfromthefirst
distillation(s).Iftheboilingpointofthesolventislowerthantheboilingpointoftheisocyanate
product,itispossibletocarryoutafirstdistillation(s)torecoverthesolvent,followedby
separationoftheisocyanateproduct.Othercombinationswillbeapparenttotheskilledperson
dependingontherelativeboilingpointsandnatureoftheisocyanateproductandthesolvents
used.Inanycase,thesolventrecoveredmayberecirculatedforuseinfurtherreactions.

Accordingtoafurtherembodiment,thefirstdistillation(s)iscarriedoutatatemperatureina
rangeoffrom50to180C.andunderapressureinarangeoffrom0.1to10bar,andthe
seconddistillation(s)iscarriedoutatatemperatureinarangeoffrom140to240C.andunder
apressureinarangeoffrom1to900mbar.Thecondensationheatofthesolventfromthefirst
apparatuscanbeusedforpartiallyvaporizingsolventinthesecondapparatus.
Recoveredreactionsolventthatisgeneratedbythisseparationisnormallymosteconomically
returnedtothereactionsolventphaseofthereactorforfurtherreactions.

Accordingtoafurtherembodiment,priortothesecondheating(stepiv.),itispossibletoadda
cosolventtothereactionmixture,forexample,1,2dichlorobenzeneor1,2,4trichlorobenzene.
Theadditionofthecosolventfurtherfacilitatesthedissolutionofthecarbamateintermediate
andtheulteriorseparationoftheisocyanateproductwithhigherpurity.Inthisway,thework
upofthereactionbecomeseasier.

Therawisocyanatesobtained,canbepurified,ifdesired,inacolumnwithatoppressureof
from1to950mbar,preferablyfrom5to250mbar,andabottomtemperatureof60250C.,
withthepureisocyanatesflowbeingwithdrawninliquidorgaseousform,preferablyinaside
streamofthecolumn.
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BouSaba,Dizon,Kasih,Stewart

Ithasbeenfoundthattheisocyanateproductsobtainedfollowingtheprocessofthepresent
inventionareessentiallypureandwithouttheneedoffurtherpurification.Therefore,the
processofthepresentinventionprovidesasimplewayfortheindustrialsynthesisofisocyanate
productswithouttheneedtoisolateand/orpurifyintermediateproductstoachievegood
yieldsandpurityofisocyanates.

Theprocessaccordingtothepresentinventioncanbecarriedouteitherbatchwiseorina
continuousprocessbyremovingcontinuouslythereactionmixturefromthereactionsystem
whilecontinuouslyfeedingthereactantsintothereactionsystem.Accordingtoone
embodimentoftheinvention,theprocessisacontinuousprocesswhereinspacevelocityisina
rangeoffrom20to40.000h1andthedistilledsolventisrecycledintothereaction.

Suitableaminesandpolyaminestobeconvertedintoisocyanatesaccordingtotheinvention
includesubstitutedandunsubstitutedarylamines,forexample,aniline,toluidine,3,3'
dimethyl44'diphenylamine,phenylendiamines,toluendiamines,24'and4,4'
methylendianiline,sulfonyldianilines,thiodianilines,diaminodiphenylmethanesandhigher
homologspolyaminopolyphenylmethanes,mphenylenediamine,1,5naphthylenediamineand
thelike,andmixturesthereof;andsubstitutedandunsubstitutedaryldiaminesorhigher
functionalitypolyaminesliketoluendiamines,diaminodiphenylmethanesor
polyaminopolyphenylmethanesoranymixturethereof.

Themetalofthecatalystaccordingtothepresentinventionpreferablyisametalselectedfrom
themetalsofGroupVIIIandmorepreferablythemetaliscobalt.Accordingtooneembodiment
ofthepresentinvention,themetalcomplexcatalystisselectedfromacobaltporphyrinof
formulaI

##STR00001##whereinR1andR2areeachindependentlyselectedfromhydrogen,cyano,
substitutedorunsubstitutedalkyl,substitutedorunsubstitutedcycloalkyl,substitutedor
unsubstitutedalkenyl,substitutedorunsubstitutedalkynyl,substitutedorunsubstitutedaryl,
substitutedorunsubstitutedheterocyclyl;orR1andR2togetherformasubstitutedor
unsubstitutedcycloalkyl,substitutedorunsubstitutedcycloalkenyl,substitutedor
unsubstitutedcycloalkynyl,substitutedorunsubstitutedaryl,substitutedorunsubstituted
heterocyclyl;R3isselectedfromhydrogen,cyano,substitutedorunsubstitutedalkyl,
substitutedorunsubstitutedcycloalkyl,substitutedorunsubstitutedalkenyl,substituted
orunsubstitutedalkynyl,substitutedorunsubstitutedaryl,substitutedorunsubstituted
heterocyclyl;oracobaltphthalocyanineofformulaII

##STR00002##whereinR1andR2havethesamemeaningasinformulaI;oracobaltShiffbase
catalystofformulaIII

##STR00003##whereinR1andR2havethesamemeaningasinformulaI;R4,R5,R6andR7are
eachindependentlyselectedfromhydrogen,cyano,substitutedorunsubstitutedlinearalkyl,
substitutedorunsubstitutedbranchedalkyl,substitutedorunsubstitutedalkoxy,OSiR10,
215

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

whereinR10isasubstitutedorunsubstitutedalkyl,substitutedorunsubstitutedcycloalkyl,
substitutedorunsubstitutedalkenyl,substitutedorunsubstitutedalkynyl,substitutedor
unsubstitutedaryl,substitutedorunsubstitutedheterocyclyl;R9andR8areeachindependently
selectedfromhydrogen,cyano,substitutedorunsubstitutedalkyl,substitutedorunsubstituted
cycloalkyl,substitutedorunsubstitutedalkenyl,substitutedorunsubstitutedalkynyl,
substitutedorunsubstitutedaryl,substitutedorunsubstitutedheterocyclyl;ormixtures
thereof.

Accordingtoonepreferredembodiment,R5andR7areeachaC1C.sub.4alkoxygroup.

Accordingtoanotherpreferredembodiment,R4,R5,R6andR7areeachindependentlyselected
fromasubstitutedorunsubstitutedbranchedalkylgroup.

Accordingtoonepreferredembodiment,thecatalystoftheinventioncomprisesasolid
support.Catalystsupportscanprovidehighsurfaceareatodisperseactivecatalystcomponents
andimmobilizetheactivecatalystcomponentsandallowaneasyrecoveryofthecatalyst.When
carbonmonoxide,oxygenandtheaminereactonthecatalystsurface,thereactionproducts
migrateintotheorganicphase,fromwhichisocyanateproductscanberecoveredby
conventionaldistillation.Usefulsupportsarewellknownintheartandmayinclude,bywayof
nonlimitingexample,activatedcarbonand/orclay,i.e.,montmorillonite;polymersupportssuchas
poly(styrenedivinylbenzene),polystyrene,andpolyimide;mesoporousmaterialssuchas
zeolite,MCM41,ZSM5,HZSM5,ammoniumZSM5andSBA15;andmetaloxidessuchas
gammaAl2O.sub.3,SiO2andTiO2,andMgO,silicaorinorganicrefractorymetaloxides.

Suchsupportedcatalystscanbepreparedbyknownmethods.Forexample,Coclaycanbe
preparedbyanchoringthesalenligandintheinterlayersofmontmorilloniteandsubsequent
complexationwithcobaltacetatebythemethoddescribedbyChoudharietal.(J.Chem.Soc.,
Chem.Commun.,1987,1505);theimmobilizationofCosalenderivativesonmesoporoussilica
gelandMCM41byusinggraftingreactions,forexample,accordingtoI.C.Chisemetal.,Chem.
Commun.1998,1949;P.Sutraetal.Chem.Commun.1996,p.2485;X.GZhouetal.Chem.
Commun.1999,1789orR.J.P.Corriuetal.,J.Mater.Chem.,2002,12,13551362orbythe
methoddescribedinUSPatentApplicationPublication2005/0131252.

Further,theprocessofthepresentinventioncanbecarriedoutintheabsenceorinthe
presenceofapromoter.Accordingtooneembodiment,thehalidepromotercanbeselected
fromalkalimetalhalides,alkalineearthmetalhalides,oniumhalides,compoundscapableof
formingoniumhalidesatthecontactingconditions,oxoacidsofhalogenatomandtheirsalts,
organichalidesandhalogenmolecules.Thosecompoundscontainingiodineareparticularly
preferred.TheseincludeKI,NaI,LiI,CsI,tetrabutylammoniumiodine,tetraheptylammonium
iodide,iodousacid,iodineandthelike.

Intheabovedefinitionoftheprocessandcompoundsandinthedescriptionandclaimsthe
followingtermshavethemeaningindicated:

216

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

"Onepot"referstoprocesseswhichdonotinvolveisolationofanyintermediatespriorto
recoveryofthefinalproduct,regardlessofthenumberofstepsrequired.

Theterm"underpressure"isunderstoodasapressureaboveatmosphericpressure,thatis,
above1atmosphere.

"Essentiallypure"referstocompoundswhichrequirenopurificationpriortofurtheruse.
Typically,aproducthavingpurityhigherthan98%w/wisconsideredessentiallypure.However,
forsomeapplicationsisocyanateproductshavingpurityhigherthan95%w/warealso
consideredessentiallypure.

"perhalogenated"referstoorganicmoleculesinwhichhydrogenissubstitutedintwoormore
positionsbyahalogengroup,preferablyinallpositions.Forexample,perhalogenatedalkyl
groupsarethoseinwhichatleasttwohydrogenatomsaresubstitutedbyahalogenatom,e.g.,
chlorine,bromine,iodine,orfluorine.

"halogenated"referstoorganicmoleculesinwhichhydrogenissubstitutedinatleastone
positionbyahalogengroup.Therefore,perhalogenatedmoleculesarecomprisedwithinthe
groupofhalogenatedmolecules.

"isocyanateproduct"referstotheproductsobtainedbyputtingintopracticetheprocess
accordingtothepresentinvention,includingisocyanatesandpolyisocyanates.

"Alkyl"referstoastraightorbranchedhydrocarbonchainradicalconsistingofcarbonand
hydrogenatoms,containingnosaturation,having112,preferablyonetoeightcarbonatoms,
andwhichisattachedtotherestofthemoleculebyasinglebond,e.g.,methyl,ethyl,npropyl,
ipropyl,nbutyl,tbutyl,npentyl,etc.Alkylradicalsmaybeoptionallysubstitutedbyoneor
moresubstituentssuchashalo,hydroxy,alkoxy,OPr,OBn,OBz,carboxy,cyano,carbonyl,acyl,
alkoxycarbonyl,amino,imino,nitro,mercaptoandalkylthio.

"Alkoxy"referstoaradicaloftheformulaORawhereRaisanalkylradicalasdefinedabove,
e.g.,methoxy,ethoxy,propoxy,butoxyetc.

"Aryloxy"referstoaradicalofformulaORbwhereinRbisanarylradicalasdefinedbelow.

"Amino"referstoaradicaloftheformulaNH2,NHRa,NRaRb.

"Aryl"referstoanaromatichydrocarbonradicalsuchasphenyl,naphthyloranthracyl.Thearyl
radicalmaybeoptionallysubstitutedbyoneormoresubstituentssuchashydroxy,mercapto,
halo,alkyl,phenyl,alkoxy,haloalkyl,nitro,cyano,dialkylamino,aminoalkyl,acyland
alkoxycarbonyl,asdefinedherein.

"Aralkyl"referstoanarylgrouplinkedtoanalkylgroup,suchasbenzylandphenethyl.

217

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

"Alcohol"makesreferencetoanalkylcomprising1to12carbonatomsandsubstitutedbyat
leastonehydroxylgroup.

"Cycloalkyl"referstoasaturatedcarbocyclicringhavingfrom3to8carbonatoms.

"Heterocyclyl"referstoastable3to15memberedringwhichconsistsofcarbonatomsand
fromonetofiveheteroatomsselectedfromthegroupconsistingofnitrogen,oxygen,and
sulfur,preferablya4to8memberedringwithoneormoreheteroatoms,morepreferablya5
or6memberedringwithoneormoreheteroatoms.Forthepurposesofthisinvention,the
heterocyclemaybeamonocyclic,bicyclicortricyclicringsystem,whichmayincludefusedring
systems;andthenitrogen,carbonorsulfuratomsintheheterocyclylradicalmaybeoptionally
oxidized;thenitrogenatommaybeoptionallyquaternized;andtheheterocyclylradicalmaybe
partiallyorfullysaturatedoraromatic.Examplesofsuchheterocyclesinclude,butare
notlimitedto,azepines,benzimidazole,benzothiazole,furan,isothiazole,imidazole,indole,
piperidine,piperazine,purine,quinoline,thiadiazole,andtetrahydrofuran.

"Aromatichalocarbon"inthepresentinventionreferstocompoundscomprisinganaromatic
residuesubstitutedwithonormorehalogenatoms.

"Complex"referstoamoleculewhichisformedbytwocomponents:adonorandanacceptor.
Bondingbetweenbothcomponentstoformthecomplexispossiblebecausethedonormay
donateanunsharedpairofelectronsorelectronsonorbitals,whichtheacceptorcan
accommodate.Inacomplexmorethanonedonorand/ormorethanoneacceptorarepossible.
Also,inthesame"complex"onedonormaybebondedtomorethanoneacceptorandvice
versa.Besidesthedonoracceptorinteractionsdescribedabove,othertypesofbondingknown
totheskilledperson,suchascovalentbonding,mayexistbetweenthedonorandtheacceptor.

Referenceshereintosubstitutedgroupsinthecompoundsofthepresentinventionrefertothe
specifiedmoietythatmaybesubstitutedatoneormoreavailablepositionsbyoneormore
suitablegroups,e.g.,halogensuchasfluoro,chloro,bromoandiodo;cyano;hydroxyl;nitro;
azido;alkanoylsuchasaC112alkanoylgroupsuchasacylandthelike;carboxamido;alkyl
groupsincludingthosegroupshaving1toabout12carbonatomsorfrom1toabout6carbon
atomsandmorepreferably13carbonatoms;alkenylandalkynylgroupsincludinggroups
havingoneormoreunsaturatedlinkagesandfrom2toabout12carbonorfrom2toabout6
carbonatoms;alkoxygroupshavingoneormoreoxygenlinkagesandfrom1toabout12
carbonatomsor1toabout6carbonatoms;aryloxysuchasphenoxy;alkylthiogroupsincluding
thosemoietieshavingoneormorethioetherlinkagesandfrom1toabout12carbonatomsor
from1toabout6carbonatoms;alkylsulfinylgroupsincludingthosemoietieshavingoneor
moresulfinyllinkagesandfrom1toabout12carbonatomsorfrom1toabout6carbonatoms;
alkylsulfonylgroupsincludingthosemoietieshavingoneormoresulfonyllinkagesandfrom1
toabout12carbonatomsorfrom1toabout6carbonatoms;aminoalkylgroupssuchasgroups
havingoneormoreNatomsandfrom1toabout12carbonatomsorfrom1toabout6carbon
atoms;carbocylicarylhaving6ormorecarbons,particularlyphenylornaphthylandaralkyl
suchasbenzyl.Unlessotherwiseindicated,anoptionallysubstitutedgroupcanhavea
218

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

substituentateachsubstitutablepositionofthegroup,andeachsubstitutionisindependentof
theother.

Unlessotherwisestated,thecompoundsobtainablebytheprocessoftheinventionarealso
meanttoincludecompoundswhichdifferonlyinthepresenceofoneormoreisotopically
enrichedatoms.Forexample,compoundsobtainablebytheprocessoftheinventionhavingthe
samestructuresexceptforthereplacementofahydrogenbyadeuteriumortritium,orthe
replacementofacarbonbya13Cor14Cenrichedcarbonor15Nenrichednitrogenarewithinthescope
ofthisinvention.

Theinventionwillbefurtherillustratedbymeansofexamples,whichshouldnotbeinterpreted
aslimitingthescopeoftheclaims.

EXAMPLES

Example1

GeneralProcedurefortheFormationofaSchiffBaseTypeLigandCatalyst

Analdehydeisrefluxedinthepresenceofthecorrespondingdiamine(2:1molarratio)inethanol
95%.FiltrationandfurtherwashingwithabsoluteethanolaffordedtheessentiallypureSchiff
basetypeligand.

TheSchiffbasetypeligandobtainedaboveisrefluxedinanalcoholicsolutiontogetherwithan
aqueoussolutionofCo(OAc)2.4H2Ounderinertatmosphere.Althoughacrystallineprecipitate
immediatelyappeared,refluxingcontinuesforaboutanhour.Theprecipitateobtainedis
filteredundervacuum,washedwithwater,ethanolandether,andthendriedundervacuum.

Example2

ImmobilizationoftheCatalysttoaSolidSupport

N,N'(bis(3,5ditertbutylsalicylidene)ethylenediamino)cobalt(II)[CotBuSalen],1.9g,
preparedfollowingtheprocedureofExample1,isaddedto125mlof2propanolwithstirring,
andthemixtureheatedto70C.Powderedsilica(5g,GraceDavisonXPO2407,specificsurface
area250m2/g)isaddedtothesolutionandtemperatureandthestirringaremaintainedfora
further5hours.Thesuspensionisfiltered,thesolidresidueiswashedwith25ml
dichloromethaneanhydrous,twice,andfinallydriedundervacuumfor5hours.

Example3

ComparativeExample

Amixtureoftheaniline(13.2mmol),thecobaltcomplex[CotBuSalen](0.25mmol)prepared
219

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

followingExample1,NaI(2,72mmol)and1butanol(20ml)ischargedina100mlautoclave.The
autoclaveisflushedwithcarbonmonoxideandoxygeninavolumetricratioof19/1toatotal
pressureof52.7bar.Thetemperatureisincreasedto110C.Thereactionismaintainedunder
constantvigorousstirringforthreehours.After3hoursthereactoriscooledtoroom
temperature,depressurisedand97.8gof1,2Dichlorobenzene(DCB)ischargedinthereactor.
Thetemperatureisincreasedto180C.underatmosphericpressure.No1butanolisrecovered
bycondensationofthevapours.Analysisofthereactionresidueconfirmstheexistenceofurea
derivativesbutnotracesofphenylisocyanatecanbefound.

Example4

SynthesisofPhenylisocyanate

Ina1000mlhighpressurestirredautoclave15.5gofaniline,7.6gofthe[CotBuSalen]/Silica
catalystofExample2,1.78gofNaIand488gof2,2,2trifluoroethanol(TFE)arecharged.The
autoclaveispressurizedwithcarbonmonoxideandoxygeninavolumetricratioof19/1.The
temperatureisincreasedto120C.andthetotalpressureismaintainedconstantat40bars.
Thereactionismaintainedunderconstantvigorousstirringforthreehours.After3hoursthe
reactoriscooledtoroomtemperature,depressurizedand97.8gof1,2dichlorobenzene(DCB)
ischargedinthereactor.Thetemperatureisincreasedto180C.underatmosphericpressure.
ThevaporsofTFEareseparated,condensed,andreusedinthefollowingexample.Inthe
bottomofthereactoramixtureofDCBandphenylisocyanateisobtained.Fromthismixture
pheylisocyanateisrecoveredbydistillationwith99%w/wpurity.

Yieldoftheintermediatecarbamatewas94%andyieldofthefinalisocyanatewas54.6%
(51.3%overallyield).

Example5

Synthesisof2,4toluendiisocyanate

Ina1000mlhighpressurestirredautoclave10gof2,4toluendiamine(TDA),7.6gof[CotBu
Salen]/SilicacatalystofExample2,1.7gofNaIand484gof2,2,2trifluoroethanol(TFE)are
charged.Theautoclaveispressurizedwithcarbonmonoxideandoxygeninavolumetricratioof
19/1.Thetemperatureisincreasedto120C.andthetotalpressureismaintainedconstantat
40bars.Thereactionismaintainedunderconstantvigorousstirringforthreehours.After3
hoursthereactoriscooledtoroomtemperature,depressurizedand97.8gof1,2
dichlorobenzene(DCB)ischargedinthereactor.Thenthetemperatureisincreasedto180C.
underatmosphericpressure.ThevaporsofTFEareseparated,condensed,andreusedinthe
followingexample.InthebottomofthereactoramixtureofDCBand2,4toluendiisocyanateis
obtained.Fromthismixture2,4toluendiisocyanateisrecoveredbydistillationwith99%w/w
purity.

Yieldoftheintermediatecarbamatewas84.1%andyieldofthefinalisocyanatewas83%
220

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

(69.8%overallyield).

Example6

Synthesisof2,4toluendiisocyanate

Ina350mlhighpressurestirredautoclave2gof2,4toluendiamine(TDA),0.37gofN,N'
(bis(3,5ditertbutylsalicylidene)ethylenediamino)cobalt(II)[CotBuSalen],synthesizedas
describedinExample1,0.18gofNaIand48.7gof2,2,2trifluoroethanol(TFE)arecharged.The
autoclaveispressurizedwithcarbonmonoxideandoxygeninavolumetricratioof19/1.The
temperatureisincreasedto120C.andthetotalpressureismaintainedconstantat40bars.
Thereactionismaintainedunderconstantvigorousstirringforthreehours.After3hoursthe
reactoriscooledtoroomtemperature,depressurizedand97.8gof1,2dichlorobenzene(DCB)
ischargedinthereactor.Thetemperatureisincreasedto180C.underatmosphericpressure.
ThevaporsofTFEareseparated,condensed,andreusedinthefollowingexample.Inthe
bottomofthereactoramixtureofDCBand2,4toluendiisocyanateisobtained.Fromthis
mixture2,4toluendiisocyanateisrecoveredbydistillationwith99%w/wpurity.

Yieldoftheintermediatecarbamatewas82%andyieldofthefinalisocyanatewas78%(64%
overallyield).

Example7

Synthesisof2,4toluendiisocyanate

Ina350mlhighpressurestirredautoclave1gof2,4toluendiamine(TDA),0.2gof(..)Trans
N,N'bis(3,5ditertbutylsalicylidene)1,2cyclohexanediaminocobalt(II),synthesizedas
describedinExample1,0.18gofNaIand48.9gof2,2,2trifluoroethanol(TFE)arecharged.The
autoclaveispressurizedwithcarbonmonoxideandoxygeninavolumetricratioof19/1.The
temperatureisincreasedupto120C.andthetotalpressureismaintainedconstantat40bars.
Thereactionismaintainedunderconstantvigorousstirringforthreehours.After3hoursthe
reactoriscooledtoroomtemperature,depressurizedand97.8gof1,2dichlorobenzene(DCB)
ischargedinthereactor.Thetemperatureisincreasedto180C.underatmosphericpressure.
ThevaporsofTFEareseparated,condensed,andreusedinthefollowingexample.Inthe
bottomofthereactoramixtureofDCBand2,4toluendiisocyanateisobtained.Fromthis
mixture2,4toluendiisocyanateisrecoveredbydistillationwith99%w/wpurity.

Yieldoftheintermediatecarbamatewas88.1%andyieldofthefinalisocyanatewas62.4%
(55%overallyield).
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221

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

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Bolzacchini,Ezio,etal.,Substituenteffectsinthecobaltcatalyzedoxidative
carbonylationofaromaticamines,JournalofMolecularCatalysis,1996,pp.281
287,vol.111.
Bassoli,Angela,etal.,Acyclicandcyclicureaformationviathecobaltcatalysed
oxidativecarbonylationofaromaticprimaryamines,JournalofMolecular
Catalysis,1990,pp.4148,vol.60.
Alper,Howard,etal.,Anexceptionallymild,catalytichomogeneousmethodforthe
conversionofaminesintocarbamateesters,J.Chem.Soc.,Chem.Commun.,1985,
pp.11411142.
Bolzacchinietal.,JournalofMolecularCatalysisA:Chemical111(1996)281287.

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Inventors

SerranoFernandez,FranciscoLuis
AlmenaMunoz,Beatriz
PadillaPolo,Ana
OrejonAlvarez,Arancha
ClaverCabrero,Carmen
CastillonMiranda,Sergio
SalagreCarnero,Pilar
Aghmiz,Ali

Assignee

REPSOLYPF,S.A.

Application
No.11765449filedon06/20/2007

USClasses:
560/341Carbonmonoxideutilized

Examiners
Primary:Puttlitz,Karl

Attorney,AgentorFirm

Hultquist;StevenJ.
IntellectualProperty/TechnologyLaw

USPatentReferences
5194660Processesforproducingcarbamatesandisocyanates
Issuedon:03/16/1993
Inventor:Leung,etal.

ForeignPatentReferences

2004262835JP09/01/2004
9856758WO12/01/1998
9947493WO09/01/1999

224

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

InternationalClass
C07C263/00

Appendix7:USPatent
4582923Processforthe
ProductionofUrethanes

225

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

USPatent4582923Processfortheproductionofurethanes

Inventor:Stammann,etal.DateIssued:April15,1986Application:06/735,249Filed:May17,
1985Inventors:Becker;Robert(Leverkusen,DE)
Grolig;Johann(Leverkusen,DE)
Stammann;Gunter(Cologne,DE)
Waldmann;Helmut(Leverkusen,DE)
Assignee:BayerAktiengesellschaft(Leverkusen,DE)PrimaryExaminer:Helfin;Bernard
AssistantExaminer:AttorneyOrAgent:Harsh;GeneGil;JosephC.Whalen;LyndanneM.U.S.
Class:546/159;546/309;548/163;548/557;548/558;549/480;549/69;560/115;560/13;
560/157;560/158;560/162;560/163;560/22;560/24;560/25;560/29;560/30FieldOfSearch:
560/24;560/25;560/32;560/163;560/157;560/162;560/158;560/115;560/30;560/29;
560/22;560/13;546/309;546/159;548/557;548/558;548/163;549/480;549/69;260/465.4
InternationalClass:U.SPatentDocuments:3641092;4236016;4251667;4260781;4266070;
4267353;4297501;4319035ForeignPatentDocuments:2910132OtherReferences:
Abstract:Urethanesaremadebyreactingaprimaryaminewithcarbonmonoxideandacompound
containingatleastonehydroxylgroupinthepresenceofanoxidizingagentandacatalyst
system.Thecatalystsystemismadeupof(i)anoblemetaland/oranoblemetalcompoundof
ametaloftheEighthSecondaryGroupofthePeriodicSystemofElementsand(ii)anoxidizing
quinoidand/oracompoundcapableofbeingconvertedtoanoxidizingquinoidcompound
underthereactionconditions.Thecatalystsystemmayoptionallyinclude(iii)metal
compoundsofelementsoftheThirdtoFifthMainGroupsand/orFirsttoEighthSecondary
GroupsofthePeriodicSystemofElementsand/or(iv)atertiaryamine.Thisreactionis
generallycarriedoutatatemperatureoffrom100.degree.to300.degree.C.andatapressure
offrom5to500bars.Theproducturethanesareusefulintheproductionofisocyanatesand
pesticides.Claim:Whatisclaimedis:

1.Aprocessfortheproductionofaurethanebyreactingaprimaryaminewithcarbon
monoxideandacompoundcontainingatleastonehydroxylgroupinthepresenceoffrom60to
500%ofthestoichiometricamountofoxygennecessarytoreactwiththeaminogroupstobe
reactedandacatalystsystem,saidcatalystsystemcomprising:

(a)palladium,apalladiumcompoundoramixturethereof;and

(b)anoxidizingquinoid,acompoundcapableofbeingconvertedtoanoxidizingquinoid
compoundunderthereactionconditions,oramixturethereofinanamountoffrom0.1to5wt
%(basedontotalweightofreactionmixture).

2.Theprocessofclaim1whereinthecatalystsystemfurthercomprisesacompoundofan
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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

elementselectedfromtheThirdtoFifthMainGroupsand/orFirsttoEighthSecondaryGroupof
thePeriodicSystemofElementswhichcompoundiscapableofundergoingaredoxreaction
underthereactionconditions.

3.Theprocessofclaim1whereinthecatalystsystemfurthercomprisesatertiaryamine.

4.Theprocessofclaim1whereincomponent(a)ofthecatalystsystemispresentinanamount
whichisfrom5ppmto100ppmexpressedasnoblemetalandbasedonthetotalweightofthe
reactionmixture.

5.Theprocessofclaim1whereinthecatalystsystemfurthercomprisesupto0.1wt.%(based
onthetotalweightofthereactionmixture)ofacompoundofanelementselectedfromthe
ThirdtoFifthMainGroupand/orFirsttoEighthSecondaryGroupofthePeriodicSystemof
Elementswhichcompoundiscapableofundergoingaredoxreactionunderthereaction
conditions.

6.Theprocessofclaim5whereinthecatalystsystemfurthercomprisesupto10wt.%(based
onthetotalweightofthereactionmixture)ofatertiaryamine.

7.Theprocessofclaim1whereinthereactioniscarriedoutatatemperatureintherangefrom
100.degree.to250.degree.C.andunderapressureoffrom5to500bars.

8.Theprocessofclaim1whereinthereactioniscarriedoutinthepresenceofupto80wt.%
(basedonthetotalweightofthereactionmixture)ofaninertsolvent.

9.Theprocessofclaim1whereintheproducturethaneisseparatedfromthecatalystsystem
andanyremainingoxidizingagentorreducedoxidizingagentbydistillationand/orfiltration.

10.Theprocessofclaim9whereintheseparatedcatalystsystemisreusedinasubsequent
reaction.

11.Theprocessofclaim1inwhichthereactioniscarriedoutinthepresencefrom100to500%
ofthestoichiometricamountofoxygennecessarytoreactwiththeaminogroupstobe
reacted.Description:BACKGROUNDOFTHEINVENTION

Thisinventionrelatestoaprocessfortheproductionofurethanes(carbamicacidestersor
carbamates).Morespecifically,itrelatestoaprocessinwhichprimaryaminesarereactedwith
organichydroxylcompoundsandcarbonmonoxideinthepresenceofanoxidizingagentandin
thepresenceofacatalystsystem.Thecatalystsystemincludesatleastonenoblemetalorat
leastonenoblemetalcompound,andaquinoidcompoundorcompoundcapableofbeing
convertedintoaquinoidcompound.

Generally,organicisocyanatesarecommerciallyproducedbyreactingthecorrespondingamine
withphosgene.However,duetothehighchlorinedemandandthehighenergycostsinvolvedin
227

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

theproductionofphosgene,considerableeffortshavebeenexertedtofindacommercially
workablemethodforproducingorganicisocyanatesinwhichthereisnoneedtousephosgene.
Inonesuchmethod,primaryaminesarereactedwithcarbonmonoxide,organichydroxyl
compoundsandanoxidizingagent(suchasairoranorganicnitrocompound)toformthe
correspondingurethanes;theurethanesthusformedarethensplitintoisocyanatesand
compoundscontaininghydroxylgroups.Thisphosgenefreeprocessforproducingurethanesis
describedinGermanOffenlegungsschriftNo.2,910,132andinGermanOffenlegungsschriftNo.
2,908,251(.dbd.EPOSNo.16346orU.S.Ser.No.125,394filedFeb.27,1980).Intheprocess
describedinGermanOffenlegunggschriftNo.2,908,251,primaryaminesarecatalytically
oxycarbonylatedbyreactionwithcarbonmonoxide,organichydroxylcompounds,anoxidizing
agentwhichiseithermolecularoxygenoranitrocompoundandacatalyst.Thedisclosed
catalystis,from1to5weight%(basedonthemixtureasawhole,)ofchloridecontaining,
inorganicsolidswhicharelargelyinsolubleinthereactionmixtureusedincombinationwitha
noblemetalcatalyst.Thislatterprocess,however,isdisadvantageousinthatthehighcontent
ofchloridecontainingcompoundscausescorrosionproblemsintheprocessapparatus.
Additionally,thefactthattheinorganiccatalystcomponentsaresubstantiallyinsoluble
seriouslyaffectsthecommercialpracticabilityoftheknownprocess.

SUMMARYOFTHEINVENTION

Itisanobjectofthepresentinventiontoprovideaprocessfortheproductionofurethanes
fromprimaryamines.

Itisanotherobjectofthepresentinventiontoprovideaprocessfortheproductionof
urethanesfromprimaryamineswhichdoesnotrequiretheuseofphosgene.

Itisalsoanobjectofthepresentinventiontoprovideaprocessfortheproductionofurethanes
fromprimaryaminesinwhichinsolubleand/orcorrosivecatalystsneednotbeused.

Theseandotherobjectswhichwillbeapparenttothoseskilledintheartareaccomplishedby
reactingaprimaryaminewithcarbonmonoxideandacompoundhavingatleastonehydroxyl
groupinthepresenceofanoxidizingagentandacatalystsystem.Asuitablecatalystsystem
includesanoblemetaland/ornoblemetalcompoundofGroupVIIIbofthePeriodicSystemof
Elementsandanoxidizingquinoidcompoundand/oracompoundcapableofbeingconverted
toanoxidizingquinoidcompoundunderthereactionconditions.

DETAILEDDESCRIPTIONOFTHEINVENTION

Thepresentinventionrelatestoaprocessfortheproductionofurethanesinwhichprimary
aminesarereactedwithcarbonmonoxideandcompoundscontainingatleastonehydroxyl
groupinthepresenceofoxidizingagentsandacatalystsystem.Appropriatecatalystsystems
containatleastonenoblemetaland/ornoblemetalcompoundfromtheEighthSecondary
GroupofthePeriodicSystemofElements,andatleastoneoxidizingquinoidcompoundand/or
atleastonecompoundwhichmaybeconvertedunderthereactionconditionsintoanoxidizing
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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

quinoidcompound.

Primaryamineswhichmaybeusedinthepracticeofthepresentinventionareanyorganic
compoundscontainingatleastoneprimaryaminogroup,particularlyprimaryamines
containingatleastonealiphatically,cycloaliphatically,aromaticallyorheterocyclicallybound
aminogroupwhichaminesmayoptionallycontainotherfunctionalgroups.Itispreferredto
usearomaticoraliphaticmonoaminesordiamines,particularlymonoamineswhichdonot
containanyoxidizablesubstituentsotherthantheprimaryaminogroups.Theaminesusedin
thepracticeofthepresentinventiongenerallyhaveamolecularweightintherangefrom31to
3000,preferablyintherangefrom31to400andmostpreferablyintherangefrom31to200.

Examplesofsuitablearomaticandheterocyclicaminesincludeaniline,1,2diaminobenzene,
1,4diaminobenzene,theisomericchloroanilines,3,4dichloroaniline,4isopropylaniline,p
toluidine,chlorotoluidines,xylidines,alkoxyanilines,4pentachloroethylaniline,2nitroaniline,
3nitroaniline,4nitroaniline,2,3diaminotoluene,2,4diaminotoluene,2,6diaminotoluene,
2,5diaminotoluene,3,4diaminotoluene,3,5diaminotoluene,2amino4nitrotoluene,2
amino3nitrotoluene,2amino5nitrotoluene,aminophenols,diaminoxylenes,
aminonitroxylenes,aminonaphthalenes,aminoanthracenes,chloroaminobenzoicacids,
chloroaminobenzoicacidesters,aminobenzenesulfonicacids,4,4'diaminodiphenylmethane,
2,2'diaminodiphenylmethane,2,4diaminodiphenylmethane,tris(4aminophenyl)methane,
aminopyridines,aminoquinolines,aminopyrroles,aminofurans,aminothiophenesand2
aminobenzothiazole.

Examplesofsuitablecycloaliphaticprimaryaminesareaminocyclobutane,aminocyclopentane,
cyclohexylamine,1,2diaminocyclohexane,1,3diaminocyclohexane,1,4diaminocyclohexane,
bis(aminocyclohexyl)methanesandtris(aminocyclohexyl)methanes.

Examplesofappropriatealiphaticprimaryaminesinclude:methylamine,ethylamine,1
propylamine,2propylamine,1butylamine,2butylamine,isobutylamine,tert.butylamine,1
pentylamine,1hexylamine,1heptylamine,1octylamine,1decylamine,1dodecylamine,
ethylenediamine,1,2diaminopropane,1,3diaminopropane,diaminobutanes,
diaminopentanes,diaminohexanes,diaminooctanes,diaminodecanes,benzylamine,bis
(aminomethyl)cyclohexanes,bis(aminomethyl)benzene,.omega.aminocarboxylicacidesters,
and.omega.aminocarboxylicacidnitriles.

Particularlypreferredprimaryaminesarearomaticprimaryamines,suchasaniline,substituted
anilines,theisomericdiaminotoluenesand4,4'diaminodiphenylmethane.

Organiccompoundscontaininghydroxylgroupswhichmaybeusedinthepracticeofthe
presentinventionareanyorganiccompoundswhichcontainatleastonealcoholicallyor
phenolicallyboundhydroxylgroupandwhichhaveamolecularweightintherangefrom32to
2000(preferablyintherangefrom32to300).Alcoholsarethepreferredhydroxymaterials.

Suitablealcoholsinclude:anylinearorbranchedmonohydricorpolyhydricalkanolsoralkenols,
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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

anymonohydricorpolyhydriccycloalkanols,cycloalkenolsandaralkanols.Anyalcohols
containinginertsubstituentssuchashalogenatoms,sulfoxidegroups,sulfonegroups,carbonyl
orcarboxylicacidestergroupsmayalsobeused.Alcoholscontainingetherbridgesarealso
suitableforthepracticeofthepresentinvention.Examplesofappropriatealcoholsare:
methanol,ethanol,npropanol,isopropanol,nbutanol,npentanol,nhexanol,cyclohexanol,
benzylalcohol,chloroethanol,ethyleneglycol,diethyleneglycol,propyleneglycol,dipropylene
glycol,glycerol,hexanetriolandtrimethylolpropane.

Ifanalcoholhavingahydroxylfunctionalitygreaterthanoneisused,amonobasicamine
shouldbeusedasthestartingcomponentintheprocessofthepresentinvention.Conversely,if
higherfunctionalityaminesareused,amonofunctionalhydroxylcompoundshouldbeusedasa
reactant.Monohydricaliphaticalcoholscontainingfrom1to6carbonatomsarethepreferred
hydroxylreactantsintheprocessofthepresentinvention.

Phenolssuitableforthepracticeofthepresentinventionarethosehavingamolecularweight
intherangefrom94to600,preferablyintherangefrom94to300.Examplesofsuchphenols
include:phenol,.alpha.naphthol,.beta.naphthol,anthranol,phenanthrol,hydroxybenzofurans
andhydroxyquinolines.Polyhydricphenolssuchasdihydroxybenzenes,dihydroxy
naphthalenes,4,4'dihydroxydiphenylmethane,bisphenolA,pyrogallolandphloroglucinolmay
alsobeused.Anyoftheabovementionedphenolscontaininginertsubstituentssuchashalogen
atoms,sulfoxidegroups,sulfonegroups,carboxylorcarboxylicacidestergroups,nitrogroups,
alkylgroups,arylgroups,alkoxygroupsandaroxygroupsarealsosuitable.Particularly
preferredphenolsarephenol,theisomericchlorophenols,bisphenolA,2isopropoxyphenol
and7hydroxy2,2dimethyl2,3dihydrobenzofuran.

Inpracticingtheprocessofthepresentinvention,theorganiccompoundscontaininghydroxyl
groupsshouldgenerallybeusedinquantitiessuchthatfrom1to200molsandpreferablyfrom
1to50molsofhydroxylgroupsarepresentforeachmolofprimaryaminogrouppresentinthe
reactionmixture.Sincehydroxylcompoundswhichareliquidunderthereactionconditionsare
generallyusedasreactants,whenusedinexcessamountsthesecompoundsmayserveasthe
reactionmedium(solvent)fortheprocessaccordingtotheinvention.

Thecarbonmonoxideisgenerallyusedinaquantitysuchthatbetween1and30molsofcarbon
monoxidearepresentforeachmolofurethanetobeproduced,i.e.from1to30molsof
carbonmonoxidearegenerallyusedforeachmolofprimaryaminogroupspresentinthe
reactionmixture.

Molecularoxygeninpureformorintheformofamixturewithaninertgas(e.g.nitrogenor
carbondioxide)suchasair,maybeusedastheoxidizingagentintheprocessofthepresent
invention.Inthepresenceofmolecularoxygen,theoxycarbonylationreactiontakesplacein
accordancewiththefollowinggeneralequation:

Itisreadilyseenfromthisequationthat1molofcarbonmonoxideand1/2molofoxygenare
requiredforeachurethanegroupformed.Ingeneral,molecularoxygenmaybeusedinan
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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

amountrangingfromasubstantiallystoichiometricquantitytoa5foldexcess(basedonthe
aminogroupstobereacted).However,wherealcoholssensitivetooxidizingagentsareusedas
reactants,itmaybeadvisabletousetheoxidizingagent(particularlyoxygen)inasub
stoichiometricquantity(basedontheaminogroupstobereacted),i.e.inaquantitywhich
correspondstobetween60and100%oftheequivalentquantityrequiredinaccordancewith
theaboveequation.Useoflessthanstoichiometricquantitieswhenoxidationsensitive
alcoholsareusedisadvantageousbecausethedecreaseinyieldofurethaneattributableto
undesirableoxidationreactionsmaybegreaterthanthedecreasewhichoccurswhen
substoichiometricquantitiesofoxidizingagentareused.Inaddition,whereasub
stoichiometricquantityofoxidizingagent,particularlyoxygen,isusedthereactionmixturewill
containreadilyrecoverablestartingaminewhichmaybereusedinasubsequentreaction.
However,whenexcessoxidizingagentispresentinareactionmixturecontainingsuchan
oxidationsensitivealcohol,thealcoholwillbedestroyedbyundesirableoxidationreactions
andcannotberecovered.

Inadditiontooxygen,othersuitableoxidizingagentsincludeanyoxidizing,inorganic,largely
ioniccompounds(particularlysaltlikecompounds)ofmetalsinrelativelyhighvalencystages
whichmetalsmayhaveseveralvalencystages.Thenatureoftheanionsinthesecompoundsis
notimportant.Appropriateanionicgroupsarechloride,bromide,hydroxide,sulfate,hydrogen
sulfate,phosphate,nitrateandcarbonateanions.Theseanionsmaybepresentsinglyorin
combinationwithoneanotherorincombinationwithoxyanions(i.e.anionsinwhichoxygenis
present).Similarly,organiccounterions,forexamplecarboxylate,sulfonate,phosphonate,
alcoholateandphenolateionsmayalsobepresentasanions.

Thelargelyioniccompoundsofmetalshavingatomicnumbers22to29,42,47,50,51,58,74,
80to83and92inhighpositivevalencystagesareparticularlypreferredinorganicoxidizing
agents.Whereinorganicoxidizingagentsofthistypeareused,itisdesirabletoselectonewhich
hasaminimalcorrosiveeffectandacertainsolubilityinthereactionmixture.Boththe
corrosionbehaviorandthesolubilityoftheinorganicoxidizingagentmaybefavorably
influencedbyformationofacomplexoftheoxidizingagentwiththemixtureofstarting
materialscontainingaminogroupsand/orwiththeorganicconstituentsofthecatalystsystem.

Wherealargelyionicinorganicoxidizingagentisused,theoxycarbonylationreactiontakes
placeinaccordancewiththefollowinggeneralequation:##EQU1##Inthisequation,M.sup.n+
isametalhavingan"n.sup.+"oxidationstate.Intheoxycarbonylationreaction,thismetaltakes
up"a"electrons.Wheretheselargelyionicinorganicoxidizingagentsaretheonlyoxidizing
agentsused,theyaregenerallyemployedinquantitiessuchthatfrom2/ato10/agram
equivalents(preferablyfrom2/ato3/agramequivalents)ofoxidizinginorganiccompoundare
availableinthereactionmixtureforeachmolofprimaryaminogroups.

Otheroxidizingagentssuitabletothepracticeofthepresentinventionarequinoidorganic
compoundswhich,byvirtueoftheiroxidationpotential,arecapableofoxidizingtheamine
underthereactionconditions.Quinoidorganiccompoundsofthistypeincludequinones,such
asobenzoquinone,pbenzoquinone,naphthoquinones,andanthraquinonesinsubstitutedor
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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

unsubstitutedform.Suitablesubstituentsareelectronattractinggroupswhichincreasethe
oxidationpotentialofthequinoidcompound,suchascarboxylicacid,sulfonicacid,cyano
groupsandhalogensubstituentseitherindividuallyorincombinationwithoneanother.Where
thesequinoidoxidizingagentsareexclusivelyused,theyshouldgenerallybeemployedin
quantitiessuchthatatleastonemolofquinoidstructuralunits(i.e.wherepbenzoquinoneis
used,atleastonemolofthisquinone)isavailableforeverymolofprimaryaminogroups.In
additiontothesequinones,thequinoidcompoundsdescribedhereinafterassuitableco
catalystsmayalsobeusedasthequinoidcompounds.

Wherequinoidoxidizingagentsareusedintheoxycarbonylationoftheprimaryaminesin
accordancewiththepresentinvention,thereactiontakesplaceasexemplyfiedwiththe
followingequation:##STR1##

Wherethesequinoidoxidizingagentsareusedintheprocessofthepresentinvention,they
shouldpreferablybeemployedinquantitiesrangingfromthestoichiometricquantity
correspondingtotheabovereactionequationtoapproximately5timesthestoichiometric
metricquantityandmostpreferablybetween1and1.5timesthestoichiometricquantity.
Whereseveraloftheabovedescribedoxidizingagentsaresimultaneouslyused,thequantityin
whicheachisusedmayofcoursebereducedaccordingly.Wheretheionicand/orquinoid
oxidizingagentsdescribedaboveareexclusivelyused,anyoxidationsensitivealcoholspresent
arelesslikelytobedestroyedbyoxidationthanwheremolecularoxygenisused.Accordingly,
theionicand/orquinoidoxidizingagentsshouldnotgenerallybeusedinsubstoichiometric
quantitiesbecausethiswouldonlyresultindecreasedyield.

Theprocessofthepresentinventioniscarriedoutinthepresenceofacatalystsystem.Sucha
catalystsystemcontains(i)atleastonenoblemetaland/oratleastonenoblemetalcompound
oftheEighthSecondaryGroupofthePeriodicSystemofElementsand(ii)atleastoneoxidizing
quinoidcompoundand/oratleastonecompoundwhichiscapableofbeingconvertedintoan
oxidizingquinoidcompoundunderthereactionconditions.

Catalystcomponent(i)maybeeitherafreenoblemetaloftheEighthSecondaryGroupofthe
PeriodicSystemoracompoundofoneofthesemetals.Thesenoblemetalsareparticularly
advantageouswhenusedintheformofcompoundssolubleinthereactionmixture,suchas
chlorides,bromides,iodides,chlorocomplexes,bromocomplexes,iodocomplexes,acetates,
acetylacetonatesandothersolublenoblemetalcompounds.Preferrednoblemetalsare
palladium,rutheniumandrhodium.Itisparticularlypreferredtousepalladium,particularlyin
theformofsolublepalladiumchlorideorpalladiumacetate.

Preferredconcentrationsforthecatalystcomponent(i)aregenerallyintherangefrom3to
1000ppmandmostpreferablyintherangefrom5to100ppm,expressedasnoblemetaland
basedonthereactionmixtureasawhole,includinganysolventused.Althoughhigher
concentrationsofnoblemetalmaybeused,suchexcessisuneconomicalanddoesnotfurther
increasetheyieldofurethane.

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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Catalystcomponent(ii)isanoxidizingquinoidcompoundand/oracompoundwhichiscapable
ofbeingconvertedintoanoxidizingquinoidcompoundunderthereactionconditions.Quinoid
compoundsarecompoundsofthetypedescribedforexamplein"TheChemistryoftheQuinoid
Compounds",PartIandII(London,Wiley1974,Editor:Patai)andfrequentlymanufacturedas
dyesordyeprecursors.Inprinciple,catalystcomponent(ii)maybeanyquinoidcompoundof
thetypecapableofoxidizingthenoblemetalpresentincatalystcomponent(i)fromthezero
oxidationstatetoapositiveoxidationstateunderthereactionconditions.Thosequinoids
whicharecapableofconvertingpalladium,fromtheoxidationstagezerototheoxidationstage
+2areparticularlypreferred.

Inadditiontotheabovedescribedquinoidcompounds,compoundscapableofbeingconverted
intosuchquinoidcompounds,i.e.compoundswhichmaybeconvertedintoaquinoid
compoundbyanoxidationreaction(e.g.bytheoxidizingagentusedintheprocessofthe
presentinvention)bysolvolysisorbyaneliminationreaction,mayalsobeusedascatalyst
component(ii).

Suitablequinoidcatalystcomponents(ii)areorthoandparaquinones,polynuclearquinones
andheterocyclicquinonesinsubstitutedandunsubstitutedformandalsotheirimino,Nalkyl
orNaryliminoderivatives.Specificexamplesofsuchcompoundsare:o
tetrachlorobenzoquinone,ptetrachlorobenzoquinone,2,5dichloro3,6dihydroxyp
benzoquinone,2chlorophenyl1,4benzoquinone,2,3dichloronaphthoquinone,
anthraquinone,1chloroanthraquinone,7chloro4hydroxy1,10anthraquinone,1
nitroanthraquinone2carboxylicacid,1,5dichloroanthraquinone,1,8dichloroanthraquinone,
2,6dichloroanthraquinone,1,4dihydroxyanthraquinone,acenaphthylenedione,5,7dichloro
1Hindol2,3dione,indigoor1,4dihydro2,3quinoxalinedione.

PolymericquinoidcompoundsofthetypedescribedforexamplebyH.G.CassidyandK.A.Kun
in"OxidationReductionPolymers"(PolymerReviewsVol.11,IntersciencePubl.NewYork
1965),arealsosuitableforuseascatalystcomponent(ii).

Preferredquinoidcompoundsarethosesubstitutedbyoneormoreelectronattracting
substituents,suchaschlorine,bromine,cyano,nitro,carboxylicacidorsulfonicacidgroups.
Suchsubstituentsincreasetheoxidationpotentialofthequinoidcompound.Quinoid
compoundswhichareparticularlypreferredascatalystcomponent(ii)areo
tetrachlorobenzoquinone,ptetrachlorobenzoquinone,2,5dichloro3,6dihydroxyp
benzoquinone,2,3dichloronaphthoquinone,7chloro4hydroxy1,10anthraquinone,1,5
dichloroanthraquinoneand1,8dichloroanthraquinone.

Compoundswhicharereadilyconvertedtoquinoidcompoundssuitableforuseascatalyst
component(ii)are,forexample,ketalsofthecorrespondingquinoidandalsohydrogenated
formsofthosecomponents,particularlythecorrespondinghydroquinones.Aromaticamines
andpolynucleararomaticcompoundswhicharesubstitutedbysulfonicacid,carboxylicacid,
nitroorcyanogroupsorwhichalreadycontainanoxygroupintheringsystemmaybe
convertedintoquinoidcatalystcomponent(ii)underthereactionconditions(e.g.bymolecular
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PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

oxygen).Compoundswhicharereadilyconvertedtoaquinoidwhichmaybeusedascatalyst
component(ii)inthepresentinventionarethehydroquinonesandketalsoftheabove
mentionedquinones,4amino2(phenylamino)benzenesulfonicacid,5amino2((4
chlorophenyl)amino)benzenesulfonicacid,4,4'diamino(1,1'biphenyl)3,3'disulfonicacid,2
aminobenzenesulfonicacidandbenzanthrone3carbonitrile.

Thecatalystcomponent(ii)shouldgenerallybeaddedtothereactionsystemin.aconcentration
from0.1wt.%to5wt.%andpreferablyinconcentrationsoffrom0.5to3wt.%(basedonthe
totalquantityofreactionmixtureincludinganysolventused).

Thequinoidcompoundsarecapableofperformingthedualfunctionofoxidizingagentand
catalystcomponent(ii).Whenusedinthisdualcapacity,itisnecessarytouselargerquantities
ofthequinoidcompoundthanspecifiedaboveforquinoidsusedonlyasanoxidizingagent.

Thecatalystcomponentofthepresentinventionmayoptionallycontaincertainmetal
compounds(iii)and/ortertiaryamines(iv)asfurthercomponents.

Theoptionalcatalystcomponent(iii)maybeamagnesiumcompound,particularlyaninorganic
oranorganicsaltofmagnesium,oracompoundofanelementoftheThirdtoFifthMainGroup
and/orFirsttoEighthSecondaryGroupofthePeriodicSystemofElementswhichiscapableof
undergoingaredoxreactionunderthereactionconditions.Compoundsofmetalswiththe
atomicnumbers12,22to29,41,47,58and92whichareatleastpartlysolubleinthereaction
mixturearepreferablyusedastheoptionalcatalystcomponent(iii).Themostpreferredcatalyst
components(iii)aretheacetates,nitratesandchloridesofchromium,manganese,cobalt,
copper,ceriumormagnesium,whichmaybeintheformofthehydratesoraminecomplexes
ofthesemetalsalts.Inconjunctionwithactivatingchlorides,(e.g.ammoniumchlorides)itisalso
possibletousetheoxidesofthesemetalsascatalystcomponent(iii).Ifcatalystcomponent(iii)
isused,itshouldgenerallybeemployedinanamountwhichisfromonetotentimesthe
requiredmolarquantity(basedoncatalystcomponent(i)).Ingeneral,thismeansthatcatalyst
component(iii)maybeusedinquantitiesofupto0.1wt.%(basedonthetotalweightofthe
reactionmixtureincludinganysolventused).

Theoptionalcatalystcomponent(iv)maybeanytertiaryaminewhich,inthecatalystsystem,
performsthefunctionofacomplexingagentfortheoxidizedformofcatalystcomponent(i).It
isparticularlyadvantageoustouseatertiaryaminewhichisalsocapableofformingacomplex
withcomponent(iii)incasethecomplexingeffectofthestartingcompoundspresentinthe
reactionmixtureisinadequateforthispurpose.Inprinciple,anytertiaryamines,i.e.tertiary
aminesofthetypecontainingaliphatically,cycloaliphatically,araliphaticallyand/oraromatically
boundtertiaryaminogroupsortertiaryaminogroupsformingpartofaheterocyclicringmay
beusedinthepracticeofthepresentinvention.Suitabletertiaryaminesare,forexample,
triethylamine,diisopropylmethylamine,cyclohexyldiethylamine,triphenylamine,N,Ndiethyl
aniline,Nphenylpiperidine,pyridine,quinoline,1,4diaza(2,2,2)bicyclooctaneandpyrimidine.
Preferredtertiaryamines(iv)aretriethylamine,N,Ndiethylanilineandpyridine.Theabove
mentionedtertiaryaminesmayalsobeusedintheformofmetalsaltcomplexesofcatalyst
234

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

component(i)andoptionally(iii).Ifcatalystcomponent(i)and/oroptionally(iii)isusedin
theoxideform,itisadvantageoustousethetertiaryaminesintheformofhydrochloridesfor
thepurposeofactivatingthis(these)component(s).Theoptionalcatalystcomponent(iv)
shouldbeusedinquantitiesofupto10wt.%,preferablyfrom0.5to6wt.%(basedonthetotal
quantityofreactionmixtureincludinganysolventused).However,catalystcomponent(iv)may
beusedinlargerquantities.

Theprocessofthepresentinventionmaybecarriedoutinthepresenceorabsenceofa
solvent.Ingeneral,thereactantorganichydroxylcompoundpreferablyusedinexcessservesas
solvent.However,itisalsopossibletouseinertsolventswhichmaymakeupasmuchas80wt.
%ofthetotalreactionmixture.Thequantityofsolventused,whetherthehydroxylcompound
usedinexcessoraninertsolvent,shouldbesuchthattheheatofreactionoftheexothermic
urethaneformingreactionmaybedissipatedwithoutanyunacceptableincreasein
temperature.Ingeneral,therefore,theprocessaccordingtotheinventioniscarriedoutusinga
concentrationofaminocompoundsoffrom5to50wt.%andpreferablyfrom5to20wt.%
(basedonthetotalreactionmixtureincludingthesolvent).

Suitablesolventsaresolventswhichareinertbothtothereactioncomponentsandtothe
catalystsystem.Suchsolventsincludearomatic,cycloaliphaticandaliphatichydrocarbons
whichmayoptionallybehalogensubstituted,suchasbenzene,toluene,xylene,chlorobenzene,
dichlorobenzene,trichlorobenzene,chloronaphthalene,cyclohexane,methylcyclohexane,
chlorocyclohexane,methylenechloride,carbontetrachloride,tetrachloroethane,
trichlorotrifluoroethaneandsimilarcompoundsaswellastertiaryaminesofthetypedescribed
ascatalystcomponent(iv).

Thereactiontemperatureshouldgenerallybeintherangefrom100toabout300.degree.C.,
preferablyintherangefrom100to250.degree.C.andmostpreferablyintherangefrom140
to220.degree.C.Thepressureshouldbesuchthatthepresenceofaliquidphaseisguaranteed.
Thispressureisgenerallyintherangefrom5to500barsandpreferablyintherangefrom30to
300bars.

Dependingupontheprimaryamineandhydroxycompoundused,thereactiontimerequired
foraquantitativereactionrangesfromafewminutestoseveralhours.

Theprocessaccordingtotheinventionmaybecarriedoutcontinuouslyorinbatches.Itis
advantageoustouseasolventinwhichtheendproduct(urethane)ishighlysoluble.Afterthe
reactionmediumhasbeenrelievedofpressureandcooledtobetween50.degree.and
80.degree.C.,catalystcomponents(i),(ii),(iii)and,incomplexedform(iv)(ifithasbeenused)
aresubstantiallyorcompletelyprecipitatedinnumeroussolvents.Insomecases,itis
advantageoustoconcentratethereactionmixturetobetween70and50%ofitsoriginalvolume
toprecipitatethecatalystmixture.Thecatalystmixturemaythenbeseparatedofffromthe
urethanecontainingsolutionbyfiltrationorcentrifugation.Thethusrecovered
catalystcomponents(i),(ii),(iii)and,optionally,(iv)mayberecycledinmostcaseseventhough
theymaybechemicallymodified.Theurethanemaybeseparatedfromthefiltrateby
235

PhosgeneFreeRoutetoTolueneDiisocyanate

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techniquesknowntothoseintheartsuchasevaporatingthesolvent.Theproducturethane
maybepurifiedforexamplebyvacuumdistillationorbycrystallization.Theproducturethane
maybesimilarlytreatedwheresaltlikeinorganicoxidizingagentsorquinonelikeoxidizing
agentsareused.Theoxidizingagentobtainedinreducedformafterthereactionhasbeen
completedcontainssubstantialamountsofcatalystcomponents(i),(ii)and(iii).Thisoxidizing
agentmaybereoxidizedandrecycledalongwiththesecatalystcomponentstothereaction
chamber.

Theendproducts(urethanes)ofthepresentinventionaresuitableforuseaspesticidesoras
intermediateproductsintheproductionofpesticides.However,theseurethanesareofprimary
interestasstartingmaterialsforproducingtheisocyanatesonwhichtheyarebased.Production
ofsuchisocyanatesiscarriedoutinknownmannerbythermaldissociationoftheurethanesof
thepresentinvention.

TheprocessaccordingtotheinventionisillustratedbythefollowingExamplesalthoughthis
inventionisinnowaylimitedtotheconditionsdisclosedintheseExamples.Theurethane
yieldsarebasedineachcaseontheamineusedandaregivenintermsofmolpercent.

EXAMPLES

EXAMPLE1

(ComparisonExample:Nocatalystcomponent(ii))

474gofamixturehavingthefollowingcompositionwereintroducedintoanenamelled1.3
literfinesteelautoclave:42ppmofpalladiumacetate,211ppmofcopper(II)acetate
monohydrate,91.4wt.%ethanoland8.6wt.%aniline.100barsofcarbonmonoxideand25
barsofairwerethenintroducedintotheautoclaveatroomtemperature.Thecontentsofthe
autoclavewerethenheatedwithstirringto180.degree.C.andlefttoreactfor1houratthat
temperature.Aftercoolingtoroomtemperature,theautoclavewasventedandasecondsimilar
reactionphasewascarriedoutwithafreshCO/airmixture.Atotalofapproximately1.4
oxidationequivalents(basedonaniline)wereintroducedintheformofatmosphericoxygen.
Analysisoftheliquidreactionmixturebygaschromatographyshowedthattheyieldofphenyl
urethanewas4.5mol%,basedontheanilineused.

EXAMPLES2TO9

TheseExamplesdemonstratethecatalyticactivityofcatalystcomponent(ii).InExamples2to
6,catalystcomponent(ii)wasaquinoidcompoundandinExamples7to9,itwasthe
preliminarystateofaquinoidcompound.Theprocedurewasthesameasthatdescribedin
Example1,withtheexceptionthat483gofamixtureofthefollowingcompositionwasused:
41ppmofpalladiumacetate,207ppmofcopper(II)acetatemonohydrate,1.8wt.%catalyst
component(ii),89.8wt.%ethanoland8.4wt.%aniline.TheresultsaresetoutinTable1.

236

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BouSaba,Dizon,Kasih,Stewart

TABLE1______________________________________YieldofphenylurethaneinExampleNo.
Catalystcomponent(ii)mol%______________________________________2ortho
tetrachlorobenzoquinone46.03paratetrachlorobenzoquinone64.042,5dichloro3,6
dihydroxy47.5parabenzoquinone52,3dichloronaphthoquinone52.561,5
dichloroanthraquinone40.97benzanthrone3carbonitrile27.185amino2(phenylamino)
29.0benzenesulfonicacid94,4'diamino(1,1'biphenyl)32.03,3'disulfonicacid
______________________________________

EXAMPLE10

TheprocedurewasthesameasthatdescribedinExample1withtheexceptionthat487gofa
mixtureofthefollowingcompositionwereused:41ppmofpalladiumacetate,206ppmof
copper(II)acetatemonohydrate,1.7wt.%ptetrachlorobenzoquinone,0.8wt.%N,N
diethylaniline,89.0wt.%ethanoland8.4wt.%aniline.Yieldofphenylurethane:72.6mol%.

EXAMPLE11

TheprocedurewasthesameasthatdescribedinExample1withtheexceptionthat483gofa
mixtureofthefollowingcompositionwereused:41ppmofpalladiumacetate,207ppmof
copper(II)acetatemonohydrate,1.8wt.%ptetrachlorobenzoquinone,48.3wt.%ethanol,8.4
wt.%anilineand41.5wt.%orthodichlorobenzene.Yieldofphenylurethane:71.8mol%.

EXAMPLES12TO17

TheseExamplesdemonstratethecatalyticactivityofvariousnoblemetalswhichmaybeused
ascatalystcomponent(i).TheprocedurewasthesameasthatdescribedinExample1,except
that483gofareactionmixturehavingthefollowingcompositionwereused:104ppmof
catalystcomponent(i),207ppmofcopper(II)acetatemonohydrate,1.8wt.%p
tetrachlorobenzoquinone,89.8wt.%ethanoland8.4wt.%aniline.Theresultsobtainedareset
outinTable2.Example12isaComparisonExampleinwhichnocatalystcomponent(i)was
used.

TABLE2______________________________________YieldofphenylExampleNo.Catalyst
component(i)urethaneinmole%______________________________________121.013
RuCl.sub.355.614RhCl.sub.338.915PdCl.sub.257.216IrCl.sub.35.517PtCl.sub.24.4
______________________________________

EXAMPLE18

ThisExampledemonstratesthatcatalystcomponents(i)and(ii)catalyzetheurethaneforming
reactionevenintheabsenceofcatalystcomponents(iii)and(iv).Theprocedurewasthesame
asthatdescribedinExample1,exceptthat482gofareactionmixtureofthefollowing
compositionwereused:44ppmofpalladiumchloride,1.8wt.%ptetrachlorobenzoquinone,
89.8wt.%ethanoland8.4wt.%aniline.Yieldofphenylurethane:54.6mol%.
237

PhosgeneFreeRoutetoTolueneDiisocyanate

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EXAMPLES19TO23

TheprocedurewasthesameasthatdescribedinExample1,exceptthata0.7literfinesteel
autoclavefilledwith223gofreactionmixtureofthefollowingcompositionwereused:22ppm
ofpalladiumchloride,1.8wt.%ptetrachlorobenzoquinone,90ppmofcatalystcomponent(iii),
89.8wt.%ethanoland8.4wt.%aniline.TheresultsareshowninTable3.

TABLE3______________________________________YieldofpolyExampleNo.Catalyst
component(iii)urethaneinmol%______________________________________19
Cr(NO.sub.3).sub.3.9H.sub.2O59.420Mn(OAc).sub.2.H.sub.2O60.221Co(OAc).sub.2.H.sub.2
O65.322Cu(OAc).sub.2.H.sub.2O62.123Mg(NO.sub.3).sub.2.6H.sub.2O60.7
______________________________________

EXAMPLE24

ThisExampledemonstratesthecatalyticactivityofarecycledcatalyst.Thesolidprecipitated
wasfilteredofffromtheproductmixtureofExample3,anddriedat50.degree.C.111gofa
mixtureofthefollowingcompositionwerethenreactedunderthesameconditionsasdescribed
inExample3ina0.3literfinesteelautoclaveusing1.8wt.%recoveredcatalystmixture,8.4
wt.%anilineand89.8wt.%ethanol.Yieldofphenylurethane:62.4mol%.

EXAMPLES25TO29

111.4gofamixtureofthefollowingcompositionwereintroducedintoa0.3literfinesteel
autoclave:90ppmofpalladiumacetate,450ppmofcopperacetatemonohydrate,1.8wt.%
tetrachloropbenzoquinone,8.4wt.%anilineand89.8wt.%hydroxycomponent(seeTable4).
100barsofcarbonmonoxideand25barsofairwereintroducedatroomtemperature.
Accordingly,approximately0.7oxidationequivalentsbasedonanilinewereintroducedinthe
formofatmosphericoxygen.Thecontentsoftheautoclavewerelefttoreactfor1hourat
180.degree.C.Aftercooling,theurethaneyieldsgiveninTable4wereobtainedaccordingto
analysisbygaschromatography.

TABLE4______________________________________YieldofNphenylHydroxycomponent
urethaneinmol%______________________________________ethanol581propanol642
propanol62cyclohexanol34benzylalcohol20______________________________________

EXAMPLE30

129.4gofamixtureofthefollowingcompositionwereintroducedintoa0.3literfinesteel
autoclave:31ppmofpalladiumacetate,232ppmofcopperacetatemonohydrate,1.5wt.%
tetrachloropbenzoquinone,5.4wt.%pyridine,8.5wt.%(0.1mol)pbenzoquinone,7.3wt.%
(0.1mol)anilineand77.3wt.%ethanol.120barsofCOwereintroducedatroomtemperature.
Afterareactiontimeof2hoursat180.degree.C.,theyieldofphenylurethaneamountedto34
238

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

mol%accordingtoanalysisbygaschromatography.

EXAMPLE31

TheprocedurewasthesameasthatdescribedinExample30withtheexceptionthat127.8gof
astartingmixtureofthefollowingcompositionwereused:31ppmofpalladiumacetate,1.6wt.
%tetrachloropbenzoquinone,5.5wt.%(0.05mol)copper(II)chloride,3.4wt.%(0.05mol)
copper(II)oxide,3.9wt.%pyridine,7.4wt.%(0.1mol)anilineand78.2wt.%ethanol.Yieldof
phenylurethane:40mol%.

EXAMPLE32

216.7gofamixtureofthefollowingcompositionwereintroducedintoa0.7literfinesteel
autoclave:50ppmofpalladiumacetate,250ppmofcopperacetatemonohydrate,2.2wt.%
2,3dichloronaphtoquinone,5.5wt.%tert.butylamineand92.3wt.%ethanol.100barsofCO
and25barsofairwereintroducedatroomtemperature.Accordingly,approximately1.2
oxidationequivalentsbasedontert.butylaminewereintroducedintheformofatmospheric
oxygen.Thecontentsoftheautoclavewerelefttoreactwithstirringfor1hourat180.degree.
C.Aftercooling,analysisbygaschromatographyshowedayieldofNtert.butylOethyl
urethaneof32mol%.
*****

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Appendix8:Aspen
SimulationReport

240

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BouSaba,Dizon,Kasih,Stewart

ASPEN PLUS
1

PLAT: WIN32

VER: 23.0

04/07/2010

PAGE

RUN CONTROL SECTION

RUN CONTROL INFORMATION
----------------------THIS COPY OF ASPEN PLUS LICENSED TO UNIV OF PENNSYLVANIA
TYPE OF RUN: NEW
INPUT FILE NAME: _4017bcc.inm
OUTPUT PROBLEM DATA FILE NAME: _4017bcc
LOCATED IN:
PDF SIZE USED FOR INPUT TRANSLATION:
NUMBER OF FILE RECORDS (PSIZE) =
0
NUMBER OF IN-CORE RECORDS
=
256
PSIZE NEEDED FOR SIMULATION
=
256
CALLING PROGRAM NAME:
LOCATED IN:

apmain
C:\PROGRA~1\ASPENT~1\ASPENP~2.1\Engine\xeq

SIMULATION REQUESTED FOR ENTIRE FLOWSHEET

DESCRIPTION
----------GENERAL SIMULATION WITH ENGLISH UNITS : F, PSI, LB/HR, LBMOL/HR,
BTU/HR, CUFT/HR. PROPERTY METHOD: NONE FLOW BASIS FOR INPUT: MOLE
STREAM REPORT COMPOSITION: MOLE FLOW

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2

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VER: 23.0

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PAGE

FLOWSHEET SECTION
FLOWSHEET CONNECTIVITY BY STREAMS
--------------------------------STREAM
PSEUDO
CO
TDA
S-100
S-125
S-102
S-104
S-128
S-106
S-112
S-113
S-118
S-108
TDI
PSEUDLIQ
S-110
WASTEWTR
S-122
S-120
S-119
S-130
S-132

SOURCE
---------R-100
R-103
C-100
R-101
F-100
D-100
D-101
D-102
P-104
SP-101
C-102
H-102
P-101
P-103
H-101
SP-100
SP-102
M-103
H-103

DEST
R-100
R-100
R-100
R-101
M-101
F-100
V-100
M-101
P-100
D-102
P-102
SP-102
C-101
------H-100
---R-102
M-102
M-100
H-104
R-102

STREAM
SOLVENT
O2
O2MAKEUP
S-124
S-123
S-101
S-103
S-109
S-117
S-115
S-107
S-111
S-116
S-129
S-105
S-114
S-121
SLUDGE
S-127
S-126
PSEUDVAP
S-131

SOURCE
---------R-103
R-102
R-101
F-100
D-100
D-101
D-102
P-100
H-100
SP-101
M-101
V-100
P-102
M-100
C-101
SP-100
SP-102
H-104
M-102

DEST
R-100
R-100
M-102
M-103
R-103
C-100
SP-100
P-101
P-104
P-103
SP-101
D-101
M-100
H-102
D-100
C-102
H-101
---M-103
M-101
---H-103

FLOWSHEET CONNECTIVITY BY BLOCKS

-------------------------------BLOCK
R-100
R-103
R-102
C-100
R-101
F-100
D-100
D-101
D-102
P-100
P-104
H-100
SP-101
C-102
M-101
H-102
V-100
P-101

INLETS
TDA O2 CO SOLVENT PSEUDO
S-123
S-122 S-132
S-101
S-100
S-102
S-105
S-111
S-112
S-106
S-117
S-110
S-107
S-114
S-125 S-126 S-128
S-129
S-104
S-109

OUTLETS
S-100
S-124 S-125
S-123
S-102
S-101 S-104
S-103 S-128
S-109 S-106
S-117 S-112
S-115 S-113
S-107
S-118
S-111
S-108 S-116
TDI
S-129
PSEUDLIQ
S-105
S-110

242

PhosgeneFreeRoutetoTolueneDiisocyanate

P-102
P-103
M-100
H-101
C-101
SP-100
SP-102

S-113
S-115
S-116 S-119
S-121
S-108
S-103
S-118

BouSaba,Dizon,Kasih,Stewart
S-114
WASTEWTR
S-121
S-122
SLUDGE
S-120 S-127
S-119 S-126

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PAGE

FLOWSHEET SECTION
FLOWSHEET CONNECTIVITY BY BLOCKS (CONTINUED)
M-103
S-127 S-124
H-104
S-130
H-103
S-131
M-102
O2MAKEUP S-120

S-130
PSEUDVAP
S-132
S-131

COMPUTATIONAL SEQUENCE
---------------------SEQUENCE
R-100
D-101
H-101

USED WAS:
R-101 C-100 F-100 SP-100 M-102 H-103 V-100 D-100 P-101 H-100
P-104 SP-102 D-102 P-103 P-102 C-102 P-100 SP-101 C-101 M-100
R-102 R-103 M-103 H-104 M-101 H-102

OVERALL FLOWSHEET BALANCE

------------------------***

MASS AND ENERGY BALANCE

IN
OUT

***
GENERATION

DIFF.
CONVENTIONAL COMPONENTS
(LBMOL/HR)
TDA
236.476
8.02549
-228.451
0.252396E-14
O2
266.020
37.5695
-228.451
0.106840E-15
CO
4351.80
3894.90
-456.901
0.835970E-15
TDI
59.0700
287.044
227.974
0.117828E-13
WATER
92.2390
549.140
456.901
0.228765E-13
TDCARB
22.8930
23.3698
0.476769
0.264209E-13
SOLVENT
11153.8
11152.9
-0.953539
0.140679E-14
TOTAL BALANCE
MOLE(LBMOL/HR)
16182.3
15952.9
-229.404
0.00000
MASS(LB/HR
)
0.129565E+07 0.129565E+07
0.539106E-15
ENTHALPY(BTU/HR )
-0.461792E+10 -0.466978E+10
0.111067E-01

RELATIVE

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PAGE

PHYSICAL PROPERTIES SECTION

COMPONENTS
---------ID
TYPE
NAME
TDA
C
O2
C
CO
C
TDI
C
WATER
C
TDCARB
C
SOLVENT C
SOLVENT
LISTID
HC-1

FORMULA
C7H10N2
O2
CO
C9H6N2O2
H2O
C13H12F6N2O4
C2H3F3O

NAME OR ALIAS
C7H10N2
O2
CO
C9H6N2O2
H2O
MISSING
MISSING

REPORT
TDA
O2
CO
TDI
WATER
TDCARB

SUPERCRITICAL COMPONENT LIST

O2 CO

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VER: 23.0

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PAGE

PROPERTY CONSTANT ESTIMATION SECTION

PURE COMPONENT PARAMETERS
------------------------------------------------------------------------------------------------COMPONENT ID: TDCARB
FORMULA: C13H12F6N2O4
------------------------------------------------------------------------METHOD OF
PROPERTY NAME
ESTIMATION
----------------PARACHOR
PARACHOR

PARAMETER

ESTIMATED

NAME

VALUE

UNITS

-------

---------

-----

PARC

-----

650.00

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PhosgeneFreeRoutetoTolueneDiisocyanate

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6

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VER: 23.0

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PROPERTY CONSTANT ESTIMATION SECTION

PURE COMPONENT PARAMETERS (CONTINUED)
------------------------------------------------------------------------COMPONENT ID: SOLVENT
FORMULA: C2H3F3O
------------------------------------------------------------------------METHOD OF
PROPERTY NAME
ESTIMATION
----------------PARACHOR
PARACHOR

PARAMETER

ESTIMATED

NAME

VALUE

UNITS

-------

---------

-----

PARC

-----

157.10

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U-O-S BLOCK SECTION

BLOCK: C-100
MODEL: HEATER
-----------------------------INLET STREAM:
S-101
OUTLET STREAM:
S-102
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
01

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

5622.44
292971.
-0.889850E+09
INPUT DATA

***
OUT

RELATIVE

5622.44
292971.
-0.939393E+09

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

0.00000
0.00000
0.527395E-

100.000
5.00000
30

***
100.00
647.67
-0.49543E+08
0.52478
2556.5

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.40234E-07
O2
1.8915
CO
3.3737
TDI
0.28536E-05
WATER
0.49719E-03
TDCARB
0.91260E-10

F(I)
0.17052E-05

X(I)
0.35883E-05

Y(I)
0.14437E-12

0.55224E-02

0.37623E-02

0.71162E-02

0.65559

0.29194

0.98490

0.34859E-04

0.73354E-04

0.20932E-09

0.41174E-02

0.86594E-02

0.43053E-05

0.36533E-08

0.76875E-08

0.70156E-18

K(I)

248

PhosgeneFreeRoutetoTolueneDiisocyanate

SOLVENT
0.11474E-01

0.33473

BouSaba,Dizon,Kasih,Stewart
0.69556

0.79807E-02

249

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8

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VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK: C-101
MODEL: HEATER
-----------------------------INLET STREAM:
S-108
OUTLET STREAM:
SLUDGE
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
01

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

0.902484
230.488
-358388.

***
OUT

0.902484
230.488
-386244.

INPUT DATA

0.00000
0.00000
0.721215E-

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

RELATIVE

140.000
5.00000
30

***
140.00
648.00
-27856.
0.0000
0.58467E+11

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.19236E-05
TDI
0.15070E-04
TDCARB
0.15722E-08

F(I)
0.47145

X(I)
0.47145

Y(I)
0.99834

0.44676E-04

0.44676E-04

0.74118E-03

0.52850

0.52850

0.91469E-03

BLOCK: C-102
MODEL: HEATER
-----------------------------INLET STREAM:
S-114
OUTLET STREAM:
TDI
PROPERTY OPTION SET:
NRTL-RK

K(I)

RENON (NRTL) / REDLICH-KWONG

250

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VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

C-102

MODEL: HEATER (CONTINUED)

***

DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR

MASS AND ENERGY BALANCE

IN

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

227.981
39662.8
-0.842921E+07
INPUT DATA

***
OUT

RELATIVE

227.981
39662.8
-0.116233E+08

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

0.00000
0.00000
0.274799

***

140.000
5.00000
30

140.00
2.0077
-0.31941E+07
0.0000
0.15340E+07

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.40867E-03
TDI
0.28459E-02
WATER
1.4360

F(I)
0.36978E-04

X(I)
0.36978E-04

Y(I)
0.33406E-05

0.99879

0.99879

0.62835

0.11707E-02

0.11707E-02

0.37164

BLOCK: D-100
MODEL: RADFRAC
------------------------------INLETS
- S-105
STAGE 11
OUTLETS - S-109
STAGE
1
S-106
STAGE 20
PROPERTY OPTION SET:
NRTL-RK

K(I)

RENON (NRTL) / REDLICH-KWONG

251

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10

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

***

DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR
01

MASS AND ENERGY BALANCE

IN

***
OUT

RELATIVE

10279.4
0.100149E+07

10279.4
0.100149E+07

0.00000
0.348725E-

-0.373429E+10

-0.383866E+10

0.271883E-

**********************
**** INPUT DATA ****
**********************
****

INPUT PARAMETERS

****

NUMBER OF STAGES
ALGORITHM OPTION
ABSORBER OPTION
INITIALIZATION OPTION
HYDRAULIC PARAMETER CALCULATIONS
INSIDE LOOP CONVERGENCE METHOD
DESIGN SPECIFICATION METHOD
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS
MAXIMUM NO. OF INSIDE LOOP ITERATIONS
MAXIMUM NUMBER OF FLASH ITERATIONS
FLASH TOLERANCE
OUTSIDE LOOP CONVERGENCE TOLERANCE
****

COL-SPECS

****

MOLAR VAPOR DIST / TOTAL DIST

MOLAR REFLUX RATIO
MOLAR DISTILLATE RATE
****
P-SPEC

PROFILES

20
STANDARD
NO
STANDARD
NO
BROYDEN
NESTED
25
10
50
0.000100000
0.000100000

LBMOL/HR

0.0
2.40000
10,189.1

****
STAGE

PRES, PSIA

2.00000

252

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VER: 23.0

04/07/2010

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U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

*******************
**** RESULTS ****
*******************

***

COMPONENT SPLIT FRACTIONS

COMPONENT:
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT
***

S-109
.19811E-03
1.0000
1.0000
.99998
1.0000
.20432E-33
1.0000

OUTLET STREAMS
-------------S-106
.99980
.11312E-47
.46459E-50
.17685E-04
.27621E-25
1.0000
.84761E-23

SUMMARY OF KEY RESULTS

TOP STAGE TEMPERATURE

BOTTOM STAGE TEMPERATURE
TOP STAGE LIQUID FLOW
BOTTOM STAGE LIQUID FLOW
TOP STAGE VAPOR FLOW
BOILUP VAPOR FLOW
MOLAR REFLUX RATIO
MOLAR BOILUP RATIO
CONDENSER DUTY (W/O SUBCOOL)
REBOILER DUTY
****

***

***
F
F
LBMOL/HR
LBMOL/HR
LBMOL/HR
LBMOL/HR
BTU/HR
BTU/HR

MAXIMUM FINAL RELATIVE ERRORS

DEW POINT
BUBBLE POINT
COMPONENT MASS BALANCE
ENERGY BALANCE

34.9811
517.842
24,453.9
90.2484
0.0
21,097.0
2.40000
233.765
-0.729901+09
0.625534+09

****

0.21152E-03
0.59523E-04
0.28139E-05
0.54301E-04

STAGE= 8
STAGE= 8
STAGE= 10 COMP=WATER
STAGE= 7

253

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VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:
****

D-100

MODEL: RADFRAC (CONTINUED)

PROFILES

****

**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST
STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS
FLOW.
STAGE TEMPERATURE
F
1
2
3
9
10
11
12
19
20
STAGE

34.981
203.05
335.21
376.12
391.96
419.97
443.06
465.75
517.84

****
STAGE

2.0000
2.2000
2.3500
3.2500
3.4000
3.5500
3.7000
4.7500
4.9000

-0.37322E+06
-61491.
-39412.
-18220.
-5602.5
3498.2
10356.
9648.5
-0.39758E+06

FLOW RATE
LBMOL/HR
LIQUID
VAPOR

VAPOR
1 0.2445E+05
2 0.1450E+05
3 0.1875E+05
9 0.1744E+05
10 0.1796E+05
11 0.2246E+05
12 0.2327E+05
19 0.2119E+05
20 90.25

ENTHALPY
BTU/LBMOL
LIQUID
VAPOR

PRESSURE
PSIA

0.000
0.3464E+05
0.2469E+05
0.2836E+05
0.2763E+05
0.2259E+05
0.2237E+05
0.2345E+05
0.2110E+05

LIQUID

VAPOR
1 0.2348E+07 0.000
2 0.2465E+07 0.3327E+07
3 0.3258E+07 0.3443E+07
9 0.2675E+07 0.3967E+07

FEED RATE
LBMOL/HR
VAPOR

MIXED

-.72990+09

.62553+09
PRODUCT RATE
LBMOL/HR
LIQUID
.10189+05

4725.1792

MASS FLOW PROFILES

FLOW RATE
LB/HR
LIQUID
VAPOR

-0.18804E+06
-0.35215E+06
-0.16057E+06
-0.12681E+06
-0.12272E+06
-50888.
33082.
43760.
41041.

HEAT DUTY
BTU/HR

5554.1851

90.2484
****

LIQUID

FEED RATE
LB/HR
VAPOR

MIXED

PRODUCT RATE
LB/HR
LIQUID
.97844+06

254

PhosgeneFreeRoutetoTolueneDiisocyanate

10
11
12
19
20

0.2522E+07
0.2962E+07
0.2953E+07
0.2640E+07
0.2305E+05

0.3654E+07
0.2971E+07
0.2938E+07
0.2865E+07
0.2617E+07

.47185+06

BouSaba,Dizon,Kasih,Stewart
.52964+06

.23049+05

255

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13

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

STAGE
TDA
1
0.82744E-06
0.44843E-01
2
0.20251E-03
0.81070E-02
3
0.70825E-03
0.51475E-03
9
0.39399
0.22183E-03
10
0.64314
0.16185E-03
11
0.81898
0.10941E-03
12
0.91773
0.54369E-06
19
0.99012
0.27673E-22
20
0.47145
0.13984E-24
STAGE
1
2
3
9
10
11
12
19
20

TDCARB
0.95647E-36
0.46356E-30
0.97937E-27
0.87891E-08
0.54666E-05
0.21310E-02
0.20573E-02
0.96808E-02
0.52850

STAGE
TDA
1
0.35569E-12
0.12752E-02
2
0.82744E-06
0.44843E-01
3
0.11928E-03
0.23267E-01
9
0.11636
0.16291E-01
10
0.24870
0.16677E-01
11
0.51121
0.16872E-01

****
MOLE-X-PROFILE
****
O2
CO
TDI
0.39851E-03
0.27281E-01
0.22375E-01
0.11130E-06

0.40953E-05

0.95220

0.16526E-07

0.64174E-06

0.99517

0.11310E-06

0.50720E-05

0.60238

0.22856E-06

0.11308E-04

0.35335

0.84008E-08

0.30590E-06

0.17713

0.16742E-11

0.46061E-10

0.80203E-01

0.13218E-45

0.53595E-46

0.19654E-03

0.50897E-49

0.14310E-49

0.44676E-04

****
MOLE-X-PROFILE
SOLVENT
0.90510
0.39487E-01
0.36027E-02
0.33990E-02
0.33317E-02
0.16523E-02
0.14382E-04
0.91988E-19
0.86615E-21

****

****
MOLE-Y-PROFILE
O2
CO
0.57760E-02
0.57760

****
TDI
0.24389E-06

0.39851E-03

0.27281E-01

0.22375E-01

0.16452E-03

0.11260E-01

0.56849

0.14319E-03

0.98018E-02

0.53013

0.14703E-03

0.10064E-01

0.38849

0.96825E-05

0.45506E-03

0.29096

WATER

WATER

256

PhosgeneFreeRoutetoTolueneDiisocyanate

12
0.82038
0.10985E-03
19
0.99949
0.57158E-20
20
0.99234
0.27791E-22
STAGE
1
2
3
9
10
11
12
19
20

TDCARB
0.63606E-46
0.95647E-36
0.27227E-30
0.60109E-11
0.55479E-08
0.43452E-05
0.71683E-05
0.45189E-04
0.74614E-02

BouSaba,Dizon,Kasih,Stewart

0.84347E-08

0.30713E-06

0.17784

0.10011E-40

0.74306E-41

0.46593E-03

0.13275E-45

0.53824E-46

0.19719E-03

****
MOLE-Y-PROFILE
SOLVENT
0.41535
0.90510
0.39670
0.32727
0.33593
0.18050
0.16590E-02
0.91468E-17
0.92377E-19

****

257

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14

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

STAGE
TDA
1
0.42987E-06
0.28437E-01
2
0.40850E-02
3
0.16841
9
0.29534
10
0.38669
11
0.62420
12
0.89393
19
1.0095
20
2.1049
STAGE
1
2
3
9
10
11
12
19
20

TDCARB
0.66501E-10
0.20626E-05
0.27798E-03
0.68366E-03
0.10149E-02
0.20391E-02
0.34844E-02
0.46679E-02
0.14118E-01

STAGE
TDA
1
0.10527E-05
0.84127E-02
2
0.14557E-03
0.85934E-03
3
0.49792E-03
0.53365E-04
9
0.31380
0.26054E-04
10
0.55943
0.20760E-04
11
0.75875
0.14947E-04
12
0.88381
0.77210E-07
19
0.97065
0.40005E-23
20
0.22552
0.98643E-26

****
K-VALUES
O2
CO
14.494
21.172
3581.0
9955.7
1266.3
643.33
1152.5
5037.3
75734.
2608.1

6662.2
17548.
1932.9
890.03
1487.5
6666.8
0.13864E+06
3761.4

****
K-VALUES
SOLVENT
0.45890
22.923
110.11
96.289
100.83
109.24
115.35
99.435
106.65

****
TDI
0.10900E-04

WATER

0.23494E-01
0.57124
0.88004
1.0994
1.6426
2.2174
2.3706
4.4139

5.5314
45.201
73.436
103.04
154.20
202.05
206.54
198.73

****

****
MASS-X-PROFILE
****
O2
CO
TDI
0.13279E-03
0.79576E-02
0.40579E-01
0.20955E-07

0.67495E-06

0.97575

0.30431E-08

0.10344E-06

0.99737

0.23594E-07

0.92621E-06

0.68395

0.52073E-07

0.22552E-05

0.43816

0.20385E-08

0.64976E-07

0.23394

0.42229E-12

0.10170E-10

0.11011

0.33940E-46

0.12046E-46

0.27467E-03

0.63771E-50

0.15694E-50

0.30466E-04

****

MASS-X-PROFILE

WATER

****

258

PhosgeneFreeRoutetoTolueneDiisocyanate

STAGE
1
2
3
9
10
11
12
19
20

TDCARB
0.37275E-35
0.10208E-29
0.21092E-26
0.21444E-07
0.14566E-04
0.60476E-02
0.60691E-02
0.29072E-01
0.77445

BouSaba,Dizon,Kasih,Stewart

SOLVENT
0.94292
0.23243E-01
0.20741E-02
0.22168E-02
0.23731E-02
0.12535E-02
0.11342E-04
0.73844E-19
0.33928E-21

259

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VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

STAGE
TDA
1
0.75001E-12
0.39651E-03
2
0.10527E-05
0.84127E-02
3
0.10450E-03
0.30058E-02
9
0.10165
0.20985E-02
10
0.22977
0.22720E-02
11
0.47493
0.23113E-02
12
0.76293
0.15064E-04
19
0.99920
0.84260E-21
20
0.97722
0.40356E-23
STAGE
1
2
3
9
10
11
12
19
20

TDCARB
0.41085E-45
0.37275E-35
0.73068E-30
0.16084E-10
0.15701E-07
0.12366E-04
0.20421E-04
0.13839E-03
0.22508E-01

****
MASS-Y-PROFILE
O2
CO
0.31901E-02
0.27924

****
TDI
0.73310E-06

0.13279E-03

0.79576E-02

0.40579E-01

0.37751E-04

0.22618E-02

0.71000

0.32762E-04

0.19631E-02

0.66016

0.35580E-04

0.21318E-02

0.51165

0.23561E-05

0.96929E-04

0.38534

0.20545E-08

0.65486E-07

0.23577

0.26212E-41

0.17031E-41

0.66401E-03

0.34239E-46

0.12152E-46

0.27682E-03

****
MASS-Y-PROFILE
SOLVENT
0.71717
0.94292
0.28459
0.23410
0.25414
0.13731
0.12634E-02
0.74878E-17
0.74491E-19

WATER

****

********************************
***** HYDRAULIC PARAMETERS *****
********************************
*** DEFINITIONS ***
MARANGONI INDEX = SIGMA - SIGMATO
FLOW PARAM = (ML/MV)*SQRT(RHOV/RHOL)
QR = QV*SQRT(RHOV/(RHOL-RHOV))
F FACTOR = QV*SQRT(RHOV)

260

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

WHERE:
SIGMA IS THE SURFACE TENSION OF LIQUID FROM THE STAGE
SIGMATO IS THE SURFACE TENSION OF LIQUID TO THE STAGE
ML IS THE MASS FLOW OF LIQUID FROM THE STAGE
MV IS THE MASS FLOW OF VAPOR TO THE STAGE
RHOL IS THE MASS DENSITY OF LIQUID FROM THE STAGE
RHOV IS THE MASS DENSITY OF VAPOR TO THE STAGE
QV IS THE VOLUMETRIC FLOW RATE OF VAPOR TO THE STAGE

261

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BLOCK:

STAGE
1
2
3
9
10
11
12
19
20

D-100

MODEL: RADFRAC (CONTINUED)

TEMPERATURE
F
LIQUID FROM
VAPOR TO
34.981
203.05
203.05
335.21
335.21
345.58
376.12
391.96
391.96
384.96
419.97
443.06
443.06
449.36
465.75
517.84
517.84
517.84

MASS FLOW
VOLUME FLOW
MOLECULAR
LB/HR
CUFT/HR
STAGE LIQUID FROM VAPOR TO
LIQUID FROM VAPOR TO
LIQUID FROM
TO
1 0.33267E+07 0.33267E+07 33267.
0.11175E+09 96.028
2 0.24647E+07 0.34431E+07 34288.
0.89262E+08 169.96
3 0.32585E+07 0.42369E+07 49126.
0.99563E+08 173.77
9 0.26751E+07 0.36536E+07 42313.
0.73878E+08 153.39
10 0.25224E+07 0.35009E+07 40916.
0.74643E+08 140.45
11 0.29615E+07 0.29385E+07 49334.
0.58129E+08 131.87
12 0.29526E+07 0.29295E+07 50190.
0.58302E+08 126.86
19 0.26404E+07 0.26173E+07 45428.
0.44806E+08 124.62
20
23049.
0.26173E+07 280.41
0.44806E+08 255.39
DENSITY
LB/CUFT
STAGE LIQUID FROM VAPOR TO
1
100.00
0.29770E-01
2
71.881
0.38573E-01
3
66.330
0.42555E-01
9
63.221
0.49454E-01
10
61.649
0.46902E-01
11
60.029
0.50551E-01
12
58.828
0.50248E-01
19
58.122
0.58415E-01
20
82.197
0.58415E-01

STAGE
1

MARANGONI INDEX
DYNE/CM

WEIGHT
VAPOR
96.028
139.45
146.40
132.24
124.37
131.37
126.36
124.06
124.06

VISCOSITY
SURFACE TENSION
CP
DYNE/CM
LIQUID FROM VAPOR TO
LIQUID FROM
0.50678
0.14129E-01
33.667
0.88676
0.10909E-01
39.173
0.49269
0.10435E-01
29.385
0.47622
0.11349E-01
29.161
0.48495
0.11335E-01
29.871
0.46044
0.98089E-02
29.321
0.43608
0.99125E-02
28.563
0.41511
0.10703E-01
27.690
0.54784
0.10703E-01
25.155

FLOW PARAM
0.17254E-01

QR
CUFT/HR
0.19284E+07

REDUCED F-FACTOR
(LB-CUFT)**.5/HR
0.19281E+08

262

PhosgeneFreeRoutetoTolueneDiisocyanate

2
3
9
10
11
12
19

5.5061
-9.7881
0.66879
0.70969
1.4709
-.75841
-.15946

0.16582E-01
0.19480E-01
0.20478E-01
0.19873E-01
0.29247E-01
0.29456E-01
0.31981E-01

BouSaba,Dizon,Kasih,Stewart
0.20683E+07
0.25227E+07
0.20671E+07
0.20596E+07
0.16876E+07
0.17046E+07
0.14212E+07

0.17531E+08
0.20539E+08
0.16429E+08
0.16165E+08
0.13069E+08
0.13069E+08
0.10829E+08

263

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
17

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

STAGE
20

D-100

MODEL: RADFRAC (CONTINUED)

MARANGONI INDEX
DYNE/CM
-2.5344

FLOW PARAM
0.23476E-03

QR
CUFT/HR
0.11949E+07

REDUCED F-FACTOR
(LB-CUFT)**.5/HR
0.10829E+08

***************************************
***** PACKING SIZING CALCULATIONS *****
***************************************
*******************
*** SECTION
1 ***
*******************
STARTING STAGE NUMBER
ENDING STAGE NUMBER
CAPACITY CALCULATION METHOD
PRESSURE DROP CALCULATION METHOD
LIQUID HOLDUP CALCULATION METHOD
PRESSURE PROFILE UPDATED

2
19
KOCH
KOCH
STICHL
NO

DESIGN PARAMETERS
----------------OVERDESIGN FACTOR
SYSTEM FOAMING FACTOR
FRAC. APP. TO MAXIMUM CAPACITY
MAXIMUM CAPACITY FACTOR
DESIGN CAPACITY FACTOR
PRESSURE DROP FOR THE SECTION
PRESSURE DROP PER UNIT HEIGHT

1.00000
1.00000
0.85000
MISSING
MISSING
MISSING
MISSING

PACKING SPECIFICATIONS
---------------------PACKING TYPE
PACKING MATERIAL
PACKING SIZE
VENDOR
PACKING FACTOR
PACKING SURFACE AREA
PACKING VOID FRACTION
FIRST STICHLMAIR CONSTANT
SECOND STICHLMAIR CONSTANT
THIRD STICHLMAIR CONSTANT
HETP

FT/SEC
FT/SEC
PSI
IN-WATER/FT

1/FT
SQFT/CUF

FT

FLEXIPAC
METAL
500Y
KOCH
67.6917
152.402
0.92000
0.77242
-0.10883
0.11184
1.33333

264

PhosgeneFreeRoutetoTolueneDiisocyanate

PACKING HEIGHT

FT

BouSaba,Dizon,Kasih,Stewart
24.0000

265

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
18

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

***** SIZING RESULTS *****

COLUMN DIAMETER
MAXIMUM FRACTIONAL CAPACITY
MAXIMUM CAPACITY FACTOR
PRESSURE DROP FOR THE SECTION
AVERAGE PRESSURE DROP/HEIGHT
MAXIMUM LIQUID HOLDUP/STAGE
MAX LIQ SUPERFICIAL VELOCITY

FT
FT/SEC
PSI
IN-WATER/FT
CUFT
FT/SEC

63.1678
0.85000
0.22360
0.21255
0.24514
120.362
0.0044702

**** RATING PROFILES AT MAXIMUM COLUMN DIAMETER ****

STAGE
2
1.333
3
1.333
4
1.333
5
1.333
6
1.333
7
1.333
8
1.333
9
1.333
10
1.333
11
1.333
12
1.333
13
1.333
14
1.333
15
1.333

HEIGHT
FROM TOP
OF SECTION
FT
0.000

FRACTIONAL
CAPACITY
0.6882

PRESSURE
PRESSURE
DROP
DROP/HEIGHT
PSI
IN-WATER/FT
0.13284E-01 0.27577

LIQUID
HOLDUP
CUFT
93.02

1.333

0.8500

0.22235E-01 0.46160

118.3

2.667

0.8445

0.21721E-01 0.45092

120.3

4.000

0.8261

0.20084E-01 0.41693

120.4

5.333

0.8057

0.18442E-01 0.38285

119.8

6.667

0.7803

0.16607E-01 0.34477

118.0

8.000

0.7444

0.14404E-01 0.29904

113.7

9.333

0.7003

0.12160E-01 0.25244

107.0

10.67

0.6955

0.11712E-01 0.24315

104.7

12.00

0.5977

0.77623E-02 0.16115

118.5

13.33

0.6041

0.78112E-02 0.16216

119.9

14.67

0.5929

0.74349E-02 0.15435

119.2

16.00

0.5840

0.71532E-02 0.14850

119.0

17.33

0.5765

0.69199E-02 0.14366

119.0

HETP
FT

266

PhosgeneFreeRoutetoTolueneDiisocyanate

16
1.333
17
1.333
18
1.333
19
1.333

BouSaba,Dizon,Kasih,Stewart

18.67

0.5696

0.67136E-02 0.13937

119.2

20.00

0.5632

0.65250E-02 0.13546

119.4

21.33

0.5567

0.63391E-02 0.13160

119.5

22.67

0.5092

0.52436E-02 0.10886

112.2

LIQUID
SUPERFICIAL
STAGE VELOCITY
FT/SEC
2
0.3039E-02
3
0.4354E-02
4
0.4467E-02
5
0.4470E-02
6
0.4440E-02
7
0.4340E-02
8
0.4107E-02
9
0.3751E-02
10
0.3627E-02
11
0.4373E-02
12
0.4449E-02
13
0.4408E-02
14
0.4397E-02
15
0.4400E-02
16
0.4409E-02
17
0.4419E-02

267

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
19

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

LIQUID
SUPERFICIAL
STAGE VELOCITY
FT/SEC
18
0.4426E-02
19
0.4027E-02

************************************
***** TRAY SIZING CALCULATIONS *****
************************************
*******************
*** SECTION
1 ***
*******************
STARTING STAGE NUMBER
ENDING STAGE NUMBER
FLOODING CALCULATION METHOD

2
19
B960

DESIGN PARAMETERS
----------------PEAK CAPACITY FACTOR
SYSTEM FOAMING FACTOR
FLOODING FACTOR
MINIMUM COLUMN DIAMETER
MINIMUM DC AREA/COLUMN AREA

1.00000
1.00000
0.80000
1.00000
0.100000

TRAY SPECIFICATIONS
------------------TRAY TYPE
NUMBER OF PASSES
TRAY SPACING

FT

FT

FLEXI
1
2.00000

***** SIZING RESULTS @ STAGE WITH MAXIMUM DIAMETER *****

STAGE WITH MAXIMUM DIAMETER
COLUMN DIAMETER
DC AREA/COLUMN AREA
DOWNCOMER VELOCITY
WEIR LENGTH

FT
FT/SEC
FT

5
9.56522
0.50000
0.38990
9.56522

268

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
20

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-100

MODEL: RADFRAC (CONTINUED)

**** SIZING PROFILES ****

STAGE
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

DIAMETER
FT
7.8870
9.4405
9.5615
9.5652
9.5332
9.4254
9.1686
8.7615
8.6156
9.4605
9.5422
9.4982
9.4867
9.4899
9.4991
9.5105
9.5181
9.0782

TOTAL AREA
SQFT
48.855
69.997
71.803
71.859
71.379
69.774
66.023
60.291
58.299
70.294
71.513
70.855
70.684
70.731
70.868
71.039
71.152
64.728

BLOCK: D-101
MODEL: RADFRAC
------------------------------INLETS
- S-111
STAGE 11
OUTLETS - S-117
STAGE
1
S-112
STAGE 20
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR
01

ACTIVE AREA
SQFT
-0.13400E-03
-0.19199E-03
-0.19695E-03
-0.19710E-03
-0.19578E-03
-0.19138E-03
-0.18109E-03
-0.16537E-03
-0.15991E-03
-0.19281E-03
-0.19615E-03
-0.19435E-03
-0.19388E-03
-0.19401E-03
-0.19438E-03
-0.19485E-03
-0.19516E-03
-0.17754E-03

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
10189.1
978444.

SIDE DC AREA
SQFT
24.428
34.999
35.902
35.929
35.690
34.887
33.012
30.145
29.150
35.147
35.757
35.428
35.342
35.366
35.434
35.520
35.576
32.364

-0.362940E+10

***
OUT

10189.1
978444.
-0.379828E+10

RELATIVE
0.00000
0.356940E0.444638E-

269

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
21

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

MODEL: RADFRAC (CONTINUED)

**********************
**** INPUT DATA ****
**********************
****

INPUT PARAMETERS

****

NUMBER OF STAGES
ALGORITHM OPTION
ABSORBER OPTION
INITIALIZATION OPTION
HYDRAULIC PARAMETER CALCULATIONS
INSIDE LOOP CONVERGENCE METHOD
DESIGN SPECIFICATION METHOD
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS
MAXIMUM NO. OF INSIDE LOOP ITERATIONS
MAXIMUM NUMBER OF FLASH ITERATIONS
FLASH TOLERANCE
OUTSIDE LOOP CONVERGENCE TOLERANCE
****

COL-SPECS

****

MOLAR VAPOR DIST / TOTAL DIST

MOLAR REFLUX RATIO
MOLAR DISTILLATE RATE
****

PROFILES

P-SPEC

20
STANDARD
NO
STANDARD
NO
BROYDEN
NESTED
200
10
50
0.000100000
0.000100000

LBMOL/HR

0.0
1.05000
9,504.23

****
STAGE

PRES, PSIA

5.00000

*******************
**** RESULTS ****
*******************
***

COMPONENT SPLIT FRACTIONS

S-117
COMPONENT:
TDA
O2
CO
TDI

.64450E-43
1.0000
1.0000
.36535E-34

***

OUTLET STREAMS
-------------S-112
1.0000
.62951E-27
.13582E-29
1.0000

270

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
22

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:
***

D-101

COMPONENT SPLIT FRACTIONS

COMPONENT:
WATER
SOLVENT
***

MODEL: RADFRAC (CONTINUED)

S-117
.19749E-04
1.0000

OUTLET STREAMS
-------------S-112
.99998
.10598E-07

SUMMARY OF KEY RESULTS

TOP STAGE TEMPERATURE

BOTTOM STAGE TEMPERATURE
TOP STAGE LIQUID FLOW
BOTTOM STAGE LIQUID FLOW
TOP STAGE VAPOR FLOW
BOILUP VAPOR FLOW
MOLAR REFLUX RATIO
MOLAR BOILUP RATIO
CONDENSER DUTY (W/O SUBCOOL)
REBOILER DUTY
****

***

***
F
F
LBMOL/HR
LBMOL/HR
LBMOL/HR
LBMOL/HR
BTU/HR
BTU/HR

MAXIMUM FINAL RELATIVE ERRORS

DEW POINT
BUBBLE POINT
COMPONENT MASS BALANCE
ENERGY BALANCE

34.0916
200.714
9,979.44
684.886
0.0
10,114.0
1.05000
14.7674
-0.351769+09
0.182883+09

****

0.11939E-03
0.39567E-03
0.67691E-06
0.11162E-03

STAGE= 1
STAGE= 13
STAGE= 11 COMP=TDI
STAGE= 13

271

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
23

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:
****

D-101

MODEL: RADFRAC (CONTINUED)

PROFILES

****

**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST
STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS
FLOW.
STAGE TEMPERATURE
F
1
2
3
4
5
9
10
11
12
19
20
STAGE

34.092
93.227
94.954
96.030
97.085
101.66
103.76
108.02
115.57
181.88
200.71

****
STAGE
VAPOR

5.0000
5.1000
5.2500
5.4000
5.5500
6.1500
6.3000
6.4500
6.6000
7.6500
7.8000

-0.39271E+06
-0.40079E+06
-0.40073E+06
-0.40067E+06
-0.40059E+06
-0.39526E+06
-0.38563E+06
-0.36353E+06
-0.31741E+06
-0.11932E+06
-96220.

FLOW RATE
LBMOL/HR
LIQUID
VAPOR

VAPOR
1 9979.
2 0.1113E+05
3 0.1114E+05
4 0.1114E+05
5 0.1114E+05
9 0.1105E+05
10 0.1080E+05
11 0.1175E+05
12 0.1137E+05
19 0.1080E+05
20 684.9

ENTHALPY
BTU/LBMOL
LIQUID
VAPOR

PRESSURE
PSIA

0.000
0.1948E+05
0.2063E+05
0.2065E+05
0.2064E+05
0.2061E+05
0.2056E+05
0.1122E+05
0.1107E+05
0.1020E+05
0.1011E+05

LIQUID

FEED RATE
LBMOL/HR
VAPOR

MIXED

-.35177+09

.18288+09
PRODUCT RATE
LBMOL/HR
LIQUID
9504.2300

1108.8416

MASS FLOW PROFILES

FLOW RATE
LB/HR
LIQUID
VAPOR

-0.10538E+06
-0.37465E+06
-0.38002E+06
-0.38000E+06
-0.37997E+06
-0.37891E+06
-0.37697E+06
-0.37777E+06
-0.36355E+06
-0.10313E+06
-0.10281E+06

HEAT DUTY
BTU/HR

9080.2743

684.8860
****

LIQUID

FEED RATE
LB/HR
VAPOR

MIXED

PRODUCT RATE
LB/HR
LIQUID

272

PhosgeneFreeRoutetoTolueneDiisocyanate

1
2
3
4
5
9
10
11

0.9770E+06
0.1113E+07
0.1115E+07
0.1114E+07
0.1114E+07
0.1089E+07
0.1033E+07
0.1089E+07

0.000
0.1908E+07
0.2044E+07
0.2045E+07
0.2045E+07
0.2036E+07
0.2019E+07
0.1101E+07

BouSaba,Dizon,Kasih,Stewart
.93051+06

.86257+06
.11587+06

273

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
24

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:
****
STAGE

D-101

MODEL: RADFRAC (CONTINUED)

MASS FLOW PROFILES

FLOW RATE
LB/HR
LIQUID
VAPOR

VAPOR
12 0.9001E+06 0.1041E+07
19 0.2334E+06 0.1839E+06
20 0.4794E+05 0.1855E+06
STAGE
TDA
1
0.0000
0.94943E-06
2
0.0000
0.57336E-05
3
0.0000
0.20730E-04
4
0.0000
0.67837E-04
5
0.0000
0.21481E-03
9
0.12837E-13
0.18800E-01
10
0.24414E-09
0.53065E-01
11
0.71727E-06
12
0.74171E-06
19
0.81779E-06
20
0.12310E-04
STAGE
1
2
3
4
5
9
10
11
12
19
20
STAGE

SOLVENT
0.97032
0.99995
0.99996
0.99991
0.99976
0.98115
0.94673
0.87248
0.70737
0.10895E-05
0.14271E-06
TDA

****

LIQUID

FEED RATE
LB/HR
VAPOR

MIXED

PRODUCT RATE
LB/HR
LIQUID

.47936+05

****
MOLE-X-PROFILE
****
O2
CO
TDI
0.42723E-03
0.29247E-01
0.0000
0.12380E-05

0.43754E-04

0.0000

0.56583E-06

0.19954E-04

0.0000

0.56769E-06

0.20037E-04

0.0000

0.57364E-06

0.20259E-04

0.0000

0.12191E-05

0.46968E-04

0.22419E-07

0.32971E-05

0.13921E-03

0.62843E-04

0.24558E-06
0.31911E-07
0.0000
0.0000

0.68582E-05
0.58985E-06
0.0000
0.0000

0.19400E-01
0.20061E-01
0.23060E-01
0.33287

****

MOLE-X-PROFILE

****

****
O2

MOLE-Y-PROFILE
CO

****
TDI

WATER

0.10811
0.27257
0.97694
0.66712

WATER

274

PhosgeneFreeRoutetoTolueneDiisocyanate

1
0.0000
0.41853E-08
2
0.0000
0.94943E-06
3
0.0000
0.35298E-05
4
0.0000
0.11624E-04
5
0.0000
0.37043E-04
9
0.0000
0.34015E-02
10
0.69020E-14
0.10109E-01
11
0.23968E-10
0.23201E-01
12
0.41475E-10
0.73525E-01
19
0.82880E-08
20
0.39588E-07

BouSaba,Dizon,Kasih,Stewart

0.71858E-02

0.82158

0.0000

0.42723E-03

0.29247E-01

0.0000

0.19746E-03

0.13496E-01

0.0000

0.19697E-03

0.13474E-01

0.0000

0.19699E-03

0.13476E-01

0.0000

0.19742E-03

0.13502E-01

0.40542E-11

0.19818E-03

0.13547E-01

0.12054E-07

0.51089E-05

0.21737E-03

0.43295E-05

0.26077E-06

0.72825E-05

0.56554E-05

0.0000
0.0000

0.0000
0.0000

0.80086E-04
0.20806E-02

0.99991
0.99792

275

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
25

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:
STAGE
1
2
3
4
5
9
10
11
12
19
20

D-101

MODEL: RADFRAC (CONTINUED)

SOLVENT
0.17124
0.97032
0.98630
0.98632
0.98629
0.98290
0.97615
0.97657
0.92646
0.10788E-04
0.11536E-05

STAGE
TDA
1
0.15481E-06
0.44076E-02
2
0.19365E-04
3
0.20644E-04
4
0.21251E-04
5
0.21865E-04
9
0.25401E-04
10
0.28267E-04
11
0.33396E-04
12
0.55817E-04
19
0.10133E-01
20
0.32159E-02
STAGE
1
2
3
4
5
9
10
11
12
19
20

SOLVENT
0.17649
0.97044
0.98640
0.98641
0.98652
1.0018
1.0311
1.1194
1.3099
9.9009
8.0842

STAGE
TDA
1
0.0000
0.17470E-06

****

MOLE-Y-PROFILE

****
K-VALUES
O2
CO
16.820
28.091
345.12
349.01
346.97
343.41
162.07
60.210
20.879
8.1887
1143.3
1258.1
****

668.50
676.38
672.46
665.17
287.73
97.497
31.815
12.371
2133.7
2337.6

K-VALUES

****

****
TDI
0.20164E-05

WATER

0.14623E-03
0.15470E-03
0.15849E-03
0.16229E-03
0.18084E-03
0.19181E-03
0.22315E-03
0.28177E-03
0.34730E-02
0.62504E-02

0.16559
0.17027
0.17136
0.17244
0.18093
0.19049
0.21458
0.26971
1.0235
1.4959

****

****
MASS-X-PROFILE
****
O2
CO
TDI
0.13963E-03
0.83676E-02
0.0000

WATER

276

PhosgeneFreeRoutetoTolueneDiisocyanate

2
0.0000
0.10325E-05
3
0.0000
0.37332E-05
4
0.0000
0.12217E-04
5
0.0000
0.38691E-04
9
0.15922E-13
0.34386E-02
10
0.31173E-09
0.99912E-02
11
0.94621E-06
0.21031E-01
12
0.11446E-05
0.62024E-01
19
0.46220E-05

BouSaba,Dizon,Kasih,Stewart

0.39600E-06

0.12251E-04

0.0000

0.18099E-06

0.55872E-05

0.0000

0.18159E-06

0.56106E-05

0.0000

0.18352E-06

0.56734E-05

0.0000

0.39607E-06

0.13357E-04

0.39641E-07

0.11026E-05

0.40752E-04

0.11439E-03

0.84852E-07

0.20743E-05

0.36482E-01

0.12898E-07

0.20869E-06

0.44131E-01

0.0000

0.0000

0.18579

0.81420

277

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
26

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

MODEL: RADFRAC (CONTINUED)

STAGE
20

TDA
0.21487E-04

STAGE
1
2
3
4
5
9
10
11
12
19
20

SOLVENT
0.99149
0.99999
0.99999
0.99998
0.99996
0.99655
0.98985
0.94248
0.89384
0.50424E-05
0.20397E-06

STAGE
TDA
1
0.0000
0.18675E-08
2
0.0000
0.17470E-06
3
0.0000
0.64198E-06
4
0.0000
0.21142E-05
5
0.0000
0.67373E-05
9
0.0000
0.62039E-03
10
0.85848E-14
0.18541E-02
11
0.29842E-10
0.42597E-02
12
0.53899E-10
0.14090E-01
19
0.56163E-07
20
0.26370E-06
STAGE
1
2
3
4

SOLVENT
0.42430
0.99149
0.99612
0.99612

****
MASS-X-PROFILE
O2
CO
0.0000
0.0000

****
TDI
0.82827

****

****

MASS-X-PROFILE

****
MASS-Y-PROFILE
O2
CO
0.56953E-02
0.57000

****
TDI
0.0000

0.13963E-03

0.83676E-02

0.0000

0.63789E-04

0.38163E-02

0.0000

0.63630E-04

0.38101E-02

0.0000

0.63638E-04

0.38106E-02

0.0000

0.63954E-04

0.38287E-02

0.71484E-11

0.64562E-04

0.38633E-02

0.21373E-07

0.16661E-05

0.62051E-04

0.76846E-05

0.88761E-07

0.21698E-05

0.10477E-04

0.0000
0.0000
****

0.0000
0.0000

MASS-Y-PROFILE

0.77364E-03
0.19757E-01

WATER
0.17171

WATER

0.99917
0.98024

****

278

PhosgeneFreeRoutetoTolueneDiisocyanate

5
9
10
11
12
19
20

BouSaba,Dizon,Kasih,Stewart

0.99612
0.99549
0.99422
0.99567
0.98590
0.59861E-04
0.62928E-05

279

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ASPEN PLUS
27

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VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

MODEL: RADFRAC (CONTINUED)

********************************
***** HYDRAULIC PARAMETERS *****
********************************

*** DEFINITIONS ***

MARANGONI INDEX = SIGMA - SIGMATO
FLOW PARAM = (ML/MV)*SQRT(RHOV/RHOL)
QR = QV*SQRT(RHOV/(RHOL-RHOV))
F FACTOR = QV*SQRT(RHOV)
WHERE:
SIGMA IS THE SURFACE TENSION OF LIQUID FROM THE STAGE
SIGMATO IS THE SURFACE TENSION OF LIQUID TO THE STAGE
ML IS THE MASS FLOW OF LIQUID FROM THE STAGE
MV IS THE MASS FLOW OF VAPOR TO THE STAGE
RHOL IS THE MASS DENSITY OF LIQUID FROM THE STAGE
RHOV IS THE MASS DENSITY OF VAPOR TO THE STAGE
QV IS THE VOLUMETRIC FLOW RATE OF VAPOR TO THE STAGE

STAGE
1
2
3
4
5
9
10
11
12
19
20

TEMPERATURE
F
LIQUID FROM
VAPOR TO
34.092
93.227
93.227
94.954
94.954
96.030
96.030
97.085
97.085
98.125
101.66
103.76
103.76
112.01
108.02
115.57
115.57
132.82
181.88
200.71
200.71
200.71

MASS FLOW
VOLUME FLOW
MOLECULAR
LB/HR
CUFT/HR
STAGE LIQUID FROM VAPOR TO
LIQUID FROM VAPOR TO
LIQUID FROM
TO
1 0.19075E+07 0.19075E+07 18769.
0.22486E+08 97.905
2 0.11133E+07 0.20438E+07 11333.
0.23195E+08 100.04
3 0.11146E+07 0.20452E+07 11367.
0.22605E+08 100.04
4 0.11144E+07 0.20449E+07 11377.
0.22029E+08 100.03
5 0.11140E+07 0.20445E+07 11386.
0.21483E+08 100.02

WEIGHT
VAPOR
97.905
99.055
99.056
99.053
99.047

280

PhosgeneFreeRoutetoTolueneDiisocyanate

9
10
11
12
19
20

0.10887E+07
0.10329E+07
0.10886E+07
0.90011E+06
0.23343E+06
47936.

0.20192E+07
0.19634E+07
0.10407E+07
0.85217E+06
0.18549E+06
0.18549E+06

11217.
10735.
11536.
9958.3
3937.7
709.86

BouSaba,Dizon,Kasih,Stewart
0.19540E+08
0.19587E+08
0.10257E+08
0.99849E+07
0.91527E+07
0.91527E+07

98.495
95.682
92.610
79.170
21.616
69.992

98.222
96.723
94.009
79.758
18.340
18.340

281

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28

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

MODEL: RADFRAC (CONTINUED)

DENSITY
LB/CUFT
STAGE LIQUID FROM VAPOR TO
1
101.63
0.84833E-01
2
98.231
0.88113E-01
3
98.061
0.90474E-01
4
97.952
0.92828E-01
5
97.844
0.95171E-01
9
97.054
0.10333
10
96.224
0.10024
11
94.364
0.10146
12
90.388
0.85346E-01
19
59.280
0.20266E-01
20
67.530
0.20266E-01

STAGE
1
2
3
4
5
9
10
11
12
19
20

MARANGONI INDEX
DYNE/CM
-5.0068
-.17269
-.10634
-.99691E-01
0.42096
1.3220
1.8600
6.6010
-.14622
-7.9724

VISCOSITY
SURFACE TENSION
CP
DYNE/CM
LIQUID FROM VAPOR TO
LIQUID FROM
0.45531
0.12204E-01
31.145
0.39955
0.12176E-01
26.139
0.39731
0.12198E-01
25.966
0.39592
0.12219E-01
25.860
0.39459
0.12241E-01
25.760
0.39289
0.12369E-01
26.131
0.39758
0.12559E-01
27.453
0.41601
0.12639E-01
29.941
0.43662
0.13203E-01
36.542
0.34980
0.12341E-01
60.993
0.44089
0.12341E-01
53.020

FLOW PARAM
0.28891E-01
0.16314E-01
0.16555E-01
0.16776E-01
0.16994E-01
0.17593E-01
0.16980E-01
0.34301E-01
0.32457E-01
0.23268E-01
0.44769E-02

QR
CUFT/HR
0.64992E+06
0.69500E+06
0.68694E+06
0.67847E+06
0.67032E+06
0.63793E+06
0.63253E+06
0.33651E+06
0.30696E+06
0.16926E+06
0.15858E+06

REDUCED F-FACTOR
(LB-CUFT)**.5/HR
0.65492E+07
0.68852E+07
0.67993E+07
0.67117E+07
0.66273E+07
0.62813E+07
0.62015E+07
0.32671E+07
0.29170E+07
0.13030E+07
0.13030E+07

282

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ASPEN PLUS
29

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

MODEL: RADFRAC (CONTINUED)

***************************************
***** PACKING SIZING CALCULATIONS *****
***************************************

*******************
*** SECTION
1 ***
*******************
STARTING STAGE NUMBER
ENDING STAGE NUMBER
CAPACITY CALCULATION METHOD
PRESSURE DROP CALCULATION METHOD
LIQUID HOLDUP CALCULATION METHOD
PRESSURE PROFILE UPDATED

2
19
KOCH
KOCH
STICHL
NO

DESIGN PARAMETERS
----------------OVERDESIGN FACTOR
SYSTEM FOAMING FACTOR
FRAC. APP. TO MAXIMUM CAPACITY
MAXIMUM CAPACITY FACTOR
DESIGN CAPACITY FACTOR
PRESSURE DROP FOR THE SECTION
PRESSURE DROP PER UNIT HEIGHT

1.00000
1.00000
0.85000
MISSING
MISSING
MISSING
MISSING

PACKING SPECIFICATIONS
---------------------PACKING TYPE
PACKING MATERIAL
PACKING SIZE
VENDOR
PACKING FACTOR
PACKING SURFACE AREA
PACKING VOID FRACTION
FIRST STICHLMAIR CONSTANT
SECOND STICHLMAIR CONSTANT
THIRD STICHLMAIR CONSTANT
HETP
PACKING HEIGHT

FT/SEC
FT/SEC
PSI
IN-WATER/FT

1/FT
SQFT/CUF

FT
FT

FLEXIPAC
METAL
500Y
KOCH
67.6917
152.402
0.92000
0.77242
-0.10883
0.11184
1.33333
24.0000

***** SIZING RESULTS *****

COLUMN DIAMETER
MAXIMUM FRACTIONAL CAPACITY

FT

32.8152
0.85000

283

PhosgeneFreeRoutetoTolueneDiisocyanate

MAXIMUM CAPACITY FACTOR

PRESSURE DROP FOR THE SECTION
AVERAGE PRESSURE DROP/HEIGHT
MAXIMUM LIQUID HOLDUP/STAGE
MAX LIQ SUPERFICIAL VELOCITY

FT/SEC
PSI
IN-WATER/FT
CUFT
FT/SEC

BouSaba,Dizon,Kasih,Stewart
0.22827
0.30464
0.35134
29.0714
0.0037890

284

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ASPEN PLUS
30

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

MODEL: RADFRAC (CONTINUED)

**** RATING PROFILES AT MAXIMUM COLUMN DIAMETER ****

STAGE
2
1.333
3
1.333
4
1.333
5
1.333
6
1.333
7
1.333
8
1.333
9
1.333
10
1.333
11
1.333
12
1.333
13
1.333
14
1.333
15
1.333
16
1.333
17
1.333
18
1.333
19
1.333

STAGE

HEIGHT
FROM TOP
OF SECTION
FT
0.000

FRACTIONAL
CAPACITY
0.8500

PRESSURE
PRESSURE
DROP
DROP/HEIGHT
PSI
IN-WATER/FT
0.37981E-01 0.78849

LIQUID
HOLDUP
CUFT
28.75

1.333

0.8414

0.36240E-01 0.75235

28.81

2.667

0.8322

0.34495E-01 0.71612

28.83

4.000

0.8233

0.32928E-01 0.68359

28.84

5.333

0.8147

0.31499E-01 0.65391

28.85

6.667

0.8061

0.30151E-01 0.62592

28.84

8.000

0.7971

0.28776E-01 0.59738

28.77

9.333

0.7864

0.27146E-01 0.56356

28.55

10.67

0.7768

0.25440E-01 0.52814

27.72

12.00

0.4513

0.61637E-02 0.12796

29.07

13.33

0.4086

0.48550E-02 0.10079

26.36

14.67

0.3266

0.28247E-02 0.58641E-01

20.83

16.00

0.2429

0.13221E-02 0.27446E-01

15.45

17.33

0.2216

0.10182E-02 0.21137E-01

14.26

18.67

0.2177

0.96932E-03 0.20123E-01

14.14

20.00

0.2159

0.94935E-03 0.19708E-01

14.13

21.33

0.2143

0.93303E-03 0.19370E-01

14.14

22.67

0.2153

0.94252E-03 0.19567E-01

14.20

HETP
FT

LIQUID
SUPERFICIAL
VELOCITY

285

PhosgeneFreeRoutetoTolueneDiisocyanate

2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

BouSaba,Dizon,Kasih,Stewart

FT/SEC
0.3722E-02
0.3733E-02
0.3737E-02
0.3740E-02
0.3741E-02
0.3739E-02
0.3727E-02
0.3684E-02
0.3526E-02
0.3789E-02
0.3271E-02
0.2298E-02
0.1468E-02
0.1302E-02
0.1285E-02
0.1284E-02
0.1285E-02
0.1293E-02

286

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
31

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

MODEL: RADFRAC (CONTINUED)

************************************
***** TRAY SIZING CALCULATIONS *****
************************************

*******************
*** SECTION
1 ***
*******************
STARTING STAGE NUMBER
ENDING STAGE NUMBER
FLOODING CALCULATION METHOD

2
19
B960

DESIGN PARAMETERS
----------------PEAK CAPACITY FACTOR
SYSTEM FOAMING FACTOR
FLOODING FACTOR
MINIMUM COLUMN DIAMETER
MINIMUM DC AREA/COLUMN AREA

1.00000
1.00000
0.80000
1.00000
0.100000

TRAY SPECIFICATIONS
------------------TRAY TYPE
NUMBER OF PASSES
TRAY SPACING

FT

FLEXI
4
2.00000

FT

***** SIZING RESULTS @ STAGE WITH MAXIMUM DIAMETER *****

STAGE WITH MAXIMUM DIAMETER
COLUMN DIAMETER
DC AREA/COLUMN AREA
SIDE DOWNCOMER VELOCITY
SIDE WEIR LENGTH

2
30.3522
0.100000
0.043509
14.5095

FT
FT/SEC
FT

**** SIZING PROFILES ****

STAGE
2
3
4
5

DIAMETER
FT
30.352
30.194
30.019
29.850

TOTAL AREA
SQFT
723.55
716.01
707.76
699.81

ACTIVE AREA
PER PANEL
SQFT
144.71
143.20
141.55
139.96

SIDE DC AREA
PER PANEL
SQFT
18.089
17.900
17.694
17.495

287

PhosgeneFreeRoutetoTolueneDiisocyanate

6
7
8
9
10
11

29.684
29.517
29.338
29.112
28.866
21.587

692.06
684.30
676.00
665.65
654.44
366.01

BouSaba,Dizon,Kasih,Stewart
138.41
136.86
135.20
133.13
130.89
73.201

17.301
17.107
16.900
16.641
16.361
9.1502

288

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
32

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-101

STAGE
12
13
14
15
16
17
18
19

MODEL: RADFRAC (CONTINUED)

DIAMETER
FT
20.329
17.834
15.128
14.394
14.257
14.191
14.135
14.171

TOTAL AREA
SQFT
324.57
249.79
179.74
162.73
159.64
158.17
156.91
157.72

BLOCK: D-102
MODEL: RADFRAC
------------------------------INLETS
- S-112
STAGE
5
OUTLETS - S-115
STAGE
1
S-113
STAGE 12
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
14
ENTHALPY(BTU/HR
01

ACTIVE AREA
PER PANEL
SQFT
64.914
49.957
35.948
32.547
31.928
31.635
31.382
31.544

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
684.886
47936.4

SIDE DC AREA
PER PANEL
SQFT
8.1143
6.2447
4.4935
4.0683
3.9910
3.9543
3.9228
3.9430

-0.658998E+08

***
OUT

684.886
47936.4
-0.643408E+08

RELATIVE
0.00000
0.546421E-0.236565E-

289

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33

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-102

MODEL: RADFRAC (CONTINUED)

**********************
**** INPUT DATA ****
**********************
****

INPUT PARAMETERS

****

NUMBER OF STAGES
ALGORITHM OPTION
ABSORBER OPTION
INITIALIZATION OPTION
HYDRAULIC PARAMETER CALCULATIONS
INSIDE LOOP CONVERGENCE METHOD
DESIGN SPECIFICATION METHOD
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS
MAXIMUM NO. OF INSIDE LOOP ITERATIONS
MAXIMUM NUMBER OF FLASH ITERATIONS
FLASH TOLERANCE
OUTSIDE LOOP CONVERGENCE TOLERANCE
****

COL-SPECS

****

MOLAR VAPOR DIST / TOTAL DIST

MOLAR REFLUX RATIO
MOLAR DISTILLATE RATE
****

PROFILES

P-SPEC

12
STANDARD
NO
STANDARD
NO
BROYDEN
NESTED
25
10
50
0.000100000
0.000100000

LBMOL/HR

0.0
0.0070000
456.905

****
STAGE

PRES, PSIA

1.00000

*******************
**** RESULTS ****
*******************
***

COMPONENT SPLIT FRACTIONS

S-115
COMPONENT:
TDA
TDI
WATER
SOLVENT

.76687E-04
.11883E-02
.99942
1.0000

***

OUTLET STREAMS
-------------S-113
.99992
.99881
.58416E-03
.67174E-09

290

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34

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04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:
***

D-102

MODEL: RADFRAC (CONTINUED)

SUMMARY OF KEY RESULTS

TOP STAGE TEMPERATURE

BOTTOM STAGE TEMPERATURE
TOP STAGE LIQUID FLOW
BOTTOM STAGE LIQUID FLOW
TOP STAGE VAPOR FLOW
BOILUP VAPOR FLOW
MOLAR REFLUX RATIO
MOLAR BOILUP RATIO
CONDENSER DUTY (W/O SUBCOOL)
REBOILER DUTY
****

F
F
LBMOL/HR
LBMOL/HR
LBMOL/HR
LBMOL/HR

PROFILES

101.705
352.201
3.19833
227.981
0.0
293.054
0.0070000
1.28543
-8,628,050.
0.101869+08

BTU/HR
BTU/HR

MAXIMUM FINAL RELATIVE ERRORS

DEW POINT
BUBBLE POINT
COMPONENT MASS BALANCE
ENERGY BALANCE
****

***

****

0.23692E-03
0.18336E-03
0.81103E-05
0.30211E-03

STAGE= 11
STAGE= 11
STAGE= 4 COMP=TDI
STAGE= 11

****

**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS
FROM THE STAGE EXCLUDING ANY SIDE PRODUCT. FOR THE FIRST
STAGE,
THE REPORTED VAPOR FLOW IS THE VAPOR DISTILLATE FLOW. FOR THE
LAST STAGE, THE REPORTED LIQUID FLOW IS THE LIQUID BOTTOMS
FLOW.
STAGE TEMPERATURE
F
1
2
3
4
5
6
8
9
10
11
12

101.70
114.50
125.29
127.19
128.03
130.69
135.56
137.89
147.84
264.38
352.20

PRESSURE
PSIA
1.0000
1.0077
1.1077
1.2077
1.3077
1.4077
1.6077
1.7077
1.8077
1.9077
2.0077

ENTHALPY
BTU/LBMOL
LIQUID
VAPOR
-0.12237E+06
-0.10078E+06
-91420.
-92769.
-95156.
-95178.
-95212.
-95123.
-86894.
-46463.
-36978.

-0.10377E+06
-0.10362E+06
-0.10348E+06
-0.10347E+06
-0.10347E+06
-0.10345E+06
-0.10340E+06
-0.10338E+06
-0.10323E+06
-90438.
-19082.

HEAT DUTY
BTU/HR
-.86281+07

.10187+08

291

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35

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VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:
STAGE

D-102

FLOW RATE
LBMOL/HR
LIQUID
VAPOR

VAPOR
1 3.198
2 0.9394
3 0.5934
4 0.4654
5 598.9
6 601.4
8 605.8
9 606.5
10 563.7
11 521.0
12 228.0
****
STAGE

MODEL: RADFRAC (CONTINUED)

LIQUID

0.000
460.1
457.8
457.5
371.4
371.0
375.7
377.8
378.5
335.7
293.1

85.9955
598.8904

227.9810

VAPOR
1 57.92
0.000
2 61.88
8331.
3 51.02
8335.
4 38.56
8325.
5 0.4641E+05 6749.
6 0.4645E+05 6744.
8 0.4654E+05 6834.
9 0.4660E+05 6875.
10 0.5309E+05 6942.
11 0.8719E+05 0.1343E+05
12 0.3966E+05 0.4752E+05
STAGE
1
2
3
4
5
6
8
9
10
11
12

TDA
0.14150E-08
0.17344E-05
0.61773E-05
0.11091E-04
0.14083E-04
0.14026E-04
0.13925E-04
0.13912E-04
0.15417E-04
0.22182E-04
0.36978E-04

MIXED

PRODUCT RATE
LBMOL/HR
LIQUID
456.9050

MASS FLOW PROFILES

FLOW RATE
LB/HR
LIQUID
VAPOR

FEED RATE
LBMOL/HR
VAPOR

****

LIQUID

FEED RATE
LB/HR
VAPOR

MIXED

PRODUCT RATE
LB/HR
LIQUID
8273.5781

.46374+05

1562.8473

.39663+05

****
MOLE-X-PROFILE
****
TDI
WATER
SOLVENT
0.59289E-03
0.99941
0.21391E-06
0.30648
0.69352
0.20262E-07
0.43526
0.56473
0.19473E-07
0.41515
0.58484
0.19954E-07
0.38083
0.61916
0.10126E-07
0.37929
0.62070
0.15836E-08
0.37658
0.62340
0.39409E-10
0.37676
0.62323
0.62633E-11
0.48783
0.51215
0.92269E-12
0.95626
0.43719E-01
0.24151E-13
0.99879
0.11707E-02
0.0000

292

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36

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-102

MODEL: RADFRAC (CONTINUED)

STAGE
1
2
3
4
5
6
8
9
10
11
12

TDA
0.68136E-11
0.14150E-08
0.49710E-08
0.94257E-08
0.12702E-07
0.13306E-07
0.14468E-07
0.15058E-07
0.18003E-07
0.77530E-06
0.10672E-04

****
MOLE-Y-PROFILE
****
TDI
WATER
SOLVENT
0.64643E-06
1.0000
0.31616E-05
0.59289E-03
0.99941
0.21391E-06
0.12205E-02
0.99878
0.21351E-06
0.11567E-02
0.99884
0.21366E-06
0.10151E-02
0.99898
0.10549E-06
0.10489E-02
0.99895
0.16349E-07
0.11130E-02
0.99889
0.40029E-09
0.11517E-02
0.99885
0.63187E-10
0.20804E-02
0.99792
0.10036E-10
0.14085
0.85915
0.15491E-11
0.92317
0.76820E-01
0.42715E-13

STAGE
1
2
3
4
5
6
8
9
10
11
12

TDA
0.48151E-02
0.81590E-03
0.80507E-03
0.84999E-03
0.90190E-03
0.94832E-03
0.10386E-02
0.10819E-02
0.11657E-02
0.34970E-01
0.28860

****
K-VALUES
TDI
WATER
0.10903E-02
1.0006
0.19345E-02
1.4411
0.28034E-02
1.7686
0.27859E-02
1.7079
0.26655E-02
1.6135
0.27655E-02
1.6094
0.29556E-02
1.6023
0.30566E-02
1.6027
0.42634E-02
1.9487
0.14733
19.647
0.92426
65.621

STAGE
1
2
3
4
5
6
8
9
10
11
12

TDA
0.95469E-08
0.32169E-05
0.87775E-05
0.16357E-04
0.22206E-04
0.22185E-04
0.22146E-04
0.22117E-04
0.19997E-04
0.16196E-04
0.25967E-04

****
MASS-X-PROFILE
****
TDI
WATER
SOLVENT
0.57023E-02
0.99430
0.11818E-05
0.81032
0.18968
0.30772E-07
0.88166
0.11833
0.22658E-07
0.87280
0.12719
0.24097E-07
0.85602
0.14396
0.13075E-07
0.85521
0.14477
0.20511E-08
0.85378
0.14620
0.51322E-10
0.85387
0.14611
0.81538E-11
0.90202
0.97959E-01
0.98001E-12
0.99528
0.47069E-02
0.14439E-13
0.99985
0.12123E-03
0.0000

STAGE
1
2
3

TDA
0.46205E-10
0.95469E-08
0.33358E-07

****
MASS-Y-PROFILE
TDI
WATER
0.62491E-05
0.99998
0.57023E-02
0.99430
0.11676E-01
0.98832

****
SOLVENT
14.780
10.558
10.967
10.709
10.417
10.323
10.156
10.088
10.874
64.109
148.35

****
SOLVENT
0.17556E-04
0.11818E-05
0.11732E-05

293

PhosgeneFreeRoutetoTolueneDiisocyanate

4
5
6
8
9
10
11

0.63286E-07
0.85389E-07
0.89419E-07
0.97178E-07
0.10111E-06
0.11992E-06
0.23675E-05

0.11071E-01
0.97274E-02
0.10048E-01
0.10657E-01
0.11024E-01
0.19755E-01
0.61314

BouSaba,Dizon,Kasih,Stewart
0.98893
0.99027
0.98995
0.98934
0.98898
0.98024
0.38686

0.11747E-05
0.58066E-06
0.89972E-07
0.22016E-08
0.34742E-09
0.54742E-10
0.38734E-11

294

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ASPEN PLUS
37

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-102

STAGE
12

MODEL: RADFRAC (CONTINUED)

TDA
0.80404E-05

****
MASS-Y-PROFILE
****
TDI
WATER
SOLVENT
0.99146
0.85342E-02
0.26352E-13

********************************
***** HYDRAULIC PARAMETERS *****
********************************
*** DEFINITIONS ***
MARANGONI INDEX = SIGMA - SIGMATO
FLOW PARAM = (ML/MV)*SQRT(RHOV/RHOL)
QR = QV*SQRT(RHOV/(RHOL-RHOV))
F FACTOR = QV*SQRT(RHOV)
WHERE:
SIGMA IS THE SURFACE TENSION OF LIQUID FROM THE STAGE
SIGMATO IS THE SURFACE TENSION OF LIQUID TO THE STAGE
ML IS THE MASS FLOW OF LIQUID FROM THE STAGE
MV IS THE MASS FLOW OF VAPOR TO THE STAGE
RHOL IS THE MASS DENSITY OF LIQUID FROM THE STAGE
RHOV IS THE MASS DENSITY OF VAPOR TO THE STAGE
QV IS THE VOLUMETRIC FLOW RATE OF VAPOR TO THE STAGE

STAGE
1
2
3
4
5
6
8
9
10
11
12

TEMPERATURE
F
LIQUID FROM
VAPOR TO
101.70
114.50
114.50
125.29
125.29
127.19
127.19
128.00
128.03
130.69
130.69
133.19
135.56
137.89
137.89
147.84
147.84
264.38
264.38
352.20
352.20
352.20
MASS FLOW
LB/HR

VOLUME FLOW
CUFT/HR

MOLECULAR WEIGHT

295

PhosgeneFreeRoutetoTolueneDiisocyanate

STAGE LIQUID FROM

TO
1
8331.5
2
61.881
3
51.021
4
38.557
5
46406.
6
46453.
8
46538.

VAPOR TO

LIQUID FROM

8331.5
8335.5
8324.6
8312.1
6743.7
6790.5
6874.8

136.04
0.87821
0.71309
0.54085
654.51
656.24
659.41

BouSaba,Dizon,Kasih,Stewart
VAPOR TO
0.28112E+07
0.25926E+07
0.23837E+07
0.23863E+07
0.16679E+07
0.15742E+07
0.14172E+07

LIQUID FROM
18.108
65.870
85.979
82.840
77.481
77.240
76.818

VAPOR
18.108
18.206
18.196
18.174
18.179
18.184
18.195

296

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PAGE

U-O-S BLOCK SECTION

BLOCK:

D-102

MODEL: RADFRAC (CONTINUED)

MASS FLOW
LB/HR
STAGE LIQUID FROM VAPOR TO
TO
9
46604.
6941.5
10
53095.
13432.
11
87185.
47523.
12
39663.
47523.

VOLUME FLOW
CUFT/HR
LIQUID FROM VAPOR TO

DENSITY
LB/CUFT
STAGE LIQUID FROM VAPOR TO
1
61.245
0.29637E-02
2
70.463
0.32151E-02
3
71.549
0.34923E-02
4
71.290
0.34833E-02
5
70.903
0.40433E-02
6
70.787
0.43137E-02
8
70.574
0.48509E-02
9
70.489
0.50913E-02
10
71.159
0.98352E-02
11
68.945
0.37563E-01
12
65.604
0.37563E-01

STAGE
1
2
3
4
5
6
8
9
10
11
12

MARANGONI INDEX
DYNE/CM
-7.8892
-3.7978
0.23428
-.78152E-02
-.23224
-.20809
-.23503
-3.2606
-19.333
-7.5865

661.16
746.15
1264.6
604.58

0.13634E+07
0.13657E+07
0.12651E+07
0.12651E+07

MOLECULAR WEIGHT
LIQUID FROM
76.845
94.189
167.33
173.97

VAPOR
18.340
40.009
162.16
162.16

VISCOSITY
SURFACE TENSION
CP
DYNE/CM
LIQUID FROM VAPOR TO
LIQUID FROM
0.68816
0.10558E-01
70.079
0.84215
0.10778E-01
62.190
0.87553
0.10817E-01
58.392
0.84165
0.10834E-01
58.626
0.80427
0.10889E-01
59.262
0.78393
0.10941E-01
59.030
0.74878
0.11037E-01
58.602
0.73401
0.11239E-01
58.367
0.76486
0.12587E-01
55.106
0.64833
0.87263E-02
35.773
0.46010
0.87263E-02
28.187

FLOW PARAM
0.69564E-02
0.50147E-04
0.42819E-04
0.32424E-04
0.51966E-01
0.53403E-01
0.56122E-01
0.57059E-01
0.46472E-01
0.42823E-01
0.19971E-01

QR
CUFT/HR
19556.
17513.
16654.
16681.
12595.
12289.
11750.
11588.
16057.
29538.
30281.

REDUCED F-FACTOR
(LB-CUFT)**.5/HR
0.15304E+06
0.14700E+06
0.14087E+06
0.14084E+06
0.10605E+06
0.10339E+06
98707.
97284.
0.13544E+06
0.24520E+06
0.24520E+06

297

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39

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BouSaba,Dizon,Kasih,Stewart

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04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

D-102

MODEL: RADFRAC (CONTINUED)

***************************************
***** PACKING SIZING CALCULATIONS *****
***************************************

*******************
*** SECTION
1 ***
*******************
STARTING STAGE NUMBER
ENDING STAGE NUMBER
CAPACITY CALCULATION METHOD
PRESSURE DROP CALCULATION METHOD
LIQUID HOLDUP CALCULATION METHOD
PRESSURE PROFILE UPDATED

2
7
KOCH
KOCH
STICHL
NO

DESIGN PARAMETERS
----------------OVERDESIGN FACTOR
SYSTEM FOAMING FACTOR
FRAC. APP. TO MAXIMUM CAPACITY
MAXIMUM CAPACITY FACTOR
DESIGN CAPACITY FACTOR
PRESSURE DROP FOR THE SECTION
PRESSURE DROP PER UNIT HEIGHT

1.00000
1.00000
0.62000
MISSING
MISSING
MISSING
MISSING

PACKING SPECIFICATIONS
---------------------PACKING TYPE
PACKING MATERIAL
PACKING SIZE
VENDOR
PACKING FACTOR
PACKING SURFACE AREA
PACKING VOID FRACTION
FIRST STICHLMAIR CONSTANT
SECOND STICHLMAIR CONSTANT
THIRD STICHLMAIR CONSTANT
HETP
PACKING HEIGHT

FT/SEC
FT/SEC
PSI
IN-WATER/FT

1/FT
SQFT/CUF

FT
FT

FLEXIPAC
METAL
2X
KOCH
15.1792
68.5808
0.97000
0.84405
-0.098801
0.33853
1.50000
9.00000

***** SIZING RESULTS *****

COLUMN DIAMETER
MAXIMUM FRACTIONAL CAPACITY

FT

3.93165
0.62000

298

PhosgeneFreeRoutetoTolueneDiisocyanate

MAXIMUM CAPACITY FACTOR

PRESSURE DROP FOR THE SECTION
AVERAGE PRESSURE DROP/HEIGHT
MAXIMUM LIQUID HOLDUP/STAGE
MAX LIQ SUPERFICIAL VELOCITY

FT/SEC
PSI
IN-WATER/FT
CUFT
FT/SEC

BouSaba,Dizon,Kasih,Stewart
0.40070
0.051517
0.15844
0.83682
0.015052

299

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U-O-S BLOCK SECTION

BLOCK:

D-102

MODEL: RADFRAC (CONTINUED)

**** RATING PROFILES AT MAXIMUM COLUMN DIAMETER ****

STAGE
2
1.500
3
1.500
4
1.500
5
1.500
6
1.500
7
1.500

HEIGHT
FROM TOP
OF SECTION
FT
0.000

FRACTIONAL
CAPACITY
0.6106

PRESSURE
PRESSURE
DROP
DROP/HEIGHT
PSI
IN-WATER/FT
0.10901E-01 0.20116

LIQUID
HOLDUP
CUFT
0.1014E-01

1.500

0.5801

0.10009E-01 0.18469

0.8813E-02

3.000

0.5802

0.10004E-01 0.18460

0.7330E-02

4.500

0.6200

0.72805E-02 0.13435

0.8351

6.000

0.6074

0.68487E-02 0.12638

0.8360

7.500

0.5958

0.64742E-02 0.11947

0.8368

HETP
FT

LIQUID
SUPERFICIAL
STAGE VELOCITY
FT/SEC
2
0.2009E-04
3
0.1632E-04
4
0.1237E-04
5
0.1498E-01
6
0.1501E-01
7
0.1505E-01

************************************
***** TRAY SIZING CALCULATIONS *****
************************************
*******************
*** SECTION
1 ***
*******************
STARTING STAGE NUMBER
ENDING STAGE NUMBER
FLOODING CALCULATION METHOD

2
10
B960

300

PhosgeneFreeRoutetoTolueneDiisocyanate

DESIGN PARAMETERS
----------------PEAK CAPACITY FACTOR
SYSTEM FOAMING FACTOR
FLOODING FACTOR
MINIMUM COLUMN DIAMETER
MINIMUM DC AREA/COLUMN AREA
TRAY SPECIFICATIONS
------------------TRAY TYPE
NUMBER OF PASSES
TRAY SPACING

FT

FT

BouSaba,Dizon,Kasih,Stewart

1.00000
1.00000
0.80000
1.00000
0.100000

FLEXI
4
2.00000

301

PhosgeneFreeRoutetoTolueneDiisocyanate

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41

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U-O-S BLOCK SECTION

BLOCK:

D-102

MODEL: RADFRAC (CONTINUED)

***** SIZING RESULTS @ STAGE WITH MAXIMUM DIAMETER *****

STAGE WITH MAXIMUM DIAMETER
COLUMN DIAMETER
DC AREA/COLUMN AREA
SIDE DOWNCOMER VELOCITY
SIDE WEIR LENGTH

2
4.19065
0.100000
0.00017687
2.00327

FT
FT/SEC
FT

**** SIZING PROFILES ****

STAGE
2
3
4
5
6
7
8
9
10

DIAMETER
FT
4.1907
4.0863
4.0893
3.6905
3.6461
3.6049
3.5667
3.5426
4.1747

TOTAL AREA
SQFT
13.793
13.114
13.134
10.697
10.441
10.207
9.9915
9.8567
13.688

BLOCK: F-100
MODEL: FLASH2
-----------------------------INLET STREAM:
S-102
OUTLET VAPOR STREAM:
S-103
OUTLET LIQUID STREAM: S-128
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR
08

ACTIVE AREA
PER PANEL
SQFT
2.7586
2.6229
2.6268
2.1394
2.0883
2.0413
1.9983
1.9713
2.7376

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
5622.44
292971.

SIDE DC AREA
PER PANEL
SQFT
0.34482
0.32786
0.32835
0.26742
0.26103
0.25516
0.24979
0.24642
0.34220

-0.939393E+09

***
OUT

5622.44
292971.
-0.939393E+09

RELATIVE
0.00000
0.198681E0.319939E-

302

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42

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PAGE

U-O-S BLOCK SECTION

BLOCK:

F-100

MODEL: FLASH2 (CONTINUED)

*** INPUT DATA

TWO
PHASE PQ FLASH
PRESSURE DROP
PSI
SPECIFIED HEAT DUTY
BTU/HR
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
***
F
PSIA

OUTLET TEMPERATURE
OUTLET PRESSURE
VAPOR FRACTION

RESULTS

***
3.00000
0.0
30
0.000100000

***
99.909
644.67
0.52499

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.40071E-07
O2
1.8937
CO
3.3769
TDI
0.28410E-05
WATER
0.49705E-03
TDCARB
0.90536E-10
SOLVENT
0.11484E-01

F(I)
0.17052E-05

X(I)
0.35898E-05

Y(I)
0.14385E-12

0.55224E-02

0.37589E-02

0.71180E-02

0.65559

0.29165

0.98489

0.34859E-04

0.73386E-04

0.20849E-09

0.41174E-02

0.86631E-02

0.43061E-05

0.36533E-08

0.76908E-08

0.69630E-18

0.33473

0.69585

0.79909E-02

BLOCK: H-100
MODEL: HEATER
-----------------------------INLET STREAM:
S-110
OUTLET STREAM:
S-111
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
01

K(I)

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
10189.1
978444.
-0.380276E+10

***
OUT

10189.1
978444.
-0.362940E+10

RELATIVE
0.00000
0.00000
-0.455879E-

303

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
43

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

H-100

MODEL: HEATER (CONTINUED)

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

INPUT DATA

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

120.000
5.00000
30

***

120.00
7.0000
0.17336E+09
0.88703
8.9245

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.36735E-04
O2
22.252
CO
35.404
TDI
0.35356E-03
WATER
0.26500
SOLVENT
1.3894

F(I)
0.82744E-06

X(I)
0.73225E-05

Y(I)
0.26899E-09

0.39851E-03

0.20075E-04

0.44671E-03

0.27281E-01

0.86560E-03

0.30645E-01

0.22375E-01

0.19751

0.69834E-04

0.44843E-01

0.12885

0.34145E-01

0.90510

0.67275

0.93469

BLOCK: H-101
MODEL: HEATER
-----------------------------INLET STREAM:
S-121
OUTLET STREAM:
S-122
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)

K(I)

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
2750.53
283360.

***
OUT

2750.53
283360.

RELATIVE
0.00000
0.00000

304

PhosgeneFreeRoutetoTolueneDiisocyanate

01

ENTHALPY(BTU/HR

-0.108016E+10

BouSaba,Dizon,Kasih,Stewart
-0.105955E+10

-0.190787E-

305

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
44

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

H-101

MODEL: HEATER (CONTINUED)

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

INPUT DATA

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

248.000
5.00000
30

***

248.00
648.00
0.20608E+08
0.0000
38286.

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.13118E-03
O2
13.800
CO
25.186
TDI
0.53076E-03
WATER
0.42010E-01
TDCARB
0.15788E-06
SOLVENT
0.23900

F(I)
0.15314E-01

X(I)
0.15314E-01

Y(I)
0.21309E-05

0.41335E-03

0.41335E-03

0.60506E-02

0.28297E-01

0.28297E-01

0.75595

0.14512E-05

0.14512E-05

0.81699E-09

0.91859E-06

0.91859E-06

0.40932E-07

0.17168E-01

0.17168E-01

0.28748E-08

0.93881

0.93881

0.23799

BLOCK: H-102
MODEL: HEATER
-----------------------------INLET STREAM:
S-129
OUTLET STREAM:
PSEUDLIQ
PROPERTY OPTION SET:
NRTL-RK
***

K(I)

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
OUT

RELATIVE

DIFF.
TOTAL BALANCE

306

PhosgeneFreeRoutetoTolueneDiisocyanate

MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR

11964.1
0.112468E+07
-0.438736E+10

BouSaba,Dizon,Kasih,Stewart
11964.1
0.112468E+07
-0.430887E+10

0.00000
0.00000
-0.178892E-

01

307

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
45

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

H-102

MODEL: HEATER (CONTINUED)

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

INPUT DATA

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

248.000
5.00000
30

***

248.00
639.67
0.78486E+08
0.84609E-01
1638.6

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.13966E-03
O2
17.117
CO
31.551
TDI
0.55075E-03
WATER
0.44733E-01
TDCARB
0.15987E-06
SOLVENT
0.23742

F(I)
0.63441E-03

X(I)
0.69304E-03

Y(I)
0.96784E-07

0.11757E-02

0.49742E-03

0.85145E-02

0.86742E-01

0.24197E-01

0.76343

0.49334E-02

0.53891E-02

0.29679E-05

0.74641E-02

0.81204E-02

0.36324E-03

0.19135E-02

0.20903E-02

0.33413E-09

0.89714

0.95901

0.22769

BLOCK: H-103
MODEL: HEATER
-----------------------------INLET STREAM:
S-131
OUTLET STREAM:
S-132
PROPERTY OPTION SET:
NRTL-RK
***

K(I)

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
OUT

RELATIVE

DIFF.
TOTAL BALANCE

308

PhosgeneFreeRoutetoTolueneDiisocyanate

MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR

922.509
26522.2
-0.440973E+08

BouSaba,Dizon,Kasih,Stewart
922.509
26522.2
-0.431146E+08

0.00000
0.00000
-0.222856E-

01

309

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
46

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

H-103

MODEL: HEATER (CONTINUED)

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

INPUT DATA

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

248.000
5.00000
30

***

248.00
639.67
0.98274E+06
1.0000
0.13429E+06

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.16787E-04
O2
15.404
CO
27.574
TDI
0.37966E-03
WATER
0.22821E-01
SOLVENT
0.16694

F(I)
0.13808E-12

X(I)
0.98552E-07

Y(I)
0.13808E-12

0.46941E-01

0.36512E-01

0.46941E-01

0.94538

0.41079

0.94538

0.20013E-09

0.63157E-05

0.20013E-09

0.41333E-05

0.21701E-02

0.41333E-05

0.76704E-02

0.55052

0.76704E-02

BLOCK: H-104
MODEL: HEATER
-----------------------------INLET STREAM:
S-130
OUTLET STREAM:
PSEUDVAP
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)

K(I)

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
3303.01
122800.

***
OUT

3303.01
122800.

RELATIVE
0.00000
0.00000

310

PhosgeneFreeRoutetoTolueneDiisocyanate

02

ENTHALPY(BTU/HR

-0.294858E+09

BouSaba,Dizon,Kasih,Stewart
-0.292992E+09

-0.633011E-

311

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
47

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

H-104

MODEL: HEATER (CONTINUED)

***
TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE
PRESSURE DROP
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
0.000100000

INPUT DATA

***

F
PSI

*** RESULTS
OUTLET TEMPERATURE
F
OUTLET PRESSURE
PSIA
HEAT DUTY
BTU/HR
OUTLET VAPOR FRACTION
PRESSURE-DROP CORRELATION PARAMETER

248.000
5.00000
30

***

248.00
639.67
0.18665E+07
1.0000
7688.1

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.59891E-04
O2
7.8302
CO
13.423
TDI
0.47549E-03
WATER
0.35964E-01
TDCARB
0.11728E-06
SOLVENT
0.23246

F(I)
0.43865E-06

X(I)
0.10585E-01

Y(I)
0.43865E-06

0.71156E-02

0.13139E-02

0.71156E-02

0.86500

0.93175E-01

0.86500

0.13015E-04

0.39581E-01

0.13015E-04

0.88935E-03

0.35753E-01

0.88935E-03

0.24178E-08

0.29812E-01

0.24178E-08

0.12698

0.78978

0.12698

BLOCK: M-100
MODEL: MIXER
----------------------------INLET STREAMS:
S-116
OUTLET STREAM:
S-121
PROPERTY OPTION SET:
NRTL-RK
***

K(I)

S-119
RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
OUT

RELATIVE

DIFF.
TOTAL BALANCE

312

PhosgeneFreeRoutetoTolueneDiisocyanate

MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR

2750.53
283360.
-0.108016E+10

BouSaba,Dizon,Kasih,Stewart
2750.53
283360.
-0.108016E+10

0.00000
0.00000
-0.220725E-

15

313

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
48

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

M-100

MODEL: MIXER (CONTINUED)

*** INPUT DATA ***

TWO
PHASE
FLASH
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
OUTLET PRESSURE: MINIMUM OF INLET STREAM PRESSURES
BLOCK: M-101
MODEL: MIXER
----------------------------INLET STREAMS:
S-125
OUTLET STREAM:
S-129
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR
15

S-126

S-128

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
OUT

11964.1
0.112468E+07

0.00000
-0.207019E-

-0.438736E+10

-0.438736E+10

0.217369E-

BLOCK: M-102
MODEL: MIXER
----------------------------INLET STREAMS:
O2MAKEUP
OUTLET STREAM:
S-131
PROPERTY OPTION SET:
NRTL-RK

DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR
15

30
0.000100000

S-120
RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
922.509
26522.2

RELATIVE

11964.1
0.112468E+07

*** INPUT DATA ***

TWO
PHASE
FLASH
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
OUTLET PRESSURE: MINIMUM OF INLET STREAM PRESSURES

***

30
0.000100000

-0.440973E+08

***
OUT

922.509
26522.2
-0.440973E+08

RELATIVE
0.00000
0.137167E-0.168958E-

314

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
49

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

M-102

MODEL: MIXER (CONTINUED)

*** INPUT DATA ***

TWO
PHASE
FLASH
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
OUTLET PRESSURE: MINIMUM OF INLET STREAM PRESSURES
BLOCK: M-103
MODEL: MIXER
----------------------------INLET STREAMS:
S-127
OUTLET STREAM:
S-130
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR

S-124
RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
3303.01
122800.
-0.294858E+09

***
OUT

***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR
02

0.00000
0.00000
0.00000

30
0.000100000

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
90.2484
23048.8

RELATIVE

3303.01
122800.
-0.294858E+09

*** INPUT DATA ***

TWO
PHASE
FLASH
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
OUTLET PRESSURE: MINIMUM OF INLET STREAM PRESSURES
BLOCK: P-100
MODEL: PUMP
---------------------------INLET STREAM:
S-106
OUTLET STREAM:
S-107
PROPERTY OPTION SET:
NRTL-RK

30
0.000100000

-0.358808E+08

***
OUT

90.2484
23048.8
-0.358388E+08

RELATIVE
0.00000
-0.157838E-0.117157E-

315

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
50

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

P-100

MODEL: PUMP (CONTINUED)

OUTLET PRESSURE PSIA

PUMP EFFICIENCY
DRIVER EFFICIENCY

***

INPUT DATA

***

653.000
0.80000
1.00000

FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS
TOLERANCE

30
0.000100000

*** RESULTS
VOLUMETRIC FLOW RATE CUFT/HR
PRESSURE CHANGE PSI
NPSH AVAILABLE
FT-LBF/LB
FLUID POWER HP
BRAKE POWER HP
ELECTRICITY KW
PUMP EFFICIENCY USED
NET WORK REQUIRED HP
HEAD DEVELOPED FT-LBF/LB
BLOCK: P-101
MODEL: PUMP
---------------------------INLET STREAM:
S-109
OUTLET STREAM:
S-110
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
05

***
280.408
648.100
0.0
13.2169
16.5211
12.3198
0.80000
16.5211
1,135.40

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
10189.1
978444.
-0.380278E+10

***
OUT

10189.1
978444.
-0.380276E+10

RELATIVE
0.00000
0.00000
-0.595160E-

316

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
51

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

P-101

MODEL: PUMP (CONTINUED)

PRESSURE CHANGE PSI

PUMP EFFICIENCY
DRIVER EFFICIENCY

***

INPUT DATA

***

10.0000
0.80000
1.00000

FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS
TOLERANCE

30
0.000100000

*** RESULTS
VOLUMETRIC FLOW RATE CUFT/HR
PRESSURE CHANGE PSI
NPSH AVAILABLE
FT-LBF/LB
FLUID POWER HP
BRAKE POWER HP
ELECTRICITY KW
PUMP EFFICIENCY USED
NET WORK REQUIRED HP
HEAD DEVELOPED FT-LBF/LB
BLOCK: P-102
MODEL: PUMP
---------------------------INLET STREAM:
S-113
OUTLET STREAM:
S-114
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
03

***
9,784.44
10.0000
0.0
7.11596
8.89495
6.63296
0.80000
8.89495
14.4000

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
227.981
39662.8
-0.843033E+07

***
OUT

227.981
39662.8
-0.842921E+07

RELATIVE
0.00000
0.00000
-0.133284E-

317

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
52

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

P-102

MODEL: PUMP (CONTINUED)

PRESSURE CHANGE PSI

DRIVER EFFICIENCY

***

INPUT DATA

***

5.00000
1.00000

FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS
TOLERANCE

30
0.000100000

*** RESULTS
VOLUMETRIC FLOW RATE CUFT/HR
PRESSURE CHANGE PSI
NPSH AVAILABLE
FT-LBF/LB
FLUID POWER HP
BRAKE POWER HP
ELECTRICITY KW
PUMP EFFICIENCY USED
NET WORK REQUIRED HP
HEAD DEVELOPED FT-LBF/LB
BLOCK: P-103
MODEL: PUMP
---------------------------INLET STREAM:
S-115
OUTLET STREAM:
WASTEWTR
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
05

***

604.575
5.00000
0.0
0.21985
0.44160
0.32930
0.49784
0.44160
10.9749

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
456.905
8273.58
-0.559105E+08

***
OUT

456.905
8273.58
-0.559101E+08

RELATIVE
0.00000
0.00000
-0.756139E-

318

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
53

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

P-103

MODEL: PUMP (CONTINUED)

PRESSURE CHANGE PSI

DRIVER EFFICIENCY

***

INPUT DATA

***

5.00000
1.00000

FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS
TOLERANCE

30
0.000100000

*** RESULTS
VOLUMETRIC FLOW RATE CUFT/HR
PRESSURE CHANGE PSI
NPSH AVAILABLE
FT-LBF/LB
FLUID POWER HP
BRAKE POWER HP
ELECTRICITY KW
PUMP EFFICIENCY USED
NET WORK REQUIRED HP
HEAD DEVELOPED FT-LBF/LB
BLOCK: P-104
MODEL: PUMP
---------------------------INLET STREAM:
S-117
OUTLET STREAM:
S-118
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
03

***

135.091
5.00000
0.0
0.049124
0.16615
0.12390
0.29566
0.16615
11.7561

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
9504.23
930508.
-0.373238E+10

***
OUT

9504.23
930508.
-0.373101E+10

RELATIVE
0.00000
0.00000
-0.367687E-

319

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
54

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

P-104

MODEL: PUMP (CONTINUED)

OUTLET PRESSURE PSIA

PUMP EFFICIENCY
DRIVER EFFICIENCY

***

INPUT DATA

***

653.000
0.80000
1.00000

FLASH SPECIFICATIONS:
LIQUID PHASE CALCULATION
NO FLASH PERFORMED
MAXIMUM NUMBER OF ITERATIONS
TOLERANCE

30
0.000100000

*** RESULTS
VOLUMETRIC FLOW RATE CUFT/HR
PRESSURE CHANGE PSI
NPSH AVAILABLE
FT-LBF/LB
FLUID POWER HP
BRAKE POWER HP
ELECTRICITY KW
PUMP EFFICIENCY USED
NET WORK REQUIRED HP
HEAD DEVELOPED FT-LBF/LB
BLOCK: R-100
MODEL: RSTOIC
-----------------------------INLET STREAMS:
TDA
PSEUDO
OUTLET STREAM:
S-100
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
0.00000
MASS(LB/HR
)
0.179866E-15
ENTHALPY(BTU/HR
0.133735E-02

9,155.70
648.000
0.0
431.483
539.354
402.196
0.80000
539.354
918.140

O2

CO

SOLVENT

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
OUT
16145.3

0.129446E+07
)

***

15901.8
0.129446E+07

***
GENERATION

RELATIVE

-243.518
-

-0.461796E+10 -0.462414E+10
***

INPUT DATA

***

320

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
55

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK: R-100
MODEL: RSTOIC (CONTINUED)
STOICHIOMETRY MATRIX:
REACTION #
1:
SUBSTREAM MIXED
TDA
-1.00
2.00
TDCARB
1.00
REACTION #
2:
SUBSTREAM MIXED
TDI
1.00

:
O2
SOLVENT
:
TDCARB

-1.00

CO

-2.00

-2.00

-1.00

REACTION CONVERSION SPECS: NUMBER=

REACTION #
1:
SUBSTREAM:MIXED
KEY COMP:TDA
REACTION #
2:
SUBSTREAM:MIXED
KEY COMP:TDCARB

SOLVENT

2.00

2
CONV FRAC: 0.8200
CONV FRAC: 0.7800

TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE F
SPECIFIED PRESSURE
PSIA
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
SERIES REACTIONS
GENERATE COMBUSTION REACTIONS FOR FEED SPECIES
OUTLET TEMPERATURE
OUTLET PRESSURE
HEAT DUTY
VAPOR FRACTION

WATER

*** RESULTS
F
PSIA
BTU/HR

***

282.765
652.670
30
0.000100000
NO
282.76
652.67
-0.61841E+07
0.35357

HEAT OF REACTIONS:
REACTION
NUMBER
1
2

REFERENCE
COMPONENT
TDA
TDCARB

HEAT OF
REACTION
BTU/LBMOL
-0.15077E+06
-12385.

REACTION EXTENTS:

321

PhosgeneFreeRoutetoTolueneDiisocyanate

REACTION
NUMBER
1
2

BouSaba,Dizon,Kasih,Stewart

REACTION
EXTENT
LBMOL/HR
193.91
169.11

322

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
56

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

R-100

MODEL: RSTOIC (CONTINUED)

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.41187E-03
O2
13.980
CO
24.243
TDI
0.15717E-02
WATER
0.92628E-01
TDCARB
0.78731E-06
SOLVENT
0.37311

F(I)
0.26768E-02

X(I)
0.41400E-02

Y(I)
0.17052E-05

0.22079E-02

0.39502E-03

0.55224E-02

0.24928

0.27042E-01

0.65559

0.14349E-01

0.22178E-01

0.34859E-04

0.30189E-01

0.44449E-01

0.41173E-02

0.29995E-02

0.46400E-02

0.36532E-08

0.69830

0.89715

0.33474

BLOCK: R-101
MODEL: FLASH2
-----------------------------INLET STREAM:
S-100
OUTLET VAPOR STREAM:
S-101
OUTLET LIQUID STREAM: S-104
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR
08

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

15901.8
0.129446E+07
-0.462414E+10

*** INPUT DATA

TWO
PHASE PQ FLASH
PRESSURE DROP
PSI
SPECIFIED HEAT DUTY
BTU/HR
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
OUTLET TEMPERATURE
OUTLET PRESSURE
VAPOR FRACTION

***
F
PSIA

K(I)

RESULTS

***
OUT

RELATIVE

15901.8
0.129446E+07
-0.462414E+10

0.00000
0.00000
0.851095E-

***

***

0.0
0.0
30
0.000100000
282.76
652.67
0.35357

323

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
57

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

R-101

MODEL: FLASH2 (CONTINUED)

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.41187E-03
O2
13.980
CO
24.243
TDI
0.15717E-02
WATER
0.92628E-01
TDCARB
0.78731E-06
SOLVENT
0.37311

F(I)
0.26768E-02

X(I)
0.41400E-02

Y(I)
0.17052E-05

0.22079E-02

0.39501E-03

0.55224E-02

0.24928

0.27042E-01

0.65559

0.14349E-01

0.22178E-01

0.34859E-04

0.30189E-01

0.44449E-01

0.41174E-02

0.29995E-02

0.46400E-02

0.36533E-08

0.69830

0.89716

0.33473

BLOCK: R-102
MODEL: RSTOIC
-----------------------------INLET STREAMS:
S-122
OUTLET STREAM:
S-123
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
0.00000
MASS(LB/HR
)
0.187838E-15
ENTHALPY(BTU/HR
0.184604E-02

REACTION #
1:
SUBSTREAM MIXED
TDA
-1.00
2.00
TDCARB
1.00
REACTION #
2:
SUBSTREAM MIXED
TDI
1.00

S-132
RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN
OUT
3673.04

3687.15

309883.

309883.

***
GENERATION

***

INPUT DATA

***

-1.00

CO

:
O2
SOLVENT
:
TDCARB

RELATIVE

14.1137
-

-0.110267E+10 -0.110063E+10

STOICHIOMETRY MATRIX:

K(I)

-2.00

WATER

-2.00

-1.00

SOLVENT

2.00

324

PhosgeneFreeRoutetoTolueneDiisocyanate

REACTION CONVERSION SPECS: NUMBER=

REACTION #
1:
SUBSTREAM:MIXED
KEY COMP:TDA
REACTION #
2:
SUBSTREAM:MIXED
KEY COMP:TDCARB

TWO
PHASE TP FLASH
SPECIFIED TEMPERATURE F
SPECIFIED PRESSURE
PSIA
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE

BouSaba,Dizon,Kasih,Stewart

2
CONV FRAC: 0.8200
CONV FRAC: 0.7200

279.500
652.670
30
0.000100000

325

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
58

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK: R-102
MODEL: RSTOIC (CONTINUED)
SERIES REACTIONS
GENERATE COMBUSTION REACTIONS FOR FEED SPECIES
OUTLET TEMPERATURE
OUTLET PRESSURE
HEAT DUTY
VAPOR FRACTION

*** RESULTS
F
PSIA
BTU/HR

NO

***

279.50
652.67
0.20356E+07
0.33545

REACTION EXTENTS:
REACTION
NUMBER
1
2

REACTION
EXTENT
LBMOL/HR
34.540
58.867

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.37863E-03
O2
15.780
CO
27.730
TDI
0.14477E-02
WATER
0.87693E-01
TDCARB
0.69111E-06
SOLVENT
0.35715

F(I)
0.20563E-02

X(I)
0.30937E-02

Y(I)
0.11714E-05

0.26850E-02

0.45068E-03

0.71113E-02

0.23890

0.23972E-01

0.66471

0.15967E-01

0.24008E-01

0.34760E-04

0.18737E-01

0.27000E-01

0.23677E-02

0.62088E-02

0.93428E-02

0.64582E-08

0.71544

0.91213

0.32578

BLOCK: R-103
MODEL: FLASH2
-----------------------------INLET STREAM:
S-123
OUTLET VAPOR STREAM:
S-124
OUTLET LIQUID STREAM: S-125
PROPERTY OPTION SET:
NRTL-RK
***

K(I)

RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
OUT

RELATIVE

DIFF.

326

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
59

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK: R-103
MODEL: FLASH2 (CONTINUED)
TOTAL BALANCE
MOLE(LBMOL/HR)
3687.15
15
MASS(LB/HR
)
309883.
ENTHALPY(BTU/HR )
-0.110063E+10
07
*** INPUT DATA
TWO
PHASE PQ FLASH
PRESSURE DROP
PSI
SPECIFIED HEAT DUTY
BTU/HR
MAXIMUM NO. ITERATIONS
CONVERGENCE TOLERANCE
OUTLET TEMPERATURE
OUTLET PRESSURE
VAPOR FRACTION

***
F
PSIA

RESULTS

3687.15

-0.123333E-

309883.
-0.110063E+10

0.00000
0.182364E-

***
0.0
0.0
30
0.000100000

***

279.50
652.67
0.33544

V-L PHASE EQUILIBRIUM :

COMP
TDA
0.37864E-03
O2
15.781
CO
27.731
TDI
0.14477E-02
WATER
0.87697E-01
TDCARB
0.69111E-06
SOLVENT
0.35714

F(I)
0.20563E-02

X(I)
0.30937E-02

Y(I)
0.11714E-05

0.26850E-02

0.45063E-03

0.71115E-02

0.23890

0.23969E-01

0.66472

0.15967E-01

0.24008E-01

0.34758E-04

0.18737E-01

0.27000E-01

0.23679E-02

0.62088E-02

0.93427E-02

0.64570E-08

0.71544

0.91214

0.32576

BLOCK: SP-100
MODEL: FSPLIT
-----------------------------INLET STREAM:
S-103
OUTLET STREAMS:
S-120
PROPERTY OPTION SET:
NRTL-RK
***
DIFF.

K(I)

S-127
RENON (NRTL) / REDLICH-KWONG

MASS AND ENERGY BALANCE

IN

***
OUT

RELATIVE

327

PhosgeneFreeRoutetoTolueneDiisocyanate

15
15

TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR

BouSaba,Dizon,Kasih,Stewart

2951.70

2951.70

84460.8
-0.147130E+09

)
***

INPUT DATA

84460.8
-0.147130E+09

0.154063E0.00000
-0.202558E-

***

328

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
60

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

SP-100

MODEL: FSPLIT (CONTINUED)

FRACTION OF FLOW

STRM=S-120
***

STREAM= S-120
ORDER=
1
S-127
2

RESULTS

SPLIT=

KEY=

0.70000

***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR

INPUT DATA

RESULTS

SPLIT=

BLOCK: SP-102
MODEL: FSPLIT
-----------------------------INLET STREAM:
S-118
OUTLET STREAMS:
S-119
PROPERTY OPTION SET:
NRTL-RK

RELATIVE
0.00000
0.157838E-

-0.358388E+08

0.00000

***

STRM=S-108
***

***
OUT

90.2484
23048.8

-0.358388E+08

FRACTION OF FLOW

STREAM-

S-116
RENON (NRTL) / REDLICH-KWONG

90.2484
23048.8

***

0
0

MASS AND ENERGY BALANCE

IN

0.30000

***
0.30000

BLOCK: SP-101
MODEL: FSPLIT
-----------------------------INLET STREAM:
S-107
OUTLET STREAMS:
S-108
PROPERTY OPTION SET:
NRTL-RK

STREAM= S-108
ORDER=
1
S-116
2

FRAC=

FRAC=

0.0100000

***
0.0100000
0.99000

KEY=

STREAM-

S-126
RENON (NRTL) / REDLICH-KWONG

329

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
61

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

U-O-S BLOCK SECTION

BLOCK:

SP-102

MODEL: FSPLIT (CONTINUED)

***

DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
15
ENTHALPY(BTU/HR

MASS AND ENERGY BALANCE

IN
9504.23
930508.

INPUT DATA

FRACTION OF FLOW

STREAM= S-119
ORDER=
1
S-126
2

RESULTS

SPLIT=

***
DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR)
MASS(LB/HR
)
ENTHALPY(BTU/HR

FRAC=

0.28000

KEY=

VALVE OUTLET PRESSURE

VALVE FLOW COEF CALC.

INPUT DATA

RESULTS
PSI

***
OUT

RELATIVE
0.00000
0.00000
0.00000

***
5.00000
NO

FLASH SPECIFICATIONS:
NPHASE
MAX NUMBER OF ITERATIONS
CONVERGENCE TOLERANCE

VALVE PRESSURE DROP

STREAM-

10279.4
0.100149E+07
-0.373429E+10

PSIA

***

RENON (NRTL) / REDLICH-KWONG

10279.4
0.100149E+07
-0.373429E+10
***

0.28000

***

MASS AND ENERGY BALANCE

IN

0.00000

***

0.72000

BLOCK: V-100
MODEL: VALVE
----------------------------INLET STREAM:
S-104
OUTLET STREAM:
S-105
PROPERTY OPTION SET:
NRTL-RK

0.00000
0.125109E-

-0.373101E+10

STRM=S-119
***

RELATIVE

9504.23
930508.

-0.373101E+10
***

***
OUT

2
30
0.000100000

***
647.670

330

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
62

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
CO O2 O2MAKEUP PSEUDLIQ PSEUDO
-----------------------------STREAM ID
PSEUDO
FROM :
TO
:

CO

O2

O2MAKEUP

PSEUDLIQ

---R-100

---R-100

---M-102

H-102
----

---R-100

VAPOR

VAPOR

MIXED

MIXED

0.0

0.0

SUBSTREAM: MIXED
PHASE:
VAPOR
COMPONENTS: LBMOL/HR
TDA
0.0
7.5920
O2
0.0
37.5670
CO
456.9050
3894.8980
TDI
0.0
59.0700
WATER
0.0
92.2390
TDCARB
0.0
22.8930
SOLVENT
0.0
1.1153+04
COMPONENTS: MOLE FRAC
TDA
0.0
04
O2
0.0
03
CO
1.0000
0.2551
TDI
0.0
03
WATER
0.0
03
TDCARB
0.0
03
SOLVENT
0.0
0.7305
COMPONENTS: LB/HR
TDA
0.0
927.5137
O2
0.0
1202.0989
CO
1.2798+04
1.0910+05
TDI
0.0
1.0288+04

191.4530

37.0000

7.5901
14.0667

0.0

0.0

1037.7956

0.0

0.0

59.0241

0.0

0.0

89.3016

0.0

0.0

22.8928

0.0

0.0

1.0733+04

0.0

0.0

6.3441-04

4.9728-

1.0000

1.0000

1.1757-03

2.4606-

0.0

0.0

8.6742-02

0.0

0.0

4.9334-03

3.8691-

0.0

0.0

7.4641-03

6.0417-

0.0

0.0

1.9135-03

1.4995-

0.0

0.0

0.8971

0.0

0.0

927.2855

6126.2663

1183.9556

450.1159

0.0

0.0

2.9069+04

0.0

0.0

1.0280+04

331

PhosgeneFreeRoutetoTolueneDiisocyanate

WATER
0.0
1661.7114
TDCARB
0.0
8567.4708
SOLVENT
0.0
1.1157+06
COMPONENTS: MASS FRAC
TDA
0.0
04
O2
0.0
04
CO
1.0000
02
TDI
0.0
03
WATER
0.0
03
TDCARB
0.0
03
SOLVENT
0.0
0.8944
TOTAL FLOW:
LBMOL/HR
456.9050
1.5267+04
LB/HR
1.2798+04
1.2475+06
CUFT/HR
5337.2006
6.5284+04
STATE VARIABLES:
TEMP
F
248.0000
248.0000
PRES
PSIA
652.6698
652.6698
VFRAC
1.0000
0.3091
LFRAC
0.0
0.6909
SFRAC
0.0
ENTHALPY:
BTU/LBMOL
-4.6396+04
3.0111+05
BTU/LB
-1656.3929
3685.1434
BTU/HR
-2.1199+07
4.5971+09

BouSaba,Dizon,Kasih,Stewart

0.0

0.0

1608.7928

0.0

0.0

8567.3938

0.0

0.0

1.0738+06

0.0

0.0

8.2449-04

7.4351-

1.0000

1.0000

4.0022-04

9.6362-

0.0

0.0

2.5847-02

8.7454-

0.0

0.0

9.1400-03

8.2467-

0.0

0.0

1.4304-03

1.3321-

0.0

0.0

7.6176-03

6.8678-

0.0

0.0

0.9547

191.4530

37.0000

1.1964+04

6126.2663

1183.9556

1.1247+06

2217.5683

428.3476

2.5080+04

248.0000

248.0000

248.0000

652.6698

653.0000

639.6698

1.0000

1.0000

8.4609-02

0.0

0.0

0.9154

0.0

0.0

0.0

1127.2831

1127.2428 -3.6015+05 -

35.2289

35.2277 -3831.1949 -

2.1582+05

4.1708+04 -4.3089+09 -

0.0

332

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
63

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
CO O2 O2MAKEUP PSEUDLIQ PSEUDO (CONTINUED)
STREAM ID
PSEUDO
ENTROPY:
BTU/LBMOL-R
91.1012
BTU/LB-R
1.1149
DENSITY:
LBMOL/CUFT
0.2339
LB/CUFT
19.1085
AVG MW
81.7103

CO

O2

O2MAKEUP

PSEUDLIQ

15.6175

-5.6828

-5.6838

-116.6837

0.5576

-0.1776

-0.1776

-1.2413

8.5608-02

8.6335-02

8.6378-02

0.4770

2.3979

2.7626

2.7640

44.8435

28.0104

31.9988

31.9988

94.0045

333

PhosgeneFreeRoutetoTolueneDiisocyanate

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VER: 23.0

04/07/2010

PAGE

STREAM SECTION
PSEUDVAP S-100 S-101 S-102 S-103
-------------------------------STREAM ID
FROM :
TO
:
100
SUBSTREAM: MIXED
PHASE:
COMPONENTS: LBMOL/HR
TDA
10
O2
21.0103
CO
2907.0878
TDI
07
WATER
02
TDCARB
15
SOLVENT
23.5866
COMPONENTS: MOLE FRAC
TDA
13
O2
03
CO
0.9849
TDI
10
WATER
06
TDCARB
19
SOLVENT
03
COMPONENTS: LB/HR
TDA
08
O2
672.3039
CO
8.1429+04
TDI
04

PSEUDVAP
H-104
----

S-100
R-100
R-101

S-101
R-101
C-100

S-102
C-100
F-100

S-103
F-100
SP-

VAPOR

MIXED

VAPOR

MIXED

VAPOR

1.4489-03

42.5657

9.5875-03

9.5875-03

4.2460-

23.5028

35.1097

31.0492

31.0492

2857.1063

3963.9824

3686.0113

3686.0113

4.2989-02

228.1766

0.1960

0.1960

6.1539-

2.9375

480.0596

23.1497

23.1497

1.2710-

7.9861-06

47.6967

2.0540-05

2.0540-05

2.0553-

419.4220

1.1104+04

1882.0240

1882.0240

4.3865-07

2.6768-03

1.7052-06

1.7052-06

1.4385-

7.1156-03

2.2079-03

5.5224-03

5.5224-03

7.1180-

0.8650

0.2493

0.6556

0.6556

1.3015-05

1.4349-02

3.4859-05

3.4859-05

2.0849-

8.8935-04

3.0189-02

4.1174-03

4.1174-03

4.3061-

2.4178-09

2.9995-03

3.6533-09

3.6533-09

6.9630-

0.1270

0.6983

0.3347

0.3347

7.9909-

0.1770

5200.2440

1.1713

1.1713

5.1873-

752.0626

1123.4676

993.5373

993.5373

8.0029+04

1.1103+05

1.0325+05

1.0325+05

7.4870

3.9739+04

34.1342

34.1342

1.0718-

334

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

WATER
52.9207 8648.4088
417.0485
417.0485
0.2290
TDCARB
2.9887-03 1.7850+04 7.6870-03 7.6870-03 7.691613
SOLVENT
4.1959+04 1.1109+06 1.8828+05 1.8828+05
2359.6160
COMPONENTS: MASS FRAC
TDA
1.4414-06 4.0173-03 3.9980-06 3.9980-06 6.141713
O2
6.1243-03 8.6790-04 3.3912-03 3.3912-03 7.959903
CO
0.6517 8.5775-02
0.3524
0.3524
0.9641
TDI
6.0969-05 3.0699-02 1.1651-04 1.1651-04 1.268909
WATER
4.3095-04 6.6811-03 1.4235-03 1.4235-03 2.711006
TDCARB
2.4338-08 1.3790-02 2.6238-08 2.6238-08 9.106718
SOLVENT
0.3417
0.8582
0.6427
0.6427 2.793702
TOTAL FLOW:
LBMOL/HR
3303.0132 1.5902+04 5622.4398 5622.4398
2951.6974
LB/HR
1.2280+05 1.2945+06 2.9297+05 2.9297+05
8.4461+04
CUFT/HR
3.8352+04 7.6529+04 6.3130+04 2.9754+04
2.7073+04
STATE VARIABLES:
TEMP
F
248.0000
282.7646
282.7646
100.0000
99.9092
PRES
PSIA
639.6698
652.6698
652.6698
647.6698
644.6698
VFRAC
1.0000
0.3536
1.0000
0.5248
1.0000
LFRAC
0.0
0.6464
0.0
0.4752
0.0
SFRAC
0.0
0.0
0.0
0.0
0.0
ENTHALPY:
BTU/LBMOL
-8.8704+04 -2.9079+05 -1.5827+05 -1.6708+05 4.9846+04
BTU/LB
-2385.9149 -3572.2443 -3037.3316 -3206.4374 1741.9918
BTU/HR
-2.9299+08 -4.6241+09 -8.8985+08 -9.3939+08 1.4713+08

335

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
65

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
PSEUDVAP S-100 S-101 S-102 S-103 (CONTINUED)
STREAM ID
ENTROPY:
BTU/LBMOL-R
12.8541
BTU/LB-R
0.4492
DENSITY:
LBMOL/CUFT
0.1090
LB/CUFT
3.1198
AVG MW
28.6143

PSEUDVAP

S-100

S-101

S-102

-0.4432

-86.2780

-26.8791

-40.1237

-1.1922-02

-1.0599

-0.5158

-0.7700

8.6125-02

0.2078

8.9061-02

0.1890

3.2020

16.9147

4.6407

9.8465

37.1783

81.4036

52.1075

52.1075

S-103

336

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
66

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-104 S-105 S-106 S-107 S-108
----------------------------STREAM ID
FROM :
101
TO
:
SUBSTREAM: MIXED
PHASE:
LIQUID
COMPONENTS: LBMOL/HR
TDA
0.4255
O2
CO
TDI
05
WATER
25
TDCARB
0.4770
SOLVENT
22
COMPONENTS: MOLE FRAC
TDA
0.4715
O2
CO
TDI
05
WATER
25
TDCARB
0.5285
SOLVENT
22
COMPONENTS: LB/HR
TDA
51.9804
O2
CO
TDI
03
WATER
24
TDCARB
178.5001

S-104
R-101

S-105
V-100

S-106
D-100

S-107
P-100

S-108
SP-

V-100

D-100

P-100

SP-101

C-101

LIQUID

MIXED

LIQUID

LIQUID

42.5561

42.5561

42.5477

42.5477

4.0605
277.9710
227.9806

4.0605
277.9710
227.9806

0.0
0.0
4.0319-03

0.0
0.0
4.0319-03

0.0
0.0
4.0319-

456.9099

456.9099

1.2620-23

1.2620-23

1.2620-

47.6967

47.6967

47.6967

47.6967

9222.1896

9222.1896

7.8168-20

7.8168-20

4.1400-03

4.1400-03

0.4715

0.4715

3.9501-04
2.7042-02
2.2178-02

3.9501-04
2.7042-02
2.2178-02

0.0
0.0
4.4676-05

0.0
0.0
4.4676-05

0.0
0.0
4.4676-

4.4449-02

4.4449-02

1.3984-25

1.3984-25

1.3984-

4.6400-03

4.6400-03

0.5285

0.5285

0.8972

0.8972

8.6615-22

8.6615-22

5199.0727

5199.0727

5198.0427

5198.0427

129.9303
7786.0794
3.9705+04

129.9303
7786.0794
3.9705+04

0.0
0.0
0.7022

0.0
0.0
0.7022

0.0
0.0
7.0220-

8231.3604

8231.3604

2.2736-22

2.2736-22

2.2736-

1.7850+04

1.7850+04

1.7850+04

1.7850+04

7.8168-

8.6615-

337

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

SOLVENT
9.2259+05 9.2259+05 7.8200-18 7.8200-18 7.820020
COMPONENTS: MASS FRAC
TDA
5.1913-03 5.1913-03
0.2255
0.2255
0.2255
O2
1.2974-04 1.2974-04
0.0
0.0
0.0
CO
7.7745-03 7.7745-03
0.0
0.0
0.0
TDI
3.9646-02 3.9646-02 3.0466-05 3.0466-05 3.046605
WATER
8.2191-03 8.2191-03 9.8643-27 9.8643-27 9.864327
TDCARB
1.7823-02 1.7823-02
0.7744
0.7744
0.7744
SOLVENT
0.9212
0.9212 3.3928-22 3.3928-22 3.392822
TOTAL FLOW:
LBMOL/HR
1.0279+04 1.0279+04
90.2484
90.2484
0.9025
LB/HR
1.0015+06 1.0015+06 2.3049+04 2.3049+04
230.4875
CUFT/HR
1.3399+04 6.3259+06
280.4083
280.9195
2.8092
STATE VARIABLES:
TEMP
F
282.7646
96.7787
517.8417
521.1076
521.1076
PRES
PSIA
652.6698
5.0000
4.9000
653.0000
653.0000
VFRAC
0.0
0.5187
0.0
0.0
0.0
LFRAC
1.0000
0.4813
1.0000
1.0000
1.0000
SFRAC
0.0
0.0
0.0
0.0
0.0
ENTHALPY:
BTU/LBMOL
-3.6328+05 -3.6328+05 -3.9758+05 -3.9711+05 3.9711+05
BTU/LB
-3728.7247 -3728.7247 -1556.7352 -1554.9114 1554.9114
BTU/HR
-3.7343+09 -3.7343+09 -3.5881+07 -3.5839+07 3.5839+05

338

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
67

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-104 S-105 S-106 S-107 S-108 (CONTINUED)
STREAM ID
ENTROPY:
BTU/LBMOL-R
187.1685
BTU/LB-R
0.7329
DENSITY:
LBMOL/CUFT
0.3213
LB/CUFT
82.0475
AVG MW
255.3923

S-104

S-105

S-106

S-107

-118.7670

-116.0471

-187.3015

-187.1685

-1.2190

-1.1911

-0.7334

-0.7329

0.7672

1.6250-03

0.3218

0.3213

74.7457

0.1583

82.1971

82.0475

97.4275

97.4275

255.3923

255.3923

S-108
-

339

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
68

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-109 S-110 S-111 S-112 S-113
----------------------------STREAM ID
FROM :
TO
:
SUBSTREAM: MIXED
PHASE:
LIQUID
COMPONENTS: LBMOL/HR
TDA
03
O2
CO
TDI
227.7057
WATER
0.2669
TDCARB
SOLVENT
14
COMPONENTS: MOLE FRAC
TDA
05
O2
CO
TDI
0.9988
WATER
03
TDCARB
SOLVENT
16
COMPONENTS: LB/HR
TDA
1.0299
O2
CO
TDI
3.9657+04
WATER
4.8083
TDCARB
SOLVENT
12
COMPONENTS: MASS FRAC
TDA
05

S-109
D-100
P-101

S-110
P-101
H-100

S-111
H-100
D-101

S-112
D-101
D-102

S-113
D-102
P-102

LIQUID

LIQUID

MIXED

LIQUID

8.4308-03

8.4308-03

8.4308-03

8.4308-03

4.0605
277.9710
227.9766

4.0605
277.9710
227.9766

4.0605
277.9710
227.9766

2.5561-27
3.7754-28
227.9766

456.9099

456.9099

456.9099

456.9009

9.7456-33
9222.1896

9.7456-33
9222.1896

9.7456-33
9222.1896

0.0
9.7737-05

0.0
6.5654-

8.2744-07

8.2744-07

8.2744-07

1.2310-05

3.6978-

3.9851-04
2.7281-02
2.2375-02

3.9851-04
2.7281-02
2.2375-02

3.9851-04
2.7281-02
2.2375-02

3.7321-30
5.5124-31
0.3329

4.4843-02

4.4843-02

4.4843-02

0.6671

1.1707-

0.0
0.9051

0.0
0.9051

0.0
0.9051

0.0
1.4271-07

0.0
2.8798-

1.0300

1.0300

1.0300

1.0300

129.9303
7786.0794
3.9704+04

129.9303
7786.0794
3.9704+04

129.9303
7786.0794
3.9704+04

8.1792-26
1.0575-26
3.9704+04

8231.3604

8231.3604

8231.3604

8231.1978

3.6472-30
9.2259+05

3.6472-30
9.2259+05

3.6472-30
9.2259+05

0.0
9.7777-03

0.0
6.5681-

1.0527-06

1.0527-06

1.0527-06

2.1487-05

2.5967-

8.43020.0
0.0

0.0
0.0

0.0
0.0

340

PhosgeneFreeRoutetoTolueneDiisocyanate

O2
CO
TDI
0.9999
WATER
04
TDCARB
SOLVENT
16
TOTAL FLOW:
LBMOL/HR
227.9810
LB/HR
3.9663+04
CUFT/HR
604.5752
STATE VARIABLES:
TEMP
F
352.2005
PRES
PSIA
2.0077
VFRAC
LFRAC
1.0000
SFRAC
ENTHALPY:
BTU/LBMOL
3.6978+04
BTU/LB
212.5500
BTU/HR
8.4303+06

BouSaba,Dizon,Kasih,Stewart

1.3279-04
7.9576-03
4.0579-02

1.3279-04
7.9576-03
4.0579-02

1.3279-04
7.9576-03
4.0579-02

1.7063-30
2.2060-31
0.8283

0.0
0.0

8.4127-03

8.4127-03

8.4127-03

0.1717

1.2123-

0.0
0.9429

0.0
0.9429

0.0
0.9429

0.0
2.0397-07

0.0
1.6560-

1.0189+04

1.0189+04

1.0189+04

684.8860

9.7844+05

9.7844+05

9.7844+05

4.7936+04

9784.4437

9784.7549

7.9572+06

709.8577

34.9811

35.0177

120.0000

200.7140

2.0000

12.0000

7.0000

7.8000

0.0
1.0000

0.0
1.0000

0.8870
0.1130

0.0
1.0000

0.0

0.0

0.0

0.0

0.0

0.0

-3.7322+05 -3.7322+05 -3.5620+05 -9.6220+04 -3886.5552 -3886.5321 -3709.3534 -1374.7336

-3.8028+09 -3.8028+09 -3.6294+09 -6.5900+07 -

341

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
69

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-109 S-110 S-111 S-112 S-113 (CONTINUED)
STREAM ID
ENTROPY:
BTU/LBMOL-R
53.4247
BTU/LB-R
0.3071
DENSITY:
LBMOL/CUFT
0.3771
LB/CUFT
65.6044
AVG MW
173.9742

S-109

S-110

S-111

S-112

-134.5877

-134.5868

-104.1612

-44.7538

-1.4015

-1.4015

-1.0847

-0.6394

1.0414

1.0413

1.2805-03

0.9648

100.0000

99.9968

0.1230

67.5296

96.0284

96.0284

96.0284

69.9918

S-113
-

342

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
70

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-114 S-115 S-116 S-117 S-118
----------------------------STREAM ID
FROM :
TO
:
102
SUBSTREAM: MIXED
PHASE:
LIQUID
COMPONENTS: LBMOL/HR
TDA
O2
4.0605
CO
277.9710
TDI
33
WATER
03
TDCARB
SOLVENT
9222.1895
COMPONENTS: MOLE FRAC
TDA
O2
04
CO
02
TDI
WATER
07
TDCARB
SOLVENT
0.9703
COMPONENTS: LB/HR
TDA
O2
129.9303
CO
7786.0794
TDI
30
WATER
0.1626
TDCARB
SOLVENT
9.2259+05

S-114
P-102
C-102

S-115
D-102
P-103

S-116
SP-101
M-100

S-117
D-101
P-104

LIQUID

LIQUID

LIQUID

LIQUID

8.4302-03
0.0

6.4653-07
0.0

42.1222
0.0

0.0

0.0

0.0
4.0605

0.0

277.9710

S-118
P-104
SP-

0.0

227.7057

0.2709

3.9916-03

8.3292-33

8.3292-

0.2669

456.6340

1.2494-23

9.0236-03

9.0236-

0.0
6.5654-14

0.0
9.7737-05

47.2197
7.7387-20

0.0
9222.1895

3.6978-05
0.0

1.4150-09
0.0

0.4715
0.0

0.0
4.2723-04

0.0
4.2723-

0.0

0.0

0.0

2.9247-02

2.9247-

0.9988
1.1707-03

5.9289-04
0.9994

4.4676-05
1.3984-25

0.0
9.4943-07

0.0
9.4943-

0.0
2.8798-16

0.0
2.1391-07

0.5285
8.6615-22

0.0
0.9703

0.0

1.0299
0.0

7.8987-05
0.0

5146.0623
0.0

0.0
129.9303

0.0

0.0

0.0

7786.0794

0.0
3.9657+04

47.1788

0.6952

1.4506-30

4.8083

8226.3895

2.2509-22

0.1626

0.0
6.5681-12

0.0
9.7777-03

1.7672+04
7.7418-18

0.0
9.2259+05

0.0

1.4506-

0.0

343

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

COMPONENTS: MASS FRAC

TDA
2.5967-05 9.5469-09
0.2255
0.0
0.0
O2
0.0
0.0
0.0
1.3963-04 1.396304
CO
0.0
0.0
0.0
8.3676-03 8.367603
TDI
0.9999 5.7023-03 3.0466-05
0.0
0.0
WATER
1.2123-04
0.9943 9.8643-27 1.7470-07 1.747007
TDCARB
0.0
0.0
0.7744
0.0
0.0
SOLVENT
1.6560-16 1.1818-06 3.3928-22
0.9915
0.9915
TOTAL FLOW:
LBMOL/HR
227.9810
456.9050
89.3459 9504.2300
9504.2300
LB/HR
3.9663+04 8273.5781 2.2818+04 9.3051+05
9.3051+05
CUFT/HR
604.5941
135.0907
278.1103 9155.6965
9176.0148
STATE VARIABLES:
TEMP
F
352.2510
101.7049
521.1076
34.0916
36.5130
PRES
PSIA
7.0077
1.0000
653.0000
5.0000
653.0000
VFRAC
0.0
0.0
0.0
0.0
0.0
LFRAC
1.0000
1.0000
1.0000
1.0000
1.0000
SFRAC
0.0
0.0
0.0
0.0
0.0
ENTHALPY:
BTU/LBMOL
-3.6973+04 -1.2237+05 -3.9711+05 -3.9271+05 3.9256+05
BTU/LB
-212.5217 -6757.7138 -1554.9114 -4011.1232 4009.6484
BTU/HR
-8.4292+06 -5.5910+07 -3.5480+07 -3.7324+09 3.7310+09

344

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
71

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-114 S-115 S-116 S-117 S-118 (CONTINUED)
STREAM ID
ENTROPY:
BTU/LBMOL-R
140.8045
BTU/LB-R
1.4382
DENSITY:
LBMOL/CUFT
1.0358
LB/CUFT
101.4065
AVG MW
97.9046

S-114

S-115

S-116

S-117

-53.4217

-38.1227

-187.1685

-140.8660

-0.3071

-2.1053

-0.7329

-1.4388

0.3771

3.3822

0.3213

1.0381

65.6024

61.2446

82.0475

101.6316

173.9742

18.1079

255.3923

97.9046

S-118
-

345

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
72

PLAT: WIN32

BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-119 S-120 S-121 S-122 S-123
----------------------------STREAM ID
FROM :
TO
:
SUBSTREAM: MIXED
PHASE:
COMPONENTS: LBMOL/HR
TDA
7.5820
O2
9.8998
CO
880.8778
TDI
58.8711
WATER
69.0867
TDCARB
22.8928
SOLVENT
2637.9430
COMPONENTS: MOLE FRAC
TDA
03
O2
03
CO
0.2389
TDI
02
WATER
02
TDCARB
03
SOLVENT
0.7154
COMPONENTS: LB/HR
TDA
926.2912
O2
316.7826
CO
2.4674+04
TDI
1.0253+04

S-119
SP-102
M-100

S-120
SP-100
M-102

S-121
M-100
H-101

S-122
H-101
R-102

S-123
R-102
R-103

LIQUID

VAPOR

LIQUID

LIQUID

MIXED

0.0

1.2738-10

42.1222

42.1222

1.1369

6.3031

1.1369

1.1369

77.8319

872.1263

77.8319

77.8319

2.3322-33

1.8462-07

3.9916-03

3.9916-03

2.5266-03

3.8130-03

2.5266-03

2.5266-03

0.0

6.1658-16

47.2197

47.2197

7.0760

2582.2131

2582.2131

0.0

1.4385-13

1.5314-02

1.5314-02

2.0563-

4.2723-04

7.1180-03

4.1335-04

4.1335-04

2.6850-

2.9247-02

0.9849

2.8297-02

2.8297-02

0.0

2.0849-10

1.4512-06

1.4512-06

1.5967-

9.4943-07

4.3061-06

9.1859-07

9.1859-07

1.8737-

0.0

6.9630-19

1.7168-02

1.7168-02

6.2088-

0.9703

7.9909-03

0.9388

0.9388

0.0

1.5562-08

5146.0623

5146.0623

36.3805

201.6912

36.3805

36.3805

2180.1022

2.4429+04

2180.1022

2180.1022

4.0617-31

3.2153-05

0.6952

0.6952

2582.2131

346

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

WATER
4.5518-02 6.8693-02 4.5518-02 4.5518-02
1244.6167
TDCARB
0.0
2.3075-13 1.7672+04 1.7672+04
8567.3891
SOLVENT
2.5833+05
707.8848 2.5833+05 2.5833+05
2.6390+05
COMPONENTS: MASS FRAC
TDA
0.0
6.1417-13 1.8161-02 1.8161-02 2.989203
O2
1.3963-04 7.9599-03 1.2839-04 1.2839-04 1.022303
CO
8.3676-03
0.9641 7.6937-03 7.6937-03 7.962302
TDI
0.0
1.2689-09 2.4533-06 2.4533-06 3.308702
WATER
1.7470-07 2.7110-06 1.6064-07 1.6064-07 4.016403
TDCARB
0.0
9.1067-18 6.2364-02 6.2364-02 2.764702
SOLVENT
0.9915 2.7937-02
0.9117
0.9117
0.8516
TOTAL FLOW:
LBMOL/HR
2661.1844
885.5092 2750.5303 2750.5303
3687.1533
LB/HR
2.6054+05 2.5338+04 2.8336+05 2.8336+05
3.0988+05
CUFT/HR
2569.2842 8121.7701 2901.2637 3511.3056
1.7095+04
STATE VARIABLES:
TEMP
F
36.5130
99.9092
74.9579
248.0000
279.5000
PRES
PSIA
653.0000
644.6698
653.0000
648.0000
652.6698
VFRAC
0.0
1.0000
0.0
0.0
0.3354
LFRAC
1.0000
0.0
1.0000
1.0000
0.6646
SFRAC
0.0
0.0
0.0
0.0
0.0
ENTHALPY:
BTU/LBMOL
-3.9256+05 -4.9846+04 -3.9271+05 -3.8522+05 2.9851+05
BTU/LB
-4009.6484 -1741.9918 -3811.9749 -3739.2476 3551.7763
BTU/HR
-1.0447+09 -4.4139+07 -1.0802+09 -1.0596+09 1.1006+09

347

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
73

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VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-119 S-120 S-121 S-122 S-123 (CONTINUED)
STREAM ID
ENTROPY:
BTU/LBMOL-R
89.5060
BTU/LB-R
1.0650
DENSITY:
LBMOL/CUFT
0.2157
LB/CUFT
18.1269
AVG MW
84.0439

S-119

S-120

S-121

S-122

-140.8045

12.8541

-141.0933

-129.1905

-1.4382

0.4492

-1.3696

-1.2540

1.0358

0.1090

0.9480

0.7833

101.4065

3.1198

97.6679

80.6995

97.9046

28.6143

103.0203

103.0203

S-123
-

348

PhosgeneFreeRoutetoTolueneDiisocyanate

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74

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VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-124 S-125 S-126 S-127 S-128
----------------------------STREAM ID
FROM :
TO
:
SUBSTREAM: MIXED
PHASE:
LIQUID
COMPONENTS: LBMOL/HR
TDA
03
O2
10.0389
CO
778.9235
TDI
0.1960
WATER
23.1370
TDCARB
05
SOLVENT
1858.4373
COMPONENTS: MOLE FRAC
TDA
06
O2
03
CO
0.2917
TDI
05
WATER
03
TDCARB
09
SOLVENT
0.6959
COMPONENTS: LB/HR
TDA
1.1713
O2
321.2334
CO
2.1818+04
TDI
34.1341

S-124
R-103
M-103

S-125
R-103
M-101

S-126
SP-102
M-101

S-127
SP-100
M-103

VAPOR

LIQUID

LIQUID

VAPOR
2.9722-10

S-128
F-100
M-101

1.4489-03

7.5805

0.0

9.5875-

8.7956

1.1042

2.9235

14.7072

822.1449

58.7330

200.1391

2034.9615

4.2989-02

58.8282

5.9970-33

4.3078-07

2.9286

66.1581

6.4970-03

8.8971-03

7.9861-06

22.8928

0.0

1.4387-15

402.9114

2235.0316

6639.9764

1.1714-06

3.0937-03

0.0

1.4385-13

3.5898-

7.1115-03

4.5063-04

4.2723-04

7.1180-03

3.7589-

0.6647

2.3969-02

2.9247-02

0.9849

3.4758-05

2.4008-02

0.0

2.0849-10

7.3386-

2.3679-03

2.7000-02

9.4943-07

4.3061-06

8.6631-

6.4570-09

9.3427-03

0.0

6.9630-19

7.6908-

0.3258

0.9121

0.9703

7.9909-03

0.1770

926.1142

0.0

3.6311-08

281.4499

35.3327

93.5498

470.6127

2.3029+04

1645.1336

5605.9771

5.7000+04

7.4869

1.0245+04

1.0444-30

7.5023-05

2.0540-

16.5106

349

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

WATER
52.7604 1191.8562
0.1170
0.1603
416.8195
TDCARB
2.9887-03 8567.3861
0.0
5.3841-13 7.687003
SOLVENT
4.0307+04 2.2359+05 6.6427+05 1651.7312
1.8592+05
COMPONENTS: MASS FRAC
TDA
2.7798-06 3.7616-03
0.0
6.1417-13 5.617506
O2
4.4199-03 1.4351-04 1.3963-04 7.9599-03 1.540603
CO
0.3616 6.6820-03 8.3676-03
0.9641
0.1046
TDI
1.1757-04 4.1614-02
0.0
1.2689-09 1.637004
WATER
8.2855-04 4.8409-03 1.7470-07 2.7110-06 1.999003
TDCARB
4.6935-08 3.4798-02
0.0
9.1067-18 3.686608
SOLVENT
0.6330
0.9082
0.9915 2.7937-02
0.8917
TOTAL FLOW:
LBMOL/HR
1236.8250 2450.3283 6843.0456 2066.1882
2670.7424
LB/HR
6.3678+04 2.4620+05 6.6997+05 5.9123+04
2.0851+05
CUFT/HR
1.3866+04 3228.6247 6606.7309 1.8951+04
2811.6950
STATE VARIABLES:
TEMP
F
279.5008
279.5008
36.5130
99.9092
99.9092
PRES
PSIA
652.6698
652.6698
653.0000
644.6698
644.6698
VFRAC
1.0000
0.0
0.0
1.0000
0.0
LFRAC
0.0
1.0000
1.0000
0.0
1.0000
SFRAC
0.0
0.0
0.0
0.0
0.0
ENTHALPY:
BTU/LBMOL
-1.5513+05 -3.7088+05 -3.9256+05 -4.9846+04 2.9665+05
BTU/LB
-3013.0852 -3691.1024 -4009.6484 -1741.9918 3799.6378
BTU/HR
-1.9187+08 -9.0877+08 -2.6863+09 -1.0299+08 7.9226+08

350

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
75

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VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-124 S-125 S-126 S-127 S-128 (CONTINUED)
STREAM ID
ENTROPY:
BTU/LBMOL-R
98.6633
BTU/LB-R
1.2637
DENSITY:
LBMOL/CUFT
0.9499
LB/CUFT
74.1582
AVG MW
78.0720

S-124

S-125

S-126

S-127

-25.7536

-121.6856

-140.8045

12.8541

-0.5002

-1.2111

-1.4382

0.4492

8.9195-02

0.7589

1.0358

0.1090

4.5922

76.2569

101.4065

3.1198

51.4850

100.4783

97.9046

28.6143

S-128
-

351

PhosgeneFreeRoutetoTolueneDiisocyanate

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76

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VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-129 S-130 S-131 S-132 SLUDGE
-----------------------------STREAM ID
SLUDGE
FROM :
TO
:
SUBSTREAM: MIXED
PHASE:
LIQUID
COMPONENTS: LBMOL/HR
TDA
0.4255
O2
CO
TDI
05
WATER
25
TDCARB
0.4770
SOLVENT
22
COMPONENTS: MOLE FRAC
TDA
0.4715
O2
CO
TDI
05
WATER
25
TDCARB
0.5285
SOLVENT
22
COMPONENTS: LB/HR
TDA
51.9804
O2
CO
TDI
03
WATER
24
TDCARB
178.5001

S-129

S-130

S-131

S-132

M-101
H-102

M-103
H-104

M-102
H-103

H-103
R-102

LIQUID

MIXED

VAPOR

VAPOR

7.5901

1.4489-03

1.2738-10

1.2738-10

14.0667
1037.7956
59.0241

23.5028
2857.1063
4.2989-02

43.3031
872.1263
1.8462-07

43.3031
872.1263
1.8462-07

0.0
0.0
4.0319-

89.3016

2.9375

3.8130-03

3.8130-03

1.2620-

22.8928

7.9861-06

6.1658-16

6.1658-16

1.0733+04

419.4220

7.0760

7.0760

6.3441-04

4.3865-07

1.3808-13

1.3808-13

1.1757-03
8.6742-02
4.9334-03

7.1156-03
0.8650
1.3015-05

4.6941-02
0.9454
2.0013-10

4.6941-02
0.9454
2.0013-10

0.0
0.0
4.4676-

7.4641-03

8.8935-04

4.1333-06

4.1333-06

1.3984-

1.9135-03

2.4178-09

6.6837-19

6.6837-19

0.8971

0.1270

7.6704-03

7.6704-03

927.2855

0.1770

1.5562-08

1.5562-08

450.1159
2.9069+04
1.0280+04

752.0626
8.0029+04
7.4870

1385.6468
2.4429+04
3.2153-05

1385.6468
2.4429+04
3.2153-05

0.0
0.0
7.0220-

1608.7928

52.9207

6.8693-02

6.8693-02

2.2736-

8567.3938

2.9887-03

2.3075-13

2.3075-13

C-101
----

7.8168-

8.6615-

352

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

SOLVENT
1.0738+06 4.1959+04
707.8848
707.8848 7.820020
COMPONENTS: MASS FRAC
TDA
8.2449-04 1.4414-06 5.8675-13 5.8675-13
0.2255
O2
4.0022-04 6.1243-03 5.2245-02 5.2245-02
0.0
CO
2.5847-02
0.6517
0.9211
0.9211
0.0
TDI
9.1400-03 6.0969-05 1.2123-09 1.2123-09 3.046605
WATER
1.4304-03 4.3095-04 2.5900-06 2.5900-06 9.864327
TDCARB
7.6176-03 2.4338-08 8.7002-18 8.7002-18
0.7744
SOLVENT
0.9547
0.3417 2.6690-02 2.6690-02 3.392822
TOTAL FLOW:
LBMOL/HR
1.1964+04 3303.0132
922.5092
922.5092
0.9025
LB/HR
1.1247+06 1.2280+05 2.6522+04 2.6522+04
230.4875
CUFT/HR
1.2669+04 3.5336+04 8556.0116 1.0976+04
2.3532
STATE VARIABLES:
TEMP
F
118.7007
208.6551
105.7438
248.0000
140.0000
PRES
PSIA
644.6698
644.6698
644.6698
639.6698
648.0000
VFRAC
0.0
0.9867
1.0000
1.0000
0.0
LFRAC
1.0000 1.3279-02
0.0
0.0
1.0000
SFRAC
0.0
0.0
0.0
0.0
0.0
ENTHALPY:
BTU/LBMOL
-3.6671+05 -8.9269+04 -4.7801+04 -4.6736+04 4.2798+05
BTU/LB
-3900.9803 -2401.1142 -1662.6564 -1625.6031 1675.7704
BTU/HR
-4.3874+09 -2.9486+08 -4.4097+07 -4.3115+07 3.8624+05

353

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
77

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
S-129 S-130 S-131 S-132 SLUDGE (CONTINUED)
STREAM ID
SLUDGE
ENTROPY:
BTU/LBMOL-R
224.3002
BTU/LB-R
0.8783
DENSITY:
LBMOL/CUFT
0.3835
LB/CUFT
97.9454
AVG MW
255.3923

S-129

S-130

S-131

S-132

-1.2859

12.4156

14.1122

-1.3474 -3.4586-02

0.4318

0.4909

-126.6648

0.9443

9.3475-02

0.1078

8.4047-02

88.7711

3.4753

3.0998

2.4164

94.0045

37.1783

28.7501

28.7501

354

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
78

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BouSaba,Dizon,Kasih,Stewart

VER: 23.0

04/07/2010

PAGE

STREAM SECTION
SOLVENT TDA TDI WASTEWTR
-----------------------STREAM ID
FROM :
TO
:
SUBSTREAM: MIXED
PHASE:
COMPONENTS: LBMOL/HR
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT
COMPONENTS: MOLE FRAC
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT
COMPONENTS: LB/HR
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT
COMPONENTS: MASS FRAC
TDA
O2
CO
TDI
WATER
TDCARB
SOLVENT
TOTAL FLOW:
LBMOL/HR
LB/HR
CUFT/HR
STATE VARIABLES:
TEMP
F
PRES
PSIA
VFRAC

SOLVENT
---R-100

TDA
---R-100

TDI
C-102
----

WASTEWTR
P-103
----

LIQUID

LIQUID

LIQUID

LIQUID

0.0
0.0
0.0
0.0
0.0
0.0
0.9530

228.8840
0.0
0.0
0.0
0.0
0.0
0.0

8.4302-03
0.0
0.0
227.7057
0.2669
0.0
6.5654-14

6.4653-07
0.0
0.0
0.2709
456.6340
0.0
9.7737-05

0.0
0.0
0.0
0.0
0.0
0.0
1.0000

1.0000
0.0
0.0
0.0
0.0
0.0
0.0

3.6978-05
0.0
0.0
0.9988
1.1707-03
0.0
2.8798-16

1.4150-09
0.0
0.0
5.9289-04
0.9994
0.0
2.1391-07

0.0
0.0
0.0
0.0
0.0
0.0
95.3385

2.7963+04
0.0
0.0
0.0
0.0
0.0
0.0

1.0299
0.0
0.0
3.9657+04
4.8083
0.0
6.5681-12

7.8987-05
0.0
0.0
47.1788
8226.3895
0.0
9.7777-03

0.0
0.0
0.0
0.0
0.0
0.0
1.0000

1.0000
0.0
0.0
0.0
0.0
0.0
0.0

2.5967-05
0.0
0.0
0.9999
1.2123-04
0.0
1.6560-16

9.5469-09
0.0
0.0
5.7023-03
0.9943
0.0
1.1818-06

0.9530
95.3385
1.1828

228.8840
2.7963+04
434.6271

227.9810
3.9663+04
538.8068

456.9050
8273.5781
135.0938

248.0000
652.6698
0.0

248.0000
652.6698
0.0

140.0000
2.0077
0.0

101.7455
6.0000
0.0

355

PhosgeneFreeRoutetoTolueneDiisocyanate

LFRAC
SFRAC
ENTHALPY:
BTU/LBMOL
BTU/LB
BTU/HR

1.0000
0.0
-3.9398+05
-3938.2172
-3.7546+05

1.0000
0.0

BouSaba,Dizon,Kasih,Stewart
1.0000
0.0

1.0000
0.0

2399.5664 -5.0984+04 -1.2237+05

19.6412 -293.0522 -6757.6627
5.4922+05 -1.1623+07 -5.5910+07

356

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
79

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VER: 23.0

04/07/2010

PAGE

STREAM SECTION
SOLVENT TDA TDI WASTEWTR (CONTINUED)
STREAM ID
ENTROPY:
BTU/LBMOL-R
BTU/LB-R
DENSITY:
LBMOL/CUFT
LB/CUFT
AVG MW

SOLVENT

TDA

TDI

WASTEWTR

-130.4803
-1.3043

-135.4934
-1.1091

-73.2656
-0.4211

-38.1216
-2.1052

0.8057
80.6007
100.0404

0.5266
64.3373
122.1699

0.4231
73.6123
173.9742

3.3821
61.2432
18.1079

357

PhosgeneFreeRoutetoTolueneDiisocyanate

ASPEN PLUS
80

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VER: 23.0

04/07/2010

PAGE

PROBLEM STATUS SECTION

BLOCK STATUS
-----------**************************************************************************
**
*
*
* Calculations were completed normally
*
*
*
* All Unit Operation blocks were completed normally
*
*
*
* All streams were flashed normally
*
*
*
* Properties estimation was completed normally
*
*
*
**************************************************************************
**

358

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

359

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Appendix9:MaterialSafety
DataSheets

360

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

Material Safety Data Sheet

Science Stuff, Inc.
1104 Newport Ave
Austin, TX 78753

Phone
Chemtrec 800-424-9300
24 Hour Emergency Assistance

Section 1 Identification
Product
Number:

Section 6 Accidental Release Mea

C2656

Health:
Flammability
Sodium
Product Name: Iodide Laboratory Reactivity
Grade, Granular Hazard Rating:
Trade/Chemical
Synonyms
Formula:

NaI

RTECS:

WB6475000

C.A.S

CAS# 7681-82-5

2
0
0

Least Slight Moderate High Extreme

0
1
2
3
4
NA = Not Applicable NE = Not
Established

Component CAS Number

Sodium
Iodide

Section 7 Handling and Storage

Store in a cool, dry, well-ventilate

from incompatible materials. Was
handling.

Section 8 Exposure Controls & Pe

Respiratory Protection:NIOSH/M
respirator
Mechanical:

Section 2 Component Mixture

Sara
313

Dispose of in a manner consistent

state and local regulations.

Protec

Ventilation:
%

Dim

Exposure Limits:

TXDS: orl-rat
CAS# 7681-82-5 100% W/W LD: 4340
mg/Kg

Section 3 Hazard Identification (Also see section 11)

Harmful if swallowed. May cause irritation. Avoid breathing vapors, or
dusts. Use with adequate ventilation. Avoid contact with eyes, skin, and
clothes. Wash thoroughly after handling. Keep container closed.
Section 4 First Aid Measures
Harmful if swallowed. May cause irritation. Avoid breathing vapors, or
dusts. Use with adequate ventilation. Avoid contact with eyes, skin, and

Local

Protec
Exhaust:
Other Protective Equipment: Use
Section 9 Physical and Chemical
Melting
Point:

651 C

Boiling
Point:

1300 C

Vapor
Pressure:
Vapor

Information
Evapora
not
Rate:
available
Information Evapora
361

Specific
Gravity
Percent
Volatile
Volume

PhosgeneFreeRoutetoTolueneDiisocyanate

BouSaba,Dizon,Kasih,Stewart

clothes. Wash thoroughly after handling. Keep container closed.

Density:

FIRST AID: SKIN: Remove contaminated clothing. Wash exposed area

with soap and water. If symptoms persist, seek medical attention

Solubility
in Water:

EYES: Wash eyes with plenty of water for at least 15 minutes, lifting lids
occasionally. Seek Medical Aid. INHALATION: Remove to fresh air. If
not breathing, give artificial respiration. If breathing is difficult, give
oxygen
INGESTION: If swallowed, induce vomiting immediately after giving two
glasses of water. Never give anything by mouth to an unconcious person.
Section 5 Fire Fighting Measures
Fire Extinguisher Any means suitable for extinguishing surrounding fire
Type:
Fire/Explosion
None
Hazards:
Wear self-contained breathing apparatus and
Fire Fighting
protective clothing to prevent contact with skin and
Procedure:
clothing.

not
available

Standard

Auto ign
Temper
White
Lower
Appearance
crystals / Flamm.
and Odor:
No odor
Limit in
Information Upper
Flash
not
Flamm.
Point:
available Limit in
Soluble

Section 10 Stability and Reactivit

Conditions to Av
Moisture
Materials to Avoid:
Hazardous Decomposition Produ
Iodine and Sodium Oxide fumes
Hazardous Polymerization:Will N
Condition to Avoid:None known
Stability: Stable

Section 11 Additional Information

Conditions aggravated/Target org

preexisting skin, eye or respirator
be more susceptible. Acute: Irrita
mucous membranes and digestive
Chronic: Iodism, bronchitis, and r

DOT Classification: Not Regulate

DOT regulations may change from

Please consult the most recent ver
relevant regulations.
Revision
Date Entered:
No:0
9/1/2006
The information contained herein is believed to be accurate and is offered in good faith for the user's consideration and investigation. No
warranty is expressed or implied regarding the completeness or accuracy of this information, whether originating from Science Stuff, Inc. or
from an alternate source. Users of this material should satisfy themselves by independent investigation of current scientific and medical
information that this material may be safely handled.

yes

S3050

SELECT CODE, [P

362

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Material Safety Data Sheet

Tolylene-2,4-diisocyanate MSDS
Section 1: Chemical Product and Company Identification
Product Name: Tolylene-2,4-diisocyanate
Catalog Codes: SLT1264
CAS#: 584-84-9
RTECS: CZ6300000
TSCA: TSCA 8(b) inventory: Tolylene-2,4-diisocyanate
CI#: Not available.
Synonym: Toluene-2,4-diisocyanate
Chemical Formula: C9H6N2O2
Contact Information:
Sciencelab.com, Inc.
14025 Smith Rd.
Houston, Texas 77396
US Sales: 1-800-901-7247
International Sales: 1-281-441-4400
Order Online: ScienceLab.com
CHEMTREC (24HR Emergency Telephone), call:
1-800-424-9300
International CHEMTREC, call: 1-703-527-3887
For non-emergency assistance, call: 1-281-441-4400

Section 2: Composition and Information on Ingredients

Composition:
Name CAS # % by Weight
Tolylene-2,4-diisocyanate 584-84-9 100
Toxicological Data on Ingredients: Tolylene-2,4-diisocyanate: ORAL (LD50): Acute: 5800 mg/kg [Rat].
VAPOR (LC50):
Acute: 14 ppm 4 hour(s) [Rat]. 10 ppm 4 hour(s) [Mouse].

Section 3: Hazards Identification

Potential Acute Health Effects:
Extremely hazardous in case of ingestion. Very hazardous in case of skin contact (irritant), of eye contact
(irritant), of inhalation. Hazardous in case of skin contact (permeator). Slightly hazardous in case of skin
contact
(corrosive). Severe over-exposure can result in death. Inflammation of the eye is characterized by
redness,
watering, and itching. Skin inflammation is characterized by itching, scaling, reddening, or, occasionally,
blistering.
Potential Chronic Health Effects:
CARCINOGENIC EFFECTS: Classified 2 (Reasonably anticipated.) by NTP.
MUTAGENIC EFFECTS: Not available.
TERATOGENIC EFFECTS: Not available.
DEVELOPMENTAL TOXICITY: Not available.
The substance is toxic to lungs, the nervous system, liver, mucous membranes.
Repeated or prolonged exposure to the substance can produce target organs damage. Repeated
exposure to an
highly toxic material may produce general deterioration of health by an accumulation in one or many
human
p. 1
organs.

Section 4: First Aid Measures

363

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Eye Contact: Check for and remove any contact lenses. Do not use an eye ointment. Seek medical
attention.
Skin Contact:
After contact with skin, wash immediately with plenty of water. Gently and thoroughly wash the
contaminated skin
with running water and non-abrasive soap. Be particularly careful to clean folds, crevices, creases and
groin.
Cover the irritated skin with an emollient. If irritation persists, seek medical attention. Wash contaminated
clothing before reusing.
Serious Skin Contact:
Wash with a disinfectant soap and cover the contaminated skin with an anti-bacterial cream. Seek
immediate
medical attention.
Inhalation: Allow the victim to rest in a well ventilated area. Seek immediate medical attention.
Serious Inhalation:
Evacuate the victim to a safe area as soon as possible. Loosen tight clothing such as a collar, tie, belt or
waistband. If breathing is difficult, administer oxygen. If the victim is not breathing, perform mouth-tomouth
resuscitation. WARNING: It may be hazardous to the person providing aid to give mouth-to-mouth
resuscitation
when the inhaled material is toxic, infectious or corrosive. Seek immediate medical attention.
Ingestion:
Do not induce vomiting. Examine the lips and mouth to ascertain whether the tissues are damaged, a
possible
indication that the toxic material was ingested; the absence of such signs, however, is not conclusive.
Loosen
tight clothing such as a collar, tie, belt or waistband. If the victim is not breathing, perform mouth-to-mouth
resuscitation. Seek immediate medical attention.
Serious Ingestion: Not available.

Section 5: Fire and Explosion Data

Flammability of the Product: May be combustible at high temperature.
Auto-Ignition Temperature: 620C (1148F)
Flash Points: CLOSED CUP: 127C (260.6F). OPEN CUP: 135C (275F).
Flammable Limits: LOWER: 0.9% UPPER: 9.5%
Products of Combustion: These products are carbon oxides (CO, CO2), nitrogen oxides (NO, NO2...).
Fire Hazards in Presence of Various Substances: Slightly flammable to flammable in presence of
oxidizing materials.
Explosion Hazards in Presence of Various Substances:
Risks of explosion of the product in presence of mechanical impact: Not available.
Risks of explosion of the product in presence of static discharge: Not available.
Slightly explosive to explosive in presence of oxidizing materials.
Fire Fighting Media and Instructions:
SMALL FIRE: Use DRY chemical powder.
LARGE FIRE: Use water spray, fog or foam. Do not use water jet.
Special Remarks on Fire Hazards: Not available.
Special Remarks on Explosion Hazards: Not available.
p. 2

Section 6: Accidental Release Measures

Small Spill: Absorb with an inert material and put the spilled material in an appropriate waste disposal.
Large Spill:
If the product is in its solid form: Use a shovel to put the material into a convenient waste disposal
container. If
the product is in its liquid form: Absorb with an inert material and put the spilled material in an appropriate
waste

364

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disposal. Be careful that the product is not present at a concentration level above TLV. Check TLV on the
MSDS
and with local authorities.

Section 7: Handling and Storage

Precautions:
Keep locked up Keep container dry. Keep away from heat. Keep away from sources of ignition. Empty
containers pose a fire risk, evaporate the residue under a fume hood. Ground all equipment containing
material.
Do not ingest. Do not breathe gas/fumes/ vapour/spray. Never add water to this product In case of
insufficient
ventilation, wear suitable respiratory equipment If ingested, seek medical advice immediately and show
the
container or the label. Avoid contact with skin and eyes Keep away from incompatibles such as moisture.
Storage:
Keep container dry. Keep in a cool place. Ground all equipment containing material. Keep container
tightly
closed. Keep in a cool, well-ventilated place. Highly toxic or infectious materials should be stored in a
separate
locked safety storage cabinet or room.

Section 8: Exposure Controls/Personal Protection

Engineering Controls:
Provide exhaust ventilation or other engineering controls to keep the airborne concentrations of vapors
below their
respective threshold limit value. Ensure that eyewash stations and safety showers are proximal to the
work-station location.
Personal Protection:
Splash goggles. Lab coat. Vapor respirator. Be sure to use an approved/certified respirator or equivalent.
Gloves.
Personal Protection in Case of a Large Spill:
Splash goggles. Full suit. Vapor respirator. Boots. Gloves. A self contained breathing apparatus should
be
used to avoid inhalation of the product. Suggested protective clothing might not be sufficient; consult a
specialist
BEFORE handling this product.
Exposure Limits:
TWA: 0.02 (ppm)
TWA: 0.14 (mg/m3)
Consult local authorities for acceptable exposure limits.

Section 9: Physical and Chemical Properties

Physical state and appearance: Liquid.
Odor: Not available.
Taste: Not available.
Molecular Weight: 174.16 g/mole
Color: Colorless to light yellow.
pH (1% soln/water): Not applicable.
p. 3
Boiling Point: 251C (483.8F)
Melting Point: 19.4C (66.9F)
Critical Temperature: Not available.
Specific Gravity: 1.2244 (Water = 1)
Vapor Pressure: 0.01 mm of Hg (@ 20C)
Vapor Density: 6 (Air = 1)
Volatility: Not available.
Odor Threshold: 0.449 ppm
Water/Oil Dist. Coeff.: Not available.

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Ionicity (in Water): Not available.

Dispersion Properties: Not available.
Solubility: Insoluble in cold water.

Section 10: Stability and Reactivity Data

Stability: The product is stable.
Instability Temperature: Not available.
Conditions of Instability: Not available.
Incompatibility with various substances: Highly reactive with moisture.
Corrosivity: Non-corrosive in presence of glass.
Special Remarks on Reactivity: Not available.
Special Remarks on Corrosivity: Not available.
Polymerization: Yes.

Section 11: Toxicological Information

Routes of Entry: Dermal contact. Eye contact. Inhalation. Ingestion.
Toxicity to Animals:
WARNING: THE LC50 VALUES HEREUNDER ARE ESTIMATED ON THE BASIS OF A 4-HOUR
EXPOSURE.
Acute oral toxicity (LD50): 5800 mg/kg [Rat].
Acute toxicity of the vapor (LC50): 10 ppm 4 hour(s) [Mouse].
Chronic Effects on Humans:
CARCINOGENIC EFFECTS: Classified 2 (Reasonably anticipated.) by NTP.
The substance is toxic to lungs, the nervous system, liver, mucous membranes.
Other Toxic Effects on Humans:
Extremely hazardous in case of ingestion.
Very hazardous in case of skin contact (irritant), of inhalation.
Hazardous in case of skin contact (permeator).
p. 4
Slightly hazardous in case of skin contact (corrosive).
Special Remarks on Toxicity to Animals: Not available.
Special Remarks on Chronic Effects on Humans: Not available.
Special Remarks on other Toxic Effects on Humans: Not available.

Section 12: Ecological Information

Ecotoxicity: Not available.
BOD5 and COD: Not available.
Products of Biodegradation:
Possibly hazardous short term degradation products are not likely. However, long term degradation
products may
arise.
Toxicity of the Products of Biodegradation: The products of degradation are more toxic.
Special Remarks on the Products of Biodegradation: Not available.

Section 13: Disposal Considerations

Waste Disposal:

Section 14: Transport Information

DOT Classification: CLASS 6.1: Poisonous material.
Identification: : Toluene diisocyanate : UN2078 PG: II
Special Provisions for Transport: Not available.

Section 15: Other Regulatory Information

Federal and State Regulations:
California prop. 65: This product contains the following ingredients for which the State of California has
found to
cause cancer, birth defects or other reproductive harm, which would require a warning under the statute:
Tolylene-2,4-diisocyanate
California prop. 65: This product contains the following ingredients for which the State of California has
found to
cause cancer which would require a warning under the statute: Tolylene-2,4-diisocyanate

366

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Pennsylvania RTK: Tolylene-2,4-diisocyanate

Massachusetts RTK: Tolylene-2,4-diisocyanate
TSCA 8(b) inventory: Tolylene-2,4-diisocyanate
SARA 302/304/311/312 extremely hazardous substances: Tolylene-2,4-diisocyanate
SARA 313 toxic chemical notification and release reporting: Tolylene-2,4-diisocyanate
CERCLA: Hazardous substances.: Tolylene-2,4-diisocyanate
Other Regulations: OSHA: Hazardous by definition of Hazard Communication Standard (29 CFR
1910.1200).
Other Classifications:
WHMIS (Canada):
CLASS D-1A: Material causing immediate and serious toxic effects (VERY TOXIC).
CLASS D-2A: Material causing other toxic effects (VERY TOXIC).
DSCL (EEC):
p. 5
R26- Very toxic by inhalation.
R38- Irritating to skin.
R41- Risk of serious damage to eyes.
R45- May cause cancer.
HMIS (U.S.A.):
Health Hazard: 3
Fire Hazard: 1
Reactivity: 2
Personal Protection: h
National Fire Protection Association (U.S.A.):
Health: 3
Flammability: 1
Reactivity: 2
Specific hazard:
Protective Equipment:
Gloves.
Lab coat.
Vapor respirator. Be sure to use an
approved/certified respirator or
equivalent. Wear appropriate respirator
when ventilation is inadequate.
Splash goggles.

Section 16: Other Information

References: Not available.
Other Special Considerations: Not available.
Created: 10/10/2005 12:06 AM
Last Updated: 11/06/2008 12:00 PM
The information above is believed to be accurate and represents the best information currently available
to us. However, we
make no warranty of merchantability or any other warranty, express or implied, with respect to such
information, and we
assume no liability resulting from its use. Users should make their own investigations to determine the
suitability of the
information for their particular purposes. In no event shall ScienceLab.com be liable for any claims,
losses, or damages of any
third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages,
howsoever arising, even
if ScienceLab.com has been advised of the possibility of such damages.
p. 6

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Material Safety Data Sheet

Gaseous Oxygen
Section 1 : PRODUCT AND COMPANY IDENTIFICATION
Section 2 : COMPOSITION/ INGREDIENT INFORMATION
Section 3 : HAZARD IDENTIFICATION
Section 4 : FIRST AID MEASURES
Section 5 : FIRE FIGHTING MEASURES
Section 6 : ACCIDENTAL RELEASE MEASURES
Section 7 : HANDLING AND STORAGE
Section 8 : EXPOSURE CONTROLS / PERSONAL PROTECTION
Section 9 : PHYSICAL AND CHEMICAL PROPERTIES
Section 10 : STABILITY AND REACTIVITY
Section 11 : TOXICOLOGICAL INFORMATION

Section 13 : DISPOSAL CONSIDERATIONS

Section 14 : TRANSPORT INFORMATION
Section 15 : REGULATORY INFORMATION
Section 16 : OTHER INFORMATION

Section 1 : PRODUCT AND COMPANY IDENTIFICATION

Product name: Oxygen (Gaseous),

Supplier/ Manufacturer: Universal Industrial Gases, Inc.

2200 Northwood Avenue, Suite
3
Easton, PA 18045-2239 USA
.

Emergency phone: (610) 559-7967.

C.A.S.

Section 2 : COMPOSITION/ INGREDIENT INFORMATION

CONCENTRATION %
Ingredient Name OSHA PEL ACGIH TLV OSHA STEL

369

PhosgeneFreeRoutetoTolueneDiisocyanate

7782-44-7

Typically > 99
(MSDS also applies to 90 - 99%)

BouSaba,Dizon,Kasih,Stewart

OXYGEN
(+N2 & Ar)

NONE

NONE

NONE

Section 3 : HAZARD IDENTIFICATION

Oxygen
gas
is
colorless,
odorless, non-toxic cryogenic liquid or
Emergency Overview:
colorless, odorless, oxidizing gas. Liquid releases will quickly
vaporize to gas.
The chief physical hazard associated with releases of the gas is
its oxidizing power which can greatly accelerate the burning rate
for both common and exotic combustible materials. Emergency
personnel must practice extreme caution when approaching
oxygen releases because of the potential for intense fire.
The primary health hazard at atmospheric pressure is respiratory
system irritation after exposure to high oxygen concentrations.
Maintain oxygen levels in air above 19.5% and below 23.5%.
While up to 50% oxygen can be breathed for more than 24 hours
without adverse effects, high concentrations in open air
accelerate combustion and increase the risk of fire and explosion
of combustible or flammable materials.
Route of entry: Inhalation, skin and eye contact.

Effects of acute exposure

Eye contact: No adverse effects expected.

Skin contact: No adverse effects expected. .

Inhalation: May cause breathing difficulty.

Prolonged exposure to high oxygen levels (>75%) can cause
central nervous system depression: signs/symptoms can include
headache, dizziness, drowsiness, poor coordination, slowed
reaction time, slurred speech, giddiness and unconsciousness.
May cause coughing and chest pain.
May cause lung damage.
May cause soreness of the throat.

Ingestion: Not a likely route of exposure.

370

PhosgeneFreeRoutetoTolueneDiisocyanate

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Effects of chronic
None known.
exposure:
Reproductive effects: Oxygen deficiency during pregnancy has produced
developmental abnormalities in humans and experimental
animals.

Section 4 : FIRST AID MEASURES

Skin contact: None required.

Eye contact: None required.

Inhalation: RESCUERS SHOULD NOT ATTEMPT TO RETRIEVE VICTIMS

OF EXPOSURE TO THIS PRODUCT WITHOUT ADEQUATE
PERSONAL PROTECTIVE EQUIPMENT. At a minimum, SelfContained Breathing Apparatus should be worn.
Remove victim(s) to fresh air, as quickly as possible. If not
breathing qualified personnel should administer artificial
respiration. Get medical attention.
IKeep person warm and at rest.

Ingestion: No first aid should be needed.

Not considered a potential route of exposure.

Section 5 : FIRE FIGHTING MEASURES

Flammability: Oxidizer.

Conditions of Contact with flammable materials.

flammability:
Vigorously accelerates combustion.

Extinguishing media: Use appropriate extinguishing media for surrounding fire.

Special procedures: Self-contained breathing apparatus required.

Firefighters should wear the usual protective gear.
Cool fire exposed containers with water spray.
Personnel should be evacuated, if necessary, to upwind area.

371

PhosgeneFreeRoutetoTolueneDiisocyanate

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Remove containers from fire area if without risk.

Auto-ignition
Not applicable.
temperature:
Flash point (C), method: Not applicable.

Lower flammability
Not applicable.
limit (% vol):
Upper flammability
Not applicable.
limit (% vol):
Explosion Data
Sensitivity to mechanical
Avoid impact against container.
impact:
Explosive power: Closed containers may rupture or explode due to pressure buildup when exposed to extreme heat.
Cylinders are equipped with temperature and pressure relief
devices but may still rupture under fire conditions.

Section 6 : ACCIDENTAL RELEASE MEASURES

Leak/Spill: Evacuate all non-essential personnel.

Stop leak without risk.
Wear gloves and goggles
Use a self-contained breathing apparatus.

Ventilate area. Monitor the surrounding area for Oxygen level

Section 7 : HANDLING AND STORAGE

Handling procedures and Protect system components against physical damage.

equipment:
Use adequate ventilation.
Avoid inhalation.
Never work on a pressurized system.
372

PhosgeneFreeRoutetoTolueneDiisocyanate

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If there is a leak, close the upstream valve, blow down the

system by venting to a safe place, then repair the leak.

Storage requirements: Use storage containers, piping, valves and fittings designed for
storage and distribution of Gaseous Oxygen. Protect cylinders
against physical damage. Store in cool, dry, well-ventilated,
fireproof area, away from flammable materials and corrosive
atmospheres. Store away from heat and ignition sources and out
of direct sunlight. Do not store near elevators, corridors or
loading docks. Do not allow area where cylinders are stored to
exceed 52C (125F).
Move cylinders with a suitable hand-truck. Do not drag, slide or
roll cylinders. Do not drop cylinders or permit them to strike each
other. Secure cylinders firmly. Leave the valve protection cap inplace (where provided) until cylinder is placed into service and
after it is taken out of service.
Use designated CGA fittings and other support equipment. Do
not use adapters. Do not heat cylinder by any means to increase
the discharge rate of the product from the cylinder. Use check
valve or trap in discharge line to prevent hazardous backflow into
the cylinder. Do not use oils or grease on gas-handling fittings or
equipment.
After use, close main cylinder valve. Replace valve protection
cap
(where provided). Mark empty cylinders "EMPTY".

Section 8 : EXPOSURE CONTROLS / PERSONAL PROTECTION

Precautionary Measures
Gloves/Type:

Respiratory/Type:
Eye/Type:
Footwear/Type:
Clothing/Type:

Wear appropriate gloves.

NIOSH/MSHA approved respirator.

As per local regulations.

Safety boots per local regulations.

Wear adequate protective clothes.

373

PhosgeneFreeRoutetoTolueneDiisocyanate

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Other/Type: Eye wash facility should be in close proximity.

Emergency shower should be in close proximity.

Ventilation requirements: Mechanical ventilation is satisfactory. Ensure oxygen

concentration remains above 19.5% and Carbon Dioxide
concentration does not exceed 5000 ppm,
Local exhaust at points of emission preferred.

Exposure limit of material Not available.

Section 9 : PHYSICAL AND CHEMICAL PROPERTIES

Physical state: Gas

Appearance & odor: Colorless, odorless gas.

Odor threshold (PPM): Odorless.

Vapor pressure : Gas@ 70F (21C)

Vapor sp. gravity (air=1): 1.11 @ 70F (21C)

Volatiles (% by volume) 100%

Boiling point : -183C (760 mmHg)
-297.4F

Freezing point : -218.8C

-361.8F

Solubility in water (%): Slight.

Section 10 : STABILITY AND REACTIVITY

Chemical stability: Product is stable.

Conditions of reactivity: Heat

Hazardous
Will not occur.
polymerization:
374

PhosgeneFreeRoutetoTolueneDiisocyanate

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Incompatible substances: Combustible materials.

Oils or grease.
Flammable materials.

Hazardous
None.
decomposition products:
Section 11 : TOXICOLOGICAL INFORMATION

LD50 of product, species

Not available.
& route:

LC50 of product, species

Not available.
& route:
Section 13 : DISPOSAL CONSIDERATIONS

Waste disposal: Gas will dissipate in air. Cylinders should be returned in the
original shipping container, properly labeled, with any valve outlet
plugs or caps secured and valve protection cap in place.

Section 14 : TRANSPORT INFORMATION

DOT/ TDG classification:

For cylinder shipments:
Oxygen, compressed
UN1072
Class 2.2 (Non-Flammable Gas)
with subsidiary risk 5.1 (Oxidizer)

North American

Emergency Response 122

Guidebook Number:
Section 15 : REGULATORY INFORMATION

WHMIS classification:
A,
C

DSL status:Appears on DSL.

375

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Section 16 : OTHER INFORMATION

Definitions and other useful data:

CAS #: The Chemical Abstract Service Number which uniquely identifies each constituent.
ACGIH - American Conference of Governmental Industrial Hygienists, a professional
association which establishes exposure limits.
TLV - Threshold Limit Value - an airborne concentration of a substance which represents
conditions under which it is generally believed that nearly all workers may be repeatedly
exposed without adverse effect.
OSHA - U.S. Occupational Safety and Health Administration.
PEL - Permissible Exposure Limit - The same value as a TLV, except it is enforceable by
OSHA.
IDLH - Immediately Dangerous to Life and Health - A concentration from which one can escape
within 30-minutes without suffering permanent injury.
NATIONAL FIRE PROTECTION ASSOCIATION:
Health Hazard Rating Scale (Blue):
0 (material that on exposure under fire conditions would offer no hazard beyond that of ordinary
combustible materials);
1 (materialsthat on exposure under fire conditions could cause irritation or minor residual
injury);
2 (materials that on intense or continued exposure under fire conditions could cause temporary
incapacitation or possible residual injury);
3 (materials that can on short exposure could cause serious temporary or residual injury);
4 (materials that under very short exposure could cause death or major residual injury).
Flammability Hazard Rating Scale (Red):
0 (minimal hazard);
1 (materials that require substantial pre-heating before burning);
2 (combustible liquid or solids; liquids with a flash point of 38-93C [100-200F]);
3 (Class IB and IC flammable liquids with flash points below 38C [100F]);
4 (Class IA flammable liquids with flash points below 23C [73F] and boiling points below 38C
[100F].
Reactivity Hazard Rating Scale(Yellow):
0 (normally stable);
1 (material that can become unstable at elevated temperatures or which can react slightly with
water);
2 (materials that are unstable but do not detonate or which can react violently with water);
3 (materials that can detonate when initiated or which can react explosively with water);
4 (materials that can detonate at normal temperatures or pressures).
376

PhosgeneFreeRoutetoTolueneDiisocyanate

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TOXICOLOGICAL INFORMATION:
Possible health hazards as derived from human data, animal studies, or from the results of
studies with similar compounds are presented. Definitions of some terms:
LD50 -Lethal Dose (solids & liquids) which kills 50% of the exposed animals;
LC50 - Lethal Concentration (gases) which kills 50% of the exposed animals;
ppm concentration expressed in parts of material per million parts of air or water;
mg/m3 concentration expressed in weight of substance per volume of air;
mg/kg quantity of material, by weight.
REGULATORY INFORMATION:
EPA is the U.S. Environmental Protection Agency.
WHMIS is the Canadian Workplace Hazardous Materials Information System.
DOT and TC are the U.S. Department of Transportation and the Transport Canada,
respectively, which assign DOT and TDG (Transportation of Dangerous Goods) identification
numbers, hazard classifications, and proper shipping name and shipping label information. This
material is hazardous as defined by 49 CFR 172.101 of the US Department of Transportation
and Dangerous Goods as defined by Transport Canada Transportation of Dangerous Goods
Regulations.

USE OF THIS INFORMATION:

Universal Industrial Gases, Inc. offers this information to customers, employees, contractors,
and the general public to promote the safe use of this product through awareness of product
hazards and safety information. Customers and others who use or transport or sell this
product to others should: 1) Disseminate this information internally to all workplace areas,
employees, agents and contractors likely to encounter this product; 2) Provide supplemental
hazards awareness, safety information, operation and maintenance procedures to the
workplace areas and employees, agents and contractors likely to encounter this product; 3)
Furnish this information to all their customers who purchase this product; and 4) Ask each
purchaser or user of the product to notify its employees and customers of the product hazards
and safety information.
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DISCLAIMER OF EXPRESSED AND IMPLIED WARRANTIES:
Universal Industrial Gases, Inc. has taken reasonable care in preparing this document,
however, since the use of this information and the conditions of use of the product are not
within the control of Universal Industrial Gases, Inc., it is the user's obligation to determine the
conditions of safe use of this product. The information in this document is offered with no
warranties or representations as to accuracy or completeness and it is the responsibility of
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each individual to determine the suitability of the information for their particular purpose(s).

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MATERIAL SAFETY DATA SHEET

PRODUCT NAME: CARBON MONOXIDE

1. Chemical Product and Company Identification
BOC Gases, Division of The BOC Group, Inc. 575 Mountain Avenue Murray Hill, NJ 07974
TELEPHONE NUMBER: (908) 464-8100
BOC Gases Division of BOC Canada Limited 5975 Falbourne Street, Unit 2 Mississauga, Ontario L5R 3W6
TELEPHONE NUMBER: (905) 501-1700 24-HOUR EMERGENCY TELEPHONE NUMBER:
CHEMTREC (800) 424-9300 24-HOUR EMERGENCY TELEPHONE NUMBER: (905) 501-0802
EMERGENCY RESPONSE PLAN NO: 20101
PRODUCT NAME: CARBON MONOXIDE CHEMICAL NAME: Carbon Monoxide COMMON
NAMES/SYNONYMS: Carbonic Oxide, Exhaust Gas, Flue Gas TDG (Canada) CLASSIFICATION: 2.3 (2.1)
WHMIS CLASSIFICATION: A, D1A, D2A, D2B, B1
PREPARED BY: Loss Control (908)464-8100/(905)501-1700 PREPARATION DATE: 6/1/95 REVIEW
DATES: 6/7/96

2.

Composition, Information on Ingredients

INGREDIENT % VOLUME PEL-OSHA

1

TLV-ACGIH
Route/Species Carbon Monoxide
FORMULA: CO CAS: 630-08-0 RTECS #:

FG3500000

1
2

100.0 50 ppm TWA 25 ppm TWA LC

As stated in 29 CFR 1910, Subpart Z (revised July 1, 1993)
As stated in the ACGIH 1994-95 Threshold Limit Values for Chemical

3.

Hazards Identification

Substances and Physical Agents

EMERGENCY OVERVIEW Inhaled Carbon Monoxide binds to the blood hemoglobin,

greatly reducing the red blood cells ability to transport oxygen to body
tissues. Effects may include headaches, dizziness, convulsions, loss of
consciousness and death. Extremely flammable gas.
MSDS: G-112 Revised: 6/7/96 Page 1 of 6
2

LD
50
50

or LC
1807 ppm/4H (rat)
50

PRODUCT NAME: CARBON MONOXIDE

ROUTE OF ENTRY: Skin Contact
No Skin Absorption
HEALTH EFFECTS: Exposure Limits
No Eye Contact
Yes Irritant
No Inhalation
Yes Ingestion
No Sensitization
No Teratogen
Synergistic Effects None Reported
Yes Reproductive Hazard
Carcinogenicity: -- NTP: No IARC: No OSHA: No
EYE EFFECTS: None reported.
SKIN EFFECTS: None reported.
INGESTION EFFECTS: None reported.
Yes Mutagen Yes
INHALATION EFFECTS: Inhaled carbon monoxide binds with blood hemoglobin to form carboxyhemoglobin.
Carboxyhemoglobin can not take part in normal oxygen transport, greatly reducing the bloods ability to transport

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oxygen. Depending on levels and duration of exposure, symptoms may include headache, dizziness, heart
palpitations, weakness, confusion, nausea, and even convulsions, eventual unconsciousness and death.
Some experimental evidence indicating teratogenic and reproductive effects.
NFPA HAZARD CODES HMIS HAZARD CODES RATINGS SYSTEM
Health:
2 Health:
2 0 = No Hazard Flammability: 4 Flammability: 4 1 = Slight Hazard Reactivity:
0 Reactivity:
0 2 = Moderate Hazard

4.

First Aid Measures

EYES: None required.

SKIN EFFECTS: None required.
INGESTION: None required.
3 = Serious Hazard 4 = Severe Hazard
MSDS: G-112 Revised: 6/7/96 Page 2 of 6
No
PRODUCT NAME: CARBON MONOXIDE
INGESTION EFFECTS: None required.
INHALATION: Conscious persons should be assisted to an uncontaminated area and be treated with supplemental
oxygen. Quick removal from the contaminated area is most important. Unconscious persons should be moved to an
uncontaminated area and be given artificial respiration and oxygen at the same time. The administering of the
oxygen at an elevated pressure (up to 2 to 2.5 atmospheres) has shown to be beneficial as has treatment in a
hyperbaric chamber. The physician should be informed that the patient has inhaled toxic quantities of carbon
monoxide. PROMPT MEDICAL ATTENTION IS MANDATORY IN ALL CASES OF OVEREXPOSURE TO
CARBON MONOXIDE. RESCUE PERSONNEL SHOULD BE EQUIPPED WITH SELF-CONTAINED
BREATHING APPARATUS AND BE COGNIZANT OF EXTREME FIRE AND EXPLOSION HAZARD.

5.

Fire Fighting Measures

Conditions of Flammability: Flammable gas Flash point:

Not Available Method: Not Applicable
Autoignition: Temperature: 116
C) LEL(%): 12.5 UEL(%): 74.0 Hazardous combustion products: None Sensitivity to mechanical shock: None
Sensitivity to static discharge: Not Available
FIRE AND EXPLOSION HAZARDS: Having almost the same density as air, it will not diffuse by rising as with
some lighter flammable gases such as hydrogen or natural gas (methane). Flammable in air over a very wide range.
It reacts violently with oxygen difluoride and barium peroxide.
EXTINGUISHING MEDIA: Water, dry chemical, carbon dioxide.
FIRE FIGHTING INSTRUCTIONS: If possible, stop flow of gas; use water spray to cool surrounding containers.

6.

Accidental Release Measures

Evacuate all personnel from affected area. Use appropriate protective equipment. If leak is in users equipment, be
certain to purge piping with inert gas prior to attempting repairs. If leak is in container or container valve, contact
the appropriate emergency telephone number listed in Section 1 or call your closest BOC location.

7.

Handling and Storage

Electrical Classification: Class 1, Group C

Earth-ground and bond all lines and equipment associated with the carbon monoxide system. Electrical equipment
should be non sparking or explosion proof.
MSDS: G-112 Revised: 6/7/96 Page 3 of 6
o

F (639
O

PRODUCT NAME: CARBON MONOXIDE

Carbon Monoxide can be handled in all commonly used metals up to approximately 500 psig (3450 kPa). Above
that pressure it forms toxic and corrosive carbonyl compounds with some metals. Carbon steels, aluminum alloys,
copper and copper alloys, low carbon stainless steels and nickel-based alloys such as Hastelloy A, B & C are
recommended for higher pressure applications.
Protect cylinders from physical damage. Store in cool, dry, well-ventilated areas away from heavily trafficked areas
and emergency exits. Do not allow the temperature where cylinders are stored to exceed 130
C). Cylinders should be stored upright and firmly secured to prevent falling or being knocked over. Full and empty
cylinders should be segregated. Use a "first in-first out" inventory system to prevent full cylinders being stored for

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excessive periods of time. Post "NO SMOKING OR OPEN FLAMES" signs in the storage area or use area. There
should be no sources of ignition in the storage area or use area.
Use only in well-ventilated areas. Valve protection caps must remain in place unless container is secured with valve
outlet piped to use point. Do not drag, slide or roll cylinders. Use a suitable hand truck for cylinder movement. Use
a pressure reducing regulator when connecting cylinder to lower pressure (<3000 psig) piping or systems. Do not
heat cylinder by any means to increase the discharge rate of product from the cylinder. Use a check valve or trap in
the discharge line to prevent hazardous back flow into the system.
ENGINEERING CONTROLS: Hood with forced ventilation. Use local exhaust to prevent accumulation above
the exposure limit. Use general mechanical ventilation in accordance with electrical codes.

8.

Exposure Controls, Personal Protection

EXPOSURE LIMITS
1

:
INGREDIENT % VOLUME PEL-OSHA
2

TLV-ACGIH
Route/Species Carbon Monoxide
FORMULA: CO CAS: 630-08-0 RTECS #:

FG3500000

100.0 50 ppm TWA 25 ppm TWA LC

Refer to individual state of provincial regulations, as applicable, for limits which may be more stringent than those listed here.
2
3

As stated in 29 CFR 1910, Subpart Z (revised July 1, 1993)

As stated in the ACGIH 1994-1995 Threshold Limit Values for Chemical Substances and Physical Agents.

EYE/FACE PROTECTION: Safety goggles or glasses.

SKIN PROTECTION: Any material protective gloves.
RESPIRATORY PROTECTION: Positive pressure air line with full-face mask and escape bottle or selfcontained breathing apparatus should be available for emergency use.
OTHER/GENERAL PROTECTION: Safety shoes.
MSDS: G-112 Revised: 6/7/96 Page 4 of 6
3
o

F (54
LD
50
50
o

or LC
1807 ppm/4H (rat)
50

PRODUCT NAME:

9.

CARBON MONOXIDE

Physical and Chemical Properties

PARAMETER VALUE UNITS Physical state (gas, liquid, solid) : Gas

Vapor pressure : >220.4 psia Vapor density (Air = 1) : Not Available Evaporation point : Not Available Boiling
point : -312.7
C Freezing point : -337.1
: -191.5
C pH : Not Available Specific gravity : 0.96 Oil/water partition coefficient : Not Available Solubility (H20) :
Very slight Odor threshold : Not Applicable Odor and appearance : Odorless; colorless gas

10.

Stability and Reactivity

STABILITY: Stable
INCOMPATIBLE MATERIALS: Oxidizers
HAZARDOUS DECOMPOSITION PRODUCTS: Carbon dioxide
HAZARDOUS POLYMERIZATION: Will not occur.

11.

Toxicological Information

: -205.1
o
o
o
o

F
F
REPRODUCTIVE: Inhalation of 150 ppm carbon monoxide for 24 hours by pregnant rats produced cardiovascular
and behavioral defects in offspring. Toxic effects to fertility were observed in female rats exposed to 1 mg/m

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for 24 hours. Similar effects observed in other mammalian species.

MUTAGENIC: Genetic changes observed in mammalian cell assay systems at exposures of 1500 to 2500 ppm for
10 minutes.
OTHER: Degenerative changes to the brain in rats chronically exposed to 30 mg/m

12.

Ecological Information

No data given.
3

.
MSDS: G-112 Revised: 6/7/96 Page 5 of 6
3

PRODUCT NAME:

13.

CARBON MONOXIDE

Disposal Considerations

Do not attempt to dispose of residual waste or unused quantities. Return in the shipping container PROPERLY
LABELED, WITH ANY VALVE OUTLET PLUGS OR CAPS SECURED AND VALVE PROTECTION CAP IN
PLACE to BOC Gases or authorized distributor for proper disposal.

14.

Transport Information

PARAMETER United States DOT Canada TDG

PROPER SHIPPING NAME: Carbon Monoxide Carbon Monoxide HAZARD CLASS: 2.3 2.3 (2.1) IDENTIFICATION
NUMBER: UN 1016 UN 1016 SHIPPING LABEL: POISON GAS, FLAMMABLE GAS POISON GAS, FLAMMABLE GAS

Additional Marking Requirement: Inhalation Hazard Additional Shipping Paper Description Requirement:
Poison-Inhalation Hazard, Zone D

15.

Regulatory Information

SARA TITLE III NOTIFICATIONS AND INFORMATION

SARA TITLE III - HAZARD CLASSES: Acute Health Hazard Chronic Health Hazard Fire Hazard Sudden
Release of Pressure Hazard

16.

Other Information

Compressed gas cylinders shall not be refilled without the express written permission of the owner. Shipment of a
compressed gas cylinder which has not been filled by the owner or with his/her (written) consent is a violation of
transportation regulations.
DISCLAIMER OF EXPRESSED AND IMPLIED WARRANTIES: Although reasonable care has been taken in
the preparation of this document, we extend no warranties and make no representations as to the accuracy or
completeness of the information contained herein, and assume no responsibility regarding the suitability of this
information for the user's intended purposes or for the consequences of its use. Each individual should make a
determination as to the suitability of the information for their particular purpose(s).
MSDS: G-112 Revised: 6/7/96 Page 6 of 6

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Product Safety Summary Toluene Diamine

This Product Safety Summary is intended to provide a general overview of the chemical substance. The
information on the Summary is basic information and is not intended to provide emergency response
information, medical information or treatment information. The summary should not be used to provide indepth safety and health information. In-depth safety and health information can be found on the Material
Safety Data Sheet (MSDS) for the chemical substance.

Chemical Identity
Abbreviation: TDA CAS Number : 25376-45-8 . Common Names: Diaminotoluene
isomers Methylphenylene diamine Tolyenediamine

Toluenediamine

Product Overview

Pure toluene diamine is a highly poisonous, colorless solid which turns dark upon exposure to air.
A majority of TDA produced in the United States is used as an 80% 2,4- and 20% 2,6toluenediamnine
mixture to make toluene diisocyanate (TDI). A smaller amount is also made from a mixture of 65% 2,4and 35% 2,6-toluenediamine. Some isolated 2,4toluenediamine is used to produce pure 2,4-TDI. 2,4 is
also used to make about 60 dyes, of which 28 are believed to be commercially significant. Other uses of
TDA include enhancement of thermal stability in polyamides, fatigue resistance and dye ability in fibers,
and the preparation of impact resistant resins, polyimides with superior wire coating properties,
benzimidazolethiols (antioxidants), hydraulic fluids, urethane foams, fungicide stabilizers, and sensitizers
for explosives.
May be fatal if swallowed, inhaled or absorbed through skin. Causes irritation to the skin, eyes and
respiratory tract. Combustible solid or liquid when heated. May cause methemoglobinemia. Affects blood,
cardiovascular system, central nervous system, liver and kidneys.
No airborne limits have been established for toluene diamine in the work environment. For further
safety and health information, the current Material Safety Data Sheet (MSDS)
should be used for this substance.

Physical/Chemical Properties
TDA is a colorless solid which darkens on exposure to light or air. It has a weak amine or fish like odor.
The specific gravity of TDA is 1.05 and is denser than water. TDA is soluble in water . The boiling
point of TDA is 292C and the melting point is approximately 99C. The flash
point of TDA is 149C, by the Tag Closed cup method.

Date: November 15, 2008 Page: 1 of 5

Health Information
TDA is a potentially hazardous material. A through knowledge of potential dangers, with strict adherence
to recommended safety practices, is essential before aniline products are handled, stored or used.
Workers must be properly instructed and supervised in the handling of TDA. No limits have been
established for allowable concentrations in the work environment. The skin is a known route of exposure.
TDA is listed as a category 2 carcinogen. Effects on the Respiratory System: Exposures to mists or dust
can produce eye, nose or lung irritation. The hot liquid may cause severe skin burns. Symptoms may
include bluish discoloration of lips and tongue, severe headache, nausea, confusion, dizziness, shock,
respiratory paralysis, death. TDA affects the ability of the blood to carry oxygen. The effects may be
delayed. Effects on the Skin: TDA may be absorbed through the skin. Symptoms of skin absorption
parallel those from inhalation exposure. May cause skin irritation and local contact may cause dermatitis.

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Effects on the Eyes: TDA vapor or dust is an eye irritant. May cause tearing and blurred vision. Splashes
may cause corneal damage. Effects of Ingestion: TDA is toxic. Symptoms of ingestion parallel those of
inhalation exposure. Chronic Hazards: TDA is a blood toxin, causing hemoglobin to convert to
methemoglobin, resulting in cyanosis. Lengthy or repeated exposures may result in decreased appetite,
anemia, weight loss, nervous system affects, and kidney, liver and bone marrow damage. Any exposure
may cause an allergic skin reaction. This substance is possibly carcinogenic to humans. May cause
genetic damage in humans.

Environmental Information
Do not wash away into sewer. Sweep spilled material into containers; if appropriate, moisten first to
prevent dust generation. Then remove to a safe place. Do not let TDA enter the environment. TDA is
expected to be very toxic to terrestrial and aquatic life. A variety of federal, state and local regulations
govern the release of any material to the land, air or surface waters. Any release or discharge of TDA
must be evaluated in reference to these regulations to determine appropriate response actions and
reporting requirements. TDA is one of the chemicals for which releases to all environmental media must
be annually reported. TDA has a reportable quantity (RQ) of 10 pounds per CERCLA. A regulation called
Resource Conservation and Recovery Act (RCRA) must be followed if a volume of TDA or material
contaminated with TDA is to be disposed of or discarded. Based on RCRA criteria, aniline or materials
contaminated with TDA will likely be considered a Hazardous Waste upon disposal and will need to
follow certain storage, handling and disposal restrictions as outlined in RCRA. Strict adherence to these
restrictions as well as proper characterization and labeling of the material is the responsibility of the
generator and handler of the waste material.

Date: November 15, 2008 Page: 2 of 5

Emphasis should be placed on the prevention of releases through careful design of equipment and
sound operating procedures. If TDA is lost from containment through a leak or spill, care should be taken
to use the proper personal protective equipment, decontamination procedures and other safety
considerations. It is important to remember that spills of TDA and materials contaminated by TDA must be
handled as RCRA hazardous wastes (U221). Any release of TDA greater than the reportable quantity,
10 pounds ,designated by the EPA in CERCLA or SARA should be reported immediately on discovery to
the National Response Center and State Emergency Response Agency (see current MSDS for reportable
quantity and pertinent phone numbers). In the event of accidental spillage of TDA to surface waters or
to a municipal water system, contact the local and state pollution control agencies immediately.

Additional Hazard Information

Protect containers against physical damage. Store in a cool, dry well-ventilated location, away from any
area where the fire hazard may be acute. Outside or detached storage is preferred. Containers should be
bonded and grounded for transfers to avoid static sparks. Storage and use areas should be no smoking
areas. Use non-sparking type tools and equipment, including explosion proof ventilation. Containers may
be hazardous when empty since they retain product residues (vapors/liquids); observe all warnings and
precaution listed for TDA.

Exposure Potential
Although potential for exposure does exist during TDA manufacture, transportation and use, enclosed
systems limit the exposure to worker populations and nearby communities. Exposure to the general
public may occur in accidental situations. TDA is not intended for the general use by the general public.
TDA vapor or dust has a fish like odor which should not be used for early detection of any potential
release. If you smell TDA, you are over the recommended exposure. TDA should only be handled by
knowledgeable, well-trained personnel who thoroughly understand the hazards associated with the
transportation, storage and use of the chemical.
Workplace exposure should be limited by the use of engineering controls. TDA vapors and dusts must be
monitored and controlled below applicable regulatory limits. TDA should be processed within a closed

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system. Worker exposure can potentially happen from leaks in piping system, during repair or
replacement of the piping system or during removal of a sample for quality control purposes. Regulations
involving hazardous chemicals are continually evolving and thus exposure guidelines are reviewed
regularly and modified whenever new information dictates a change. It is important that all companies
handling aniline are aware of the current legislative requirements. The guidelines established by OSHA,
ACGIH, NIOSH and others, represent current thinking and are believed to be conservative and protective
of occupational workers. There is not guarantee of absolute safety.

Date: November 15, 2008 Page: 3 of 5

Risk Management
The potential hazards associated with TDA can be avoided if workers are adequately instructed in
supervised on the proper procedures of handling TDA. Personal protective equipment (PPE) should be
selected based on the potential for exposure to particular chemical(s), and the unique properties of that
chemical. In general, PPE is not an adequate substitute for appropriate workplace controls (such as
ventilation), or other safe work practices. There may be situations when the only practical means of
preventing employee exposure is through the effective use of PPE. When PPE is provided to employees,
they must be trained in how, where, when, and why the equipment should be used. The facility must also
have provisions for decontaminating and replacing such equipment as necessary.
Eye protection in the form of chemical splash goggles should be worn to prevent TDA from accidentally
splashing in an employees eye. Goggles should be non-vented, and designed specifically to protect
against chemical splash. If an employee wears corrective lenses, chemical goggles should be worn over
the lenses. Contact lenses are not recommended for use in areas where there is a potential for exposure
to aniline. Corrosive vapors or dust can collect behind contact lenses and may cause severe damage to
the eye and/or cause the contact lenses to adhere to the eyes.
Skin protection may be found in many forms. Hand protection such as chemical resistant gloves,
protective arm sleeves, aprons, full body coveralls, boots, and head coverings are among the types
available. Skin protection must be made of a material impervious to TDA. Personal protective equipment
should be selected on the basis of potential exposure, e.g., gloves may be required for sample collection
while full body clothing including gloves, boot covers, head covering may be necessary for spill clean-up.
Skin protection for the purpose of preventing chemical exposure may be worn in conjunction with other
types of PPE. For example, steel toe safety shoes may be required to prevent a persons foot from being
crushed, but an additional boot cover may be required to prevent TDA permeation into the safety shoe.
Skin protection PPE is available in a variety of sizes, and should be available in a size that fits the
employee wearing it. Improperly sized PPE may compromise its effectiveness and create additional
safety hazards. When skin protection PPE is used, there must be a means of cleaning or
disposal/replacement of the PPE. Respiratory protection is available in two basic varieties, air purifying,
and air supplied. In general, air purifying respirators provide less protection than air supplied respirators.
Both types, however, have their particular advantages and limitations. The appropriate type of respirator
must be selected to provide the appropriate level of protection for the anticipated degree of exposure to
airborne aniline (vapor or mist). Detailed guidance for the selection of respiratory protection can be found
in The American National Standards Institute Document Z88.2. Respiratory protective equipment should
be approved by NIOSH. It must be carefully maintained, inspected, and cleaned. All employees required
to wear respiratory protection must be medically cleared to do so (this ensures their physical capability to
wear a respirator) and trained to use and care for the equipment. OSHA requirements for respiratory
protection can be found in 29 CFR 1910.134.
Properly designed emergency showers and eyewash fountains should be placed in convenient locations
wherever acrylic acid is used. All employees should know the location and operation of this equipment.
All equipment must be frequently inspected to make sure they are in proper working condition.

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Date: November 15, 2008 Page: 4 of 5

Federal/Science Findings (optional) U.S. Environmental Protection Agency Integrated Risk

Information System (IRIS) http://www.epa.gov/ncea/iris/subst/0536.htm U.S. Environmental
Protection Agency http://www.epa.gov/ttn/atw/hlthef/diamino.html U.S Department of Labor
Occupational Safety and Health Administration (OSHA)
http://www.osha.gov/dts/chemicalsampling/data/CH_272300.html

American Conference of Governmental Industrial Hygienists (ACGIH)

http://www.acgih.org
Contact Information
MSDS

http://www.basf.com
http://worldaccount.basf.com/wa/PublicMSDS~en_US/Search
References
IMPORTANT: While the data and information contained herein are presented in good faith and
believed to be accurate, it is provided for your guidance only. No warranties of any kind, either
express or implied, are made regarding the data or information provided. Further, it is expressly
understood that the data and information furnished by BASF hereunder are given gratis and BASF
assumes no obligation or liability for the data and information given, all such data and information
being given and accepted at your risk.

Date: November 15, 2008 Page: 5 of 5

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P 343 / Canada Issuing date 11.12.2008 / Report version 1.0 Copyright 2008, SOLVAY FLUORIDES, LLC A subsidiary of SOLVAY Chemicals All Rights Reserved
www.solvaychemicals.us

SAFETY DATA SHEET

North American Version

TFE (TRIFLUOROETHANOL)
1. PRODUCT AND COMPANY IDENTIFICATION
1.1. Identification of the substance or preparation Product name : TFE (TRIFLUOROETHANOL)
Chemical Name : 2.2.2-Trifluoroethanol Synonyms : Trifluoroethanol Molecular formula : C2H3F3O
Structural formula CF3CH2OH Molecular Weight : 100 g/mol
1.2. Use of the Substance/Preparation Recommended use : - Chemical intermediate
- Solvent 1.3. Company/Undertaking Identification
Address : SOLVAY FLUORIDES, LLC 3333 RICHMOND AVENUE HOUSTON TX
77098-3099
United States
1.4. Emergency and contact telephone numbers Emergency telephone : 1 (800) 424-9300
CHEMTREC (USA & Canada)
Contact telephone number (product information):

2. HAZARDS IDENTIFICATION
01-800-00-214-00 (MEX. REPUBLIC)
: US: +1-800-765-8292 (Product information) US: +1-713-525-6500 (Product information)
2.1. Emergency Overview: NFPA : H= 3 F= 3 I= 0 S= None
HMIS : H= 3 F= 3 R= 0 PPE = Supplied by User; dependent on local conditions
General Information
Main effects

Appearance : liquid Colour : colourless Odour : characteristic

- Flammable - Harmful by inhalation, in contact with skin and if swallowed. - Irritating to skin. - Risk of
serious damage to eyes. - Harmful: danger of serious damage to health by prolonged exposure through
inhalation.
TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

- Possible risk of impaired fertility. - In case of decomposition, releases hydrogen fluoride.

2.2. Potential Health Effects:
Inhalation

- Irritating to mucous membranes - At high concentrations, cough and difficulty in breathing.

Eye contact

- Severe eye irritation, watering, redness and swelling of the eyelids. - Causes burns. - Risk of serious or
permanent eye lesions.
Skin contact

- Dermal absorption possible - Irritation.

Ingestion

- Nausea, vomiting and diarrhea.

Other toxicity effects

- See section 11: Toxicological Information 2.3. Environmental Effects:

- See section 12: Ecological Information

3. COMPOSITION/INFORMATION ON INGREDIENTS
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2,2,2-Trifluoroethanol CAS-No. : 75-89-8 Concentration : > 99,5 %

4. FIRST AID MEASURES

4.1. Inhalation - Remove to fresh air.
- Oxygen or artificial respiration if needed. - Consult a physician.
4.2. Eye contact - Rinse immediately with plenty of water, also under the eyelids, for at least 15 minutes.
- In the case of difficulty of opening the lids, administer an analgesic eye wash (oxybuprocaine). - Consult
with an ophthalmologist immediately in all cases.
4.3. Skin contact - Remove contaminated shoes, socks and clothing; wash the affected skin with running
water.
- Wash contaminated clothing before re-use. - Consult a physician.
4.4. Ingestion - Consult a physician.
If victim is conscious:

- Clean mouth with water and drink afterwards plenty of water.

If victim is unconscious but breathing:

- Artificial respiration and/or oxygen may be necessary.

P 343 / Canada Issuing date 11.12.2008 / Report version 1.0 Copyright 2008, SOLVAY FLUORIDES, LLC A subsidiary of SOLVAY Chemicals All Rights Reserved
www.solvaychemicals.us

2/10
TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

5. FIRE-FIGHTING MEASURES
5.1. Suitable extinguishing media - powder
- Alcohol-resistant foam - Carbon dioxide (CO2) - Water spray
5.2. Extinguishing media which shall not be used for safety reasons - None.
5.3. Special exposure hazards in a fire - Flammable.
- Hazardous decomposition products - Heating can release hazardous gases. - Gas/vapours are heavier
than air and so may travel along the ground; remote ignition possible. - Vapours may form explosive
mixtures with air.
5.4. Hazardous decomposition products - Hydrogen fluoride
- Fluorophosgene - Carbon monoxide
5.5. Special protective equipment for fire-fighters - Evacuate personnel to safe areas.
- Intervention only by capable personnel who are trained and aware of the hazards of the product. - In the
event of fire, wear self-contained breathing apparatus. - Fire fighters must wear fire resistant personnel
protective equipment. - When intervention in close proximity wear acid resistant over suit. - Protect
intervention team with a water spray as they approach the fire. - Clean contaminated surface thoroughly.
5.6. Other information - If safe to do so, remove the exposed containers, or cool with large quantities of
water.
- Approach from upwind. - Avoid propagating the fire when directing the extinguishing agent as a jet onto
the surface of the burning
liquid. - After the fire, proceed rapidly to clean the surfaces exposed to the fumes in order to limit the
damage to the
equipment. - As for any fire, ventilate and clean the rooms before re-entry.

6. ACCIDENTAL RELEASE MEASURES

6.1. Personal precautions - Refer to protective measures listed in sections 7 and 8.
- Prevent further leakage or spillage if safe to do so. - Keep away from open flames, hot surfaces and
sources of ignition. - Keep away from incompatible products - Approach from upwind. - Suppress (knock
down) gases/vapours/mists with a water spray jet. - Protect intervention team with water spray.
6.2. Environmental precautions - Do not flush into surface water or sanitary sewer system.
- If the product contaminates rivers and lakes or drains inform respective authorities.
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TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

6.3. Methods for cleaning up - If possible, dam large quantities of liquid with sand or earth.
- Prevent product from entering drains. - Soak up with inert absorbent material (e.g. sand, silica gel, acid
binder, universal binder, sawdust). - Place everything into a closed, labelled container compatible with the
product. - Store in a place accessible by authorized persons only. - Treat recovered material as described
in the section "Disposal considerations". - Flush with plenty of water.

7. HANDLING AND STORAGE

7.1. Handling - Used in closed system
- Handle small quantities under a lab hood. - Use only in well-ventilated areas. - No sparking tools should
be used. - Prevent any product decomposition from contacting hot spots. - Use only equipment and
materials which are compatible with the product. - Keep away from heat and sources of ignition. - Keep
away from incompatible products
7.2. Storage - Keep in a cool, well-ventilated place.
- Keep away from heat and sources of ignition. - Keep away from incompatible products - Keep under
inert gas. - Keep in a bunded area. - Information about special precautions needed for bulk handling is
available on request.
7.3. Packaging material - Steel drum
- Stainless steel 7.4. Other information
- No open flames or sparks, no smoking. - Provide electrical equipment safe for hazardous locations. Ensure all equipment is electrically grounded before beginning transfer operations. - Take measures to
prevent the build up of electrostatic charge. - Warn people about the dangers of the product. - Refer to
protective measures listed in sections 7 and 8.

8. EXPOSURE CONTROLS/PERSONAL PROTECTION

8.1. Exposure Limit Values 2,2,2-Trifluoroethanol
- US. ACGIH Threshold Limit Values Remarks: none established
8.2. Engineering controls - Ensure adequate ventilation.
- Provide local ventilation appropriate to the product decomposition risk (see section 10). - Apply technical
measures to comply with the occupational exposure limits.
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TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

8.3. Personal protective equipment

8.3.1. Respiratory protection

- Self-contained breathing apparatus in medium confinement/insufficient oxygen/in case of large

uncontrolled emissions/in all circumstances when the mask and cartridge do not give adequate
protection.
- Use only respiratory protection that conforms to international/ national standards. - Use NIOSH
approved respiratory protection.
8.3.2. Hand protection

- Wear suitable gloves. - Recommended materials: Neoprene, rubber

8.3.3. Eye protection

- Chemical resistant goggles must be worn.

8.3.4. Skin and body protection

- Protective suit - Apron/boots of neoprene if risk of splashing.

8.3.5. Hygiene measures

- Shower and eye wash stations. - Handle in accordance with good industrial hygiene and safety practice.

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9. PHYSICAL AND CHEMICAL PROPERTIES

9.1. General Information Appearance : liquid
Colour : colourless Odour : characteristic
9.2. Important health safety and environmental information pH : Remarks: neutral
Boiling point/boiling range : 73,6 C ( 164,5 F ) Flash point : 33 C ( 91 F )
Remarks: Flammable. Flammability : Upper explosion limit :
P 343 / Canada Issuing date 11.12.2008 / Report version 1.0 Copyright 2008, SOLVAY FLUORIDES, LLC A subsidiary of SOLVAY Chemicals All Rights Reserved
www.solvaychemicals.us

28,8 %(V) Lower explosion limit : 8,4 %(V)

Explosive properties : Vapour pressure : 52 mbar
Temperature: 20 C ( 68 F ) Relative density / Density : = 1,38 Solubility : Water
Remarks: completely miscible Partition coefficient:
n-octanol/water : log Pow :
= 0,652
Method: calculated value Viscosity : Viscosity
1,24 mPa.s
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TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

Temperature: 38 C ( 100 F ) Vapour density : Remarks: no data available

9.3. Other data

Melting point/range : -43,5 C ( -46,3 F ) Decomposition
temperature : 315 C ( 599 F )

10. STABILITY AND REACTIVITY

10.1. Stability - Stable under recommended storage conditions.
10.2. Conditions to avoid - Heat.
- Naked flames, sparks. - Exposure to moisture. - Keep at temperature not exceeding: 315 C ( 599 F )
10.3. Materials to avoid - Oxidizing agents
- Strong bases 10.4. Hazardous decomposition products
- Hydrogen fluoride - Fluorophosgene - Carbon monoxide

11. TOXICOLOGICAL INFORMATION

Toxicological data
Acute oral toxicity

- LD50, rat, 210 - 590 mg/kg

Acute inhalation toxicity

- LC50, 6 h, rat, 1.922 - 2.618 mg/m3

Acute dermal irritation/corrosion

- LD50, rabbit, 1.680 mg/kg

Skin irritation

- rabbit, irritant (skin)

Eye irritation

- rabbit, Risk of serious damage to eyes.

Chronic toxicity

- Oral, after a single exposure, rat, Target Organs: gastro-intestinal system, testes, hematology system,
observed effect
- Inhalation, Repeated exposure, rat, Target Organs: testes, NOEL: 50 ppm, observed effect
Genetic toxicity in vitro

- in vitro, Animal testing did not show any mutagenic effects.

Toxicity to reproduction

- Effect on fertility
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TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

Remarks

- Harmful by inhalation, in contact with skin and if swallowed. - corrosive effects - Effects on fertility

12. ECOLOGICAL INFORMATION

12.1. Ecotoxicity effects
Acute toxicity

- Fishes, Pimephales promelas, LC50, 96 h, 119 mg/l

Chronic toxicity

- Remarks: no data available 12.2. Mobility

- Water/soil Remarks: considerable solubility and mobility
- Soil/sediments Remarks: non-significant adsorption
12.3. Persistence and degradability
Abiotic degradation

- Result: no data available

Biodegradation

- Remarks: no data available 12.4. Bioaccumulative potential

- Bioconcentration: log Pow = 0,652 Result: Bioaccumulation is unlikely. Remarks: calculated value
12.5. Other adverse effects - no data available
12.6. Remarks - Hazard for the environment is limited due to product properties:
-

. low toxicity for aquatic organisms. - . high mobility. - Does not bioaccumulate.

13. DISPOSAL CONSIDERATIONS

13.1. Waste from residues / unused products - In accordance with local and national regulations.
- Refer to manufacturer/supplier for information on recovery/recycling. - Or - Must be incinerated in a
suitable incineration plant holding a permit delivered by the competent authorities. - The incinerator must
be equipped with a system for the neutralisation or recovery of HF.
13.2. Packaging treatment - To avoid treatments, as far as possible, use dedicated containers.
13.3. RCRA Hazardous Waste - Listed RCRA Hazardous Waste (40 CFR 302) - No
- Unlisted RCRA Hazardous Waste (40 CFR 302) - Yes - D001 (ignitable waste)
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TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

14. TRANSPORT INFORMATION

UN-Number 1987 UN-Number 1987
IATA-DGR
Class 3 Packing group III ICAO-Labels FLAMMABLE LIQUID
Proper shipping name: ALCOHOLS, N.O.S. (TRIFLUOROETHANOL)
IMDG Class 3
Packing group III ICAO-Labels Flammable Liquids HI/UN No. 1987
Proper shipping name: ALCOHOLS, N.O.S. (TRIFLUOROETHANOL)
U.S. Dept of Transportation Class (Subsidiary) 3
Packing group III Label (Subsidiary) Flammable liquid Marine pollutant: no Emergency info: ERG: 127
Proper shipping name: ALCOHOLS, N.O.S. (TRIFLUOROETHANOL)
Canada (TDG) Class (Subsidiary) 3
Packing group III Label (Subsidiary) Flammable Liquid Marine pollutant: no Emergency info: ERG: 127
Proper shipping name: ALCOHOLS, N.O.S. (TRIFLUOROETHANOL)
- DOT Packing Group: III

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15. REGULATORY INFORMATION

15.1. Other regulations
US. EPA Emergency Planning and Community Right-To-Know Act (EPCRA) SARA Title III Section
302 Extremely Hazardous Substance (40 CFR 355, Appendix A)
- not regulated. SARA Hazard Designation (SARA 311/312)
- Acute Health Hazard: Yes.
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TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

- Fire Hazard: Yes. US. EPA Emergency Planning and Community Right-To-Know Act (EPCRA)
SARA Title III Section 313 Toxic
Chemicals (40 CFR 372.65) - Supplier Notification Required - not regulated.
US. EPA CERCLA Hazardous Substances (40 CFR 302) - not regulated.
US. New Jersey Worker and Community Right-to-Know Act (New Jersey Statute Annotated
Section 34:5A-5) - not regulated.
US. Pennsylvania Worker and Community Right-to-Know Law (34 Pa. Code Chap. 301-323) - not
regulated.
US. California Safe Drinking Water & Toxic Enforcement Act (Proposition 65) - not regulated.
15.2. Classification and labelling
Canada. Canadian Environmental Protection Act (CEPA). WHMIS Ingredient Disclosure List (Can.
Gaz., Part II, Vol. 122, No. 2)
- B2 Flammable Liquid - D2B Toxic Material Causing Other Toxic Effects
Remarks: This product has been classified in accordance with the hazard criteria of the Controlled
Products Regulations and the MSDS contains all the information required by the Controlled Products
Regulations.
EC Label - Classification and labelling according to Directive 67/548/EEC.
Symbol(s) Xn Harmful R-phrase(s) R10 Flammable.
R20/21/22 Harmful by inhalation, in contact with skin and if swallowed. R38 Irritating to skin. R41
Risk of serious damage to eyes. R48/20 Harmful: danger of serious damage to health by prolonged
exposure through inhalation. R62 Possible risk of impaired fertility.
S-phrase(s) S21 When using do not smoke. S37/39 Wear suitable gloves and eye/face protection.
S26 In case of contact with eyes, rinse immediately with plenty of
water and seek medical advice.

16. OTHER INFORMATION

Ratings : NFPA (National Fire Protection Association)
Health = 3 Flammability = 3 Instability = 0 Special =None HMIS (Hazardous Material Information
System)
Health = 3 Fire = 3 Reactivity = 0 PPE : Supplied by User; dependent on local conditions
P 343 / Canada Issuing date 11.12.2008 / Report version 1.0 Copyright 2008, SOLVAY FLUORIDES, LLC A subsidiary of SOLVAY Chemicals All Rights Reserved
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TFE (TRIFLUOROETHANOL) SAFETY DATA SHEET

Further information
- Update This data sheet contains changes from the previous version in section(s): 8.1
- Distribute new edition to clients
Material Safety Data Sheets contain country specific regulatory information; therefore, the MSDS's
provided are for use only by customers of the company mentioned in section 1 in North America. If you
are located in a country other than Canada, Mexico or the United States, please contact the Solvay

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Group company in your country for MSDS information applicable to your location. The previous
information is based upon our current knowledge and experience of our product and is not exhaustive. It
applies to the product as defined by the specifications. In case of combinations or mixtures, one must
confirm that no new hazards are likely to exist. In any case, the user is not exempt from observing all
legal, administrative and regulatory procedures relating to the product, personal hygiene, and integrity of
the work environment. (Unless noted to the contrary, the technical information applies only to pure
product). To our actual knowledge, the information contained herein is accurate as of the date of this
document. However, neither the company mentioned in section 1 nor any of its affiliates makes any
warranty, express or implied, including merchantability or fitness for use, or accepts any liability in
connection with this information or its use. This information is for use by technically skilled persons at their
own discretion and risk and does not relate to the use of this product in combination with any other
substance or any other process. This is not a license under any patent or other proprietary right. The user
alone must finally determine suitability of any information or material for any contemplated use, the
manner of use and whether any patents are infringed. This information gives typical properties only and
is not to be used for specification purposes. The company mentioned in section 1 reserves the right to
make additions, deletions or modifications to the information at any time without prior notification.
Trademarks and/or other products of the company mentioned in section 1 referenced herein are either
trademarks or registered trademarks of the company mentioned in section 1 or its affiliates, unless
otherwise indicated. This product has been classified in accordance with the hazard criteria of the
Controlled Products Regulations and the MSDS contains all the information required by the Controlled
Products Regulations. Copyright 2008, Company mentioned in Section 1. All Rights Reserved.
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MATERIAL SAFETY DATA SHEET

PRODUCT NAME: PHOSGENE

MSDS: G-67
Revised: 6/7/96 Page 1 of 7

1. Chemical Product and Company Identification

BOC Gases,
Division of
The BOC Group, Inc.
575 Mountain Avenue
Murray Hill, NJ 07974
TELEPHONE NUMBER: (908) 464-8100
BOC Gases
Division of
BOC Canada Limited
5975 Falbourne Street, Unit 2
Mississauga, Ontario L5R 3W6
TELEPHONE NUMBER: (905) 501-1700
24-HOUR EMERGENCY TELEPHONE NUMBER:
CHEMTREC (800) 424-9300
24-HOUR EMERGENCY TELEPHONE NUMBER:
(905) 501-0802
EMERGENCY RESPONSE PLAN NO: 20101
PRODUCT NAME: PHOSGENE
CHEMICAL NAME: Phosgene
COMMON NAMES/SYNONYMS: Carbon Oxychloride; Carbonyl Chloride; Carbonyl Dichloride;
Diphosgene

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TDG (Canada) CLASSIFICATION: 2.3 (8)

WHMIS CLASSIFICATION: A, E, F, D1A
PREPARED BY: Loss Control (908)464-8100/(905)501-1700
PREPARATION DATE: 6/1/95
REVIEW DATES: 6/7/96

2. Composition, Information on Ingredients

INGREDIENT % VOLUME PEL-OSHA1 TLV-ACGIH2 LD50 or LC50
Route/Species
Phosgene
FORMULA: CCl20
CAS: 75-44-5
RTECS #: SY5600000
100.0 0.1 ppm TWA 0.1 ppm TWA LC50
800 ppm
(human)
1 As stated in 29 CFR 1910, Subpart Z (revised July 1, 1993)
2 As stated in the ACGIH 1994-95 Threshold Limit Values for Chemical Substances and Physical Agents

3. Hazards Identification+
EMERGENCY OVERVIEW
Corrosive to exposed tissues. Inhalation of vapors may result in pulmonary edema and chemical
pneumonitis. Nonflammable. Reacts violently and decomposes to toxic compounds, including
chlorine, on contact with moisture.
ROUTE OF ENTRY:
Skin Contact
Yes
Skin Absorption
No
Eye Contact
Yes
Inhalation
Yes
Ingestion
No
PRODUCT NAME: PHOSGENE
MSDS: G-67
Revised: 6/7/96 Page 2 of 7
HEALTH EFFECTS:
Exposure Limits
Yes
Irritant
Yes
Sensitization
No
Teratogen
No
Reproductive Hazard
No
Mutagen
No
Synergistic Effects
None Reported
Carcinogenicity: -- NTP: No ARC: No OSHA: No
EYE EFFECTS:
None known.
SKIN EFFECTS:
None known.
INGESTION EFFECTS:
None known.

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INHALATION EFFECTS:
Immediate symptoms from inhalation are choking, coughing, tightness of the chest, catching of the breath,
lacrimation, difficulty in and painful breathing and eventual cyanosis. Serious symptoms are pulmonary edema
and asphyxiation which may not be manifested for several hours after overexposure. Long lasting (several
months) symptoms may be coughing, bloody sputum and general malaise.
NFPA HAZARD CODES HMIS HAZARD CODES RATINGS SYSTEM
Health: 4 Health: 4 0 = No Hazard
Flammability: 0 Flammability: 0 1 = Slight Hazard
Reactivity: 1 Reactivity: 1 2 = Moderate Hazard
3 = Serious Hazard
4 = Severe Hazard

4. First Aid Measures

EYES:
None required.
SKIN:
None required.
INGESTION:
None required.
PRODUCT NAME: PHOSGENE
MSDS: G-67
Revised: 6/7/96 Page 3 of 7
INHALATION:
Conscious persons should be assisted to an uncontaminated area and inhale fresh air. Unconscious persons
should be moved to an uncontaminated area, and given artificial resuscitation and supplemental oxygen. Keep
the victim warm and quiet. Assure that mucous does not obstruct the airway by positional drainage. Delayed
pulmonary edema may occur. Keep patient under medical observation for at least 48 hours. Treatment should
be symptomatic and supportive.
PROMPT MEDICAL ATTENTION IS MANDATORY IN ALL CASES OF OVEREXPOSURE TO
PHOSGENE. RESCUE PERSONNEL SHOULD BE EQUIPPED WITH SELF-CONTAINED BREATHING
APPARATUS.

5. Fire Fighting Measures

Conditions of Flammability: Nonflammable
Flash point:
None
Method:
Not Applicable
Autoignition
Temperature: None
LEL(%): None UEL(%): None
Hazardous combustion products: None
Sensitivity to mechanical shock: None
Sensitivity to static discharge: None
FIRE AND EXPLOSION HAZARDS:
Nonflammable.
FIRE FIGHTING INSTRUCTIONS:
NONE. Material is not flammable. See spill and leaks information for protective equipment when fighting a
spill.

6. Accidental Release Measures

Evacuate all personnel from affected area. Use appropriate protective equipment. If leak is in users equipment,
be certain to purge piping with inert gas prior to attempting repairs. If leak is in container or container valve,
contact the appropriate emergency telephone number listed in Section 1 or call your closest BOC location.

7. Handling and Storage

Moist phosgene is corrosive to most metals. Hastelloy A or B as well as tantalum, platinum and gold show good
corrosive resistance to moist phosgene.
Protect cylinders from physical damage. Store in cool, dry, well-ventilated area away from heavily trafficked

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areas and emergency exits. Do not allow the temperature where cylinders are stored to exceed 130oF (54oC).
Cylinders should be stored upright and firmly secured to prevent falling or being knocked over. Full and empty
cylinders should be segregated. Use a "first in-first out" inventory system to prevent full cylinders being stored
for excessive periods of time.
PRODUCT NAME: PHOSGENE
MSDS: G-67
Revised: 6/7/96 Page 4 of 7
Use only in well-ventilated areas. Valve protection caps and valve outlet threaded plugs must remain in place
unless container is secured with valve outlet piped to use point. Do not drag, slide or roll cylinders. Use a
suitable hand truck for cylinder movement. Use a pressure reducing regulator when connecting cylinder to
lower pressure (less than 75 psig) piping or systems. Do not heat cylinder by any means to increase the
discharge rate of product from the cylinder. Use a check valve or trap in the discharge line to prevent hazardous
back flow into the cylinder.
For additional storage and handling recommendations, consult Compressed Gas Associations Pamphlet P-1.
Never carry a compressed gas cylinder or a container of a gas in cryogenic liquid form in an enclosed space such
as a car trunk, van or station wagon. A leak can result in a fire, explosion, asphyxiation or a toxic exposure.

8. Exposure Controls, Personal Protection

EXPOSURE LIMITS1:
INGREDIENT % VOLUME PEL-OSHA2 TLV-ACGIH3 LD50 or LC50
Route/Species
Phosgene
FORMULA: CCl20
CAS: 75-44-5
RTECS #: SY5600000
100.0 0.1 ppm TWA 0.1 ppm TWA LC50
800 ppm
(human)
1 Refer to individual state of provincial regulations, as applicable, for limits which may be more stringent than
those listed here.
2 As stated in 29 CFR 1910, Subpart Z (revised July 1, 1993)
3 As stated in the ACGIH 1994-1995 Threshold Limit Values for Chemical Substances and Physical Agents.

IDLH: 2 ppm
ENGINEERING CONTROLS:
Use a laboratory hood with forced ventilation for handling small quantities. Use local exhaust to prevent
accumulation above the exposure limits.
EYE/FACE PROTECTION:
Gas tight chemical goggles or full-face piece respirator.
SKIN PROTECTION:
Rubber or Teflon protective gloves.
RESPIRATORY PROTECTION:
Positive pressure air line with full-face mask and escape bottle or self-contained breathing apparatus should be
available for emergency use and routine use when exposures are above set limits.
OTHER/GENERAL PROTECTION:
Safety shoes, safety shower, eyewash "fountain".
PRODUCT NAME: PHOSGENE
MSDS: G-67
Revised: 6/7/96 Page 5 of 7

9. Physical and Chemical Properties

PARAMETER VALUE UNITS
Physical state (gas, liquid, solid) : Gas
Vapor pressure : 22.6 psia
Vapor density (Air = 1) : 3.41
Evaporation point : Not Available
Boiling point : 45.6
: 7.55
oF
oC
Freezing point : -198

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: -127
oF
oC
pH : Not Available
Specific gravity : Not Available
Oil/water partition coefficient : Not Available
Solubility (H20) : Decomposes
Odor threshold : Not Available
Odor and appearance : Colorless gas with sweet odor in low
concentrations, becoming suffocating in high
concentrations

10. Stability and Reactivity

STABILITY:
Stable at temperatures below 572oF (300oC).
INCOMPATIBLE MATERIALS:
May react violently with water, ammonia, primary amines.
HAZARDOUS DECOMPOSITION PRODUCTS:
Hydrochloric acid and carbon dioxide. Carbon monoxide, chlorine.
HAZARDOUS POLYMERIZATION:
Will not occur.

11. Toxicological Information

No chronic effects data unrelated to phosgenes corrosivity given in the Registry of Toxic Effects of Chemical
Substances (RTECS) or Sax, Dangerous Properties of Industrial Materials, 7th ed.

12. Ecological Information

No data given.

13. Disposal Considerations

Do not attempt to dispose of residual waste or unused quantities. Return in the shipping container PROPERLY
LABELED, WITH ANY VALVE OUTLET PLUGS OR CAPS SECURED AND VALVE PROTECTION CAP
IN PLACE to BOC Gases or authorized distributor for proper disposal.
PRODUCT NAME: PHOSGENE
MSDS: G-67
Revised: 6/7/96 Page 6 of 7

14. Transport Information

PARAMETER United States DOT Canada TDG
PROPER SHIPPING NAME: Phosgene Phosgene
HAZARD CLASS: 2.3 2.3 (8)
IDENTIFICATION NUMBER: UN 1076 UN 1076
SHIPPING LABEL: POISON GAS, CORROSIVE POISON GAS, CORROSIVE

Additional Marking Requirement: Inhalation Hazard

If net weight of product > 10 pounds, the container must be also marked with the letters RQ.
Additional Shipping Paper Description Requirement: Poison Inhalation Hazard, Zone A
If net weight of product > 10 pounds, the shipping papers must be also marked with the
letters RQ.

15. Regulatory Information

Phosgene is listed under the accident prevention provisions of section 112(r) of the Clean Air Act (CAA) with a
threshold quantity (TQ) of 500 pounds.
SARA TITLE III NOTIFICATIONS AND INFORMATION
Phosgene is listed as an extremely hazardous substance (EHS) subject to state and local reporting under Section
304 of SARA Title III (EPCRA).
The presence of phosgene in quantities in excess of the threshold planning quantity (TPQ) of 10 pounds requires
certain emergency planning activities to be conducted.
Releases of phosgene in quantities equal to or greater than the reportable quantity (RQ) of 10 pounds are subject
to reporting to the National Response Center under CERCLA, Section 304 SARA Title III.
SARA TITLE III - HAZARD CLASSES:
Acute Health Hazard

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Chronic Health Hazard

Sudden Release of Pressure Hazard
Reactivity Hazard
Fire Hazard
SARA TITLE III - SECTION 313 SUPPLIER NOTIFICATION:
This product contains the following toxic chemicals subject to the reporting requirements of section 313 of the
Emergency Planning and Community Right-To-Know Act (EPCRA) of 1986 and of 40 CFR 372:
CAS NUMBER INGREDIENT NAME PERCENT BY VOLUME
75-44-5 PHOSGENE ~ 100.0
This information must be included on all MSDSs that are copied and distributed for this material.

16. Other Information

Compressed gas cylinders shall not be refilled without the express written permission of the owner. Shipment of
a compressed gas cylinder which has not been filled by the owner or with his/her (written) consent is a violation
of transportation regulations.
PRODUCT NAME: PHOSGENE
MSDS: G-67
Revised: 6/7/96 Page 7 of 7
DISCLAIMER OF EXPRESSED AND IMPLIED WARRANTIES:
Although reasonable care has been taken in the preparation of this document, we extend no warranties and make
no representations as to the accuracy or completeness of the information contained herein, and assume no
responsibility regarding the suitability of this information for the users intended purposes or for the
consequences of its use. Each individual should make a determination as to the suitability of the information for
their particular purpose(s).

398