FACULTY OF CHEMICAL & NATURAL RESOURCES

ENGINEERING
UNIVERSITY MALAYSIA PAHANG


BKF 3553
PROCESS SIMULATION & COMPUTER AIDED DESIGN
LECTURER: DR ING- RIZZA BIN OTHMAN



MINI PROJECT



PREPARED BY:
CHOO WEI CHUN KE11037
HOR CHEE HENG KE11029
TAN YONG CHAI KA11206
LEE HON KIT KA11182
LEE JHIN ONN KA11178

DATE OF SUBMISSION:
27
th
MAY 2014



2

Table of Contents
1.0 INTRODUCTION ............................................................................................................ 3
1.1 Process Description ............................................................................................................ 3
1.1.1 Background................................................................................................................... 3
1.1.2 History of formaldehyde production ............................................................................ 4
1.1.3 Objectives...................................................................................................................... 4
1.1.4 Scope of study............................................................................................................... 5
1.2 PFD (Process Flow Diagram) ............................................................................................ 5
1.3 Reaction kinetics ................................................................................................................. 8
1.4 Operating conditions .......................................................................................................... 9
2.0 MODELLING & SIMULATION METHODOLOGY ............................................... 10
2.1 Chemical components definition ..................................................................................... 10
2.2 Thermodynamic properties selection ............................................................................. 10
2.3 Flowsheet design ............................................................................................................... 11
2.4 Plant capacity .................................................................................................................... 12
2.5 Input parameters setup for each unit operation ............................................................ 13
2.6 Mass balance of major equipments ................................................................................. 14
3.0 RESULTS & DISCUSSION .......................................................................................... 16
4.0 CONCLUSION & RECOMMENDATION ....................................................................... 18
References ................................................................................................................................... 19


3

1.0 INTRODUCTION
1.1 Process Description
1.1.1 Background
Formaldehyde is also known as Methanal, Methylene oxide or Formalin. It is the first in
the series of aliphatic aldehydes, with the structure H2C=O. Formaldehyde is a reactive
and versatile chemical intermediate. Pure formaldehyde is a colourless gas with a
pungent and suffocating odour at ordinary temperatures. The ignition temperature of
formaldehyde gas is 430C (Gerberich and Seaman, 2004).
Mixtures with air are explosive. It is stable at 80 - 100C when pure, but small amounts
of impurities such as water cause rapid polymerisation to poly (oxymethylenes).
Formaldehyde liquefies at -19.2C and solidifies at -118C, giving a white paste. At
temperatures of up to 80C, the liquid and gas forms of formaldehyde polymerise
rapidly.
Formaldehyde (CH2O), the target product of this project, acts as a synthesis baseline for
many other chemical compounds including phenol formaldehyde, urea formaldehyde
and melamine resin that subsequently used as adhesives and binders for particle board
and plywood. The most widely produced grade is formalin (37 wt. % formaldehyde in
water) aqueous solution. In this projects study, formaldehyde is to be produced through
a catalytic vapor-phase oxidation reaction involving methanol and oxygen according to
the following reactions:

The first desired reaction is exothermic while the second is an endothermic reaction. The
projects target is to design a plant with a capacity of 50,000 metric ton formalin/annum
with the operating days of 49weeks/343 days in a year. This plant is to include three
major units; a reactor, an absorber and a distillation column. Also it includes pumps,
compressors and heat exchangers. All are to be designed and operated according to this
production capacity.

4

1.1.2 History of formaldehyde production
In 1859, Aleksandr Butlerov, a Russian chemist, discovered formaldehyde. After 10
years, another chemist form German who named August Hofmann finally identified
formaldehyde. The production of formaldehyde began in the beginnings of the twentieth
century. The annual growth rate for formaldehyde production averaged to 11.7%
between 1958 and 1968. The production was 54% of capacity in the mid-1970s. Annual
growth rate of formaldehyde was 2.7% per year from 1988 to 1997. The production of
formaldehyde was ranked 22
nd
among the top 50 chemicals manufactured in the United
States in 1992. The total annual formaldehyde capacity in 1998 was estimated by 11.3
billion pounds and its production capacity is increasing exponentially in the global until
it reaches a worlds production of 32.5 million metric tons by 2012. The demand of the
formaldehyde becomes high because of its low costs compared to other materials and its
receptivity for reaching high purities. It is also the center of many chemical researches
and alternatives manufacture methods.
Applications of formaldehyde in industries include building block for organic
compounds, photographing washing, woodworking, cabinet-making industries, glues,
adhesives, paints, explosives, disinfecting agents, tissue preservation and drug testing
field.

1.1.3 Objectives
1. To study an integrated design of a plant for formaldehyde production with
specified capacity in a point of view in chemical engineering.
2. To investigate the entire process unit design of the plant such as process flow
diagrams and operation parameters.




5

1.1.4 Scope of study
1. To apply knowledge of mass and heat transfer, fluid dynamics, unit operations,
reaction kinetics and process control in the project.
2. To perform mass and energy balances, Hysys simulation of the Process Flow
Diagrams, design of the reactor, design of heat exchangers, design of the absorber
and distillation column and energy optimization in the project.

1.2 PFD (Process Flow Diagram)

Figure 1.2.1: Formalin process flow diagram (Turton et al., 2009)
Figure 1.2.1 is a process of producing formalin (37 wt% formaldehyde in water) from
methanol using the silver catalyst process.
Air (0.21% Oxygen; 0.79% Nitrogen; 25 C; 1 atm) is compressed and mixed the
methanol (30 C; 1.2 bar) which has been preheated, fresh and recycled to provide
reactor feed. The feed mixture contains around 39 mol% methanol in air, which is more
6

than upper flammability limit for methanol. (For methanol, UFL= 36 mol%; LFL= 6
mol%).
In the PFR reactor, there are two reactions happen:


The reactor (length 0.347m and diameter 0.050799m) is using the silver catalyst (Bed
voidage 0.5 and particle density 1500 kg/cum), in the form of wire gauze, suspended
above a heat exchanger tube bank. It is a must to the remove the heat produced in the
adiabatic reactor section due to the net reaction is highly exothermic, thus the close
proximity of the heat exchanger tubes. Inside the heat exchanger, there is a pool of water
on the shell side. The set point on a level controller is adjusted when it detects the
temperature of the effluent is very high. The level controller will send signal to the
boiler so that to increase the feed water rate entering from the reboiler to the heat
exchanger to increase the water vaporization rate to remove more heat. In general, the
liquid-level controller on the boiler feed water is adjusted to keep the tube bundle fully
immersed. The reactor effluent enters an absorber in which most of the methanol and
formaldehyde are absorbed into water, with most of the remaining light gas purged into
the off-gas stream. The formaldehyde, the methanol, and water enter a distillation
column, in which the overhead product, methanol is recycled; the bottom product,
formaldehyde/ water mixture that contains <1 wt% methanol as an inhibitor. Due to
there are some batch downstream process, this mixture send to a storage tank after
cooling. A suitable amount of water is added inside the storage tank when the
downstream process draws from the storage tank because the composition in the storage
tank exceeds 37 wt% formaldehyde. The storage tank contents must be maintained
between 35C and 45C to prevent unfavourable conditions like polymerization and
formic acid formation from happening. Figure 1.2.2 shows the block flow diagram of
formalin production.
7

Figure 1.2.2: Formalin block flow diagram

8

1.3 Reaction kinetics
Kinetic information for the methanol oxidation reaction:

The rate expression is:

Where p is a partial pressure in atm, and m refers to methanol. The rate expression is
only valid when oxygen is present in excess. The constants are defined as:

Where T is in Kelvin, the rate data as follows for the side reaction:

The rate expression is:

Standard enthalpies of reaction (298 K, 1 atm) for the two reactions are given as:

9

1.4 Operating conditions
The process that will be applied in this project is the production of formaldehyde
through the vapor phase oxidation reaction between methanol and air (Oxygen).
In this process, a reactor, an absorber and a distiller are required for the production of
formaldehyde. First and foremost, two streams; first stream is a mixture of fresh
methanol (25C, 1atm) and second stream is recycled methanol (68.3C and 1.2atm)
pumped to 3atm and vaporized to 150C are received by a reactor. The reactor is
designed for 87.4% methanol conversion. Secondly, the absorber receives the outlet
stream of methanol from the reactor at 343C and a fresh stream of water (30C,
138KPa). Absorption of 99% is expected where the liquid outlet is heated to 102C.
Next, the mixed liquid from the absorber is received by the distillation column and
further separated the overhead stream (68.3C, 1.2atm) then recycles it back to methanol
fresh feed mixing point. The bottom formaldehyde stream is pumped and mixed with
demonized water forming (37 wt. % formaldehyde) formalin stream that is sent for
storage.

10

2.0 MODELLING & SIMULATION METHODOLOGY
2.1 Chemical components definition

Figure 2.1: Chemical components involve in formalin production.

2.2 Thermodynamic properties selection

Figure 2.2: Properties method selection in Aspen Plus V8.0.

11

The NRTL model can describe Vapor-Liquid Equilibrium and Liquid-Liquid
Equilibrium of strongly non-ideal solutions. The NRTL model can handle any
combination of polar and non-polar compounds, up to very strong non-ideality.
Parameters should be fitted in the temperature, pressure, and composition range of
operation. No component should be close to its critical temperature. The vapor phase
EOS name for NRTL-HOC property method is Non-Random Two-Liquid on Hayden-O
Connell. Do not use the Hayden-O'Connell-based property methods at pressures
exceeding 10 to 15 atm.
(Renon & Prausnitz, 1968)


2.3 Flowsheet design

Figure 2.3: Flowsheet design using Aspen Plus V8.0.

12

2.4 Plant capacity
Formalin Production statistics:
Optimum Operating hour given:
/ 343 days
Production Rate Given: (50,000 metric tonnes/yr)
Production rate per year =

()

Since CH
2
O and H
2
O has the same no. of mole of CH
2
(OH)
2
produced, therefore, no. of
mole of CH
2
O and H
2
O feed is

.

Table 2.4: Calculation of Molar and Mass Feed rate.
Species Mole (kmol/yr) Mass (MT/yr)
Formaldehyde 1041666.67 31280.00
Water 1041666.67 18720.00
Formalin 1041666.67 50,000.00


13

2.5 Input parameters setup for each unit operation
Table 2.5: Input parameters setup for each unit operation
Equipment Description
Mixer 1 Mixing of pure methanol and recycled methanol.
Inlet and outlet temperature 30
o
C and pressure 1.5 bar.
Inlet and outlet flow rate 76.92 kmol/hr.
Pump Outlet pressure of methanol at 3 bar.
Heater 1 To heat the reactant from 30
o
C to 150
o
C
To decrease pressure from 3 bar to 2.65 bar.
Vapour-liquid valid phase.
Compressor Compress air.
Inlet temperature and pressure are 25
o
C and 1 atm.
Outlet temperature and pressure are 174
o
C and 3 bar.
Inlet and outlet flow rate 145.94 mol/hr
Oxygen mole fraction: 0.21
Nitrogen mole fraction: 0.79
Heater 2 To heat the reactant from 174
o
C to 200
o
C
To decrease pressure from 3 bar to 2.65 abr.
Vapour-liquid valid phase.
Mixer 2 To mix methanol and air.
Outlet temperature is 175
o
C after mixing.
PFR Operation set at 200
o
C
Reactor length 0.347m and diameter 0.050799m
Catalyst present in the reactor
Bed voidage is 0.5
Particle density is 1500 kg/cum
Chiller Decrease temperature to 100
o
C and pressure to 1.5 bar.
Vapour-liquid valid phase.
Absorption Tower Rate-based calculation type
30 number of stages
Condenser pressure 1.5 bar
Feed streams above stage 1 (intermediate product)
Feed streams on stage 30 (water)
Distillation
Column
Equilibrium calculation type
31 number of stages
Total condenser
Reflux ratio of 37.34
Bottom rate is 1 kmol/hr
Condenser pressure 1.5 bar
Feed stream at 18th stages


14

2.6 Mass balance of major equipments
Reactor

Assumption:
Adiabatic
No pressure drop


Absorber

n
8
= 319.67 kmol/hr
x
CH3OH
= 0.240622
x
O2
= 0.096041
x
H2O
= 0.302024
x
N2
= 0.3613067
n
11
= 143 kmol/hr
x
H2O
= 1

n
12
= 327.79 kmol/hr
x
CH3OH
= 0.0283
x
O2
= 0.06096
x
CH2O
= 0.06819
x
H2O
= 0.41101
x
H2
= 0.07965
x
N2
= 0.35193
n
10
= 356.46 kmol/hr
x
CH3OH
= 0.0825945
x
O2
= 0.0561529
x
CH2O
= 0.1331915
x
H2O
= 0.3308004
x
H2
= 0.0732467
x
N2
= 0.3240139
n
13
= 171.67 kmol/hr
x
CH3OH
= 0.117542
x
O2
= 0.0002
x
CH2O
= 0.14636
x
H2O
= 0.73508
x
H2
= 0
x
N2
= 0.0008
n
9
= 356.46 kmol/hr
x
CH3OH
= 0.0825945
x
O2
= 0.0561529
x
CH2O
= 0.1331915
x
H2O
= 0.3308004
x
H2
= 0.0732467
x
N2
= 0.3240139
15

Distillation column




Assumption:
Light key component is methanol
Heavy key component is water
Non-heavy key is formaldehyde



n
13
= 171.67 kmol/hr
x
CH3OH
= 0.117542
x
O2
= 0.0002
x
CH2O
= 0.14636
x
H2O
= 0.73508
x
H2
= 0
x
N2
= 0.0008
n
13
= 96.811 kmol/hr
x
CH3OH
= 0
x
O2
= 0.00056
x
CH2O
= 0
x
H2O
= 0.997285
x
H2
= 0.00002
x
N2
= 0.00214
n
13
= 149 kmol/hr
x
CH3OH
= 0.135425
x
O2
= 0
x
CH2O
= 0.01765
x
H2O
= 0.8469
x
H2
= 0
x
N2
= 0
16

3.0 RESULTS & DISCUSSION
Table 3.1: Stream results.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
MIX1 PUMP1 HEATER1 MIX2 COM1 CHILLER1 MIX2 PFR1 CHILLER2 ASB1 ASB1 DIST1 MIX1
MIX1 PUMP1 HEATER1 COM1 CHILLER1 MIX2 PFR1 CHILLER2 ASB1 ASB1 DIST1 DIST1
LIQUID LIQUID LIQUID VAPOR VAPOR VAPOR VAPOR VAPOR VAPOR VAPOR LIQUID VAPOR LIQUID LIQUID LIQUID
Substream: MIXED
Mole Flow kmol/hr
METHANOL 76.9200 76.9200 76.9200 76.9200 0.0000 0.0000 0.0000 76.9200 29.4420 29.4420 0.0000 9.2637 20.1783 0.0000 20.1783
OXYGEN 0.0000 0.0542 0.0542 0.0542 30.6474 30.6474 30.6474 30.7016 20.0165 20.0165 0.0000 19.9816 0.0350 0.0542 0.0000
FORMA-01 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 47.4780 47.4780 0.0000 22.3521 25.1260 0.0000 2.6307
WATER 0.0000 96.5484 96.5484 96.5484 0.0000 0.0000 0.0000 96.5484 117.9185 117.9185 143.0000 134.7275 126.1910 96.5484 126.1910
HYDROGEN 0.0000 0.0019 0.0019 0.0019 0.0000 0.0000 0.0000 0.0019 26.1098 26.1098 0.0000 26.1084 0.0015 0.0019 0.0000
NITROGEN 0.0000 0.2068 0.2068 0.2068 115.2926 115.2926 115.2926 115.4994 115.4994 115.4994 0.0000 115.3617 0.1376 0.2068 0.0000
Mole Frac
METHANOL 1.0000 0.4428 0.4428 0.4428 0.0000 0.0000 0.0000 0.2406 0.0826 0.0826 0.0000 0.0283 0.1175 0.0000 0.1354
OXYGEN 0.0000 0.0003 0.0003 0.0003 0.2100 0.2100 0.2100 0.0960 0.0562 0.0562 0.0000 0.0610 0.0002 0.0006 0.0000
FORMA-01 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1332 0.1332 0.0000 0.0682 0.1464 0.0000 0.0177
WATER 0.0000 0.5557 0.5557 0.5557 0.0000 0.0000 0.0000 0.3020 0.3308 0.3308 1.0000 0.4110 0.7351 0.9973 0.8469
HYDROGEN 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0732 0.0732 0.0000 0.0796 0.0000 0.0000 0.0000
NITROGEN 0.0000 0.0012 0.0012 0.0012 0.7900 0.7900 0.7900 0.3613 0.3240 0.3240 0.0000 0.3519 0.0008 0.0021 0.0000
Mass Flow kg/hr
METHANOL 2464.6830 2464.6830 2464.6830 2464.6830 0.0000 0.0000 0.0000 2464.6830 943.3853 943.3853 0.0000 296.8288 646.5566 0.0000 646.5565
OXYGEN 0.0000 1.7334 1.7334 1.7334 980.6800 980.6800 980.6800 982.4134 640.5046 640.5046 0.0000 639.3862 1.1184 1.7334 0.0000
FORMA-01 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 1425.5880 1425.5880 0.0000 671.1491 754.4387 0.0000 78.9901
WATER 0.0000 1739.3460 1739.3460 1739.3460 0.0000 0.0000 0.0000 1739.3460 2124.3350 2124.3350 2576.1850 2427.1530 2273.3660 1739.3460 2273.3660
HYDROGEN 0.0000 0.0039 0.0039 0.0039 0.0000 0.0000 0.0000 0.0039 52.6343 52.6343 0.0000 52.6314 0.0030 0.0039 0.0000
NITROGEN 0.0000 5.7923 5.7923 5.7923 3229.7470 3229.7470 3229.7470 3235.5390 3235.5390 3235.5390 0.0000 3231.6840 3.8556 5.7923 0.0000
Mass Frac
METHANOL 1.0000 0.5852 0.5852 0.5852 0.0000 0.0000 0.0000 0.2926 0.1120 0.1120 0.0000 0.0406 0.1757 0.0000 0.2156
OXYGEN 0.0000 0.0004 0.0004 0.0004 0.2329 0.2329 0.2329 0.1166 0.0761 0.0761 0.0000 0.0874 0.0003 0.0010 0.0000
FORMA-01 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.1693 0.1693 0.0000 0.0917 0.2050 0.0000 0.0263
WATER 0.0000 0.4130 0.4130 0.4130 0.0000 0.0000 0.0000 0.2065 0.2522 0.2522 1.0000 0.3316 0.6179 0.9957 0.7581
HYDROGEN 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0062 0.0062 0.0000 0.0072 0.0000 0.0000 0.0000
NITROGEN 0.0000 0.0014 0.0014 0.0014 0.7671 0.7671 0.7671 0.3842 0.3842 0.3842 0.0000 0.4416 0.0010 0.0033 0.0000
Total Flow kmol/hr 76.9200 173.7313 173.7313 173.7313 145.9400 145.9400 145.9400 319.6713 356.4642 356.4642 143.0000 327.7949 171.6693 96.8113 149.0000
Total Flow kg/hr 2464.6830 4211.5590 4211.5590 4211.5590 4210.4270 4210.4270 4210.4270 8421.9860 8421.9860 8421.9860 2576.1850 7318.8320 3679.3380 1746.8760 2998.9130
Total Flow l/min 52.1992 82.3914 82.4082 37588.4600 59481.0300 30178.8500 36135.6900 72856.2000 87930.6300 122158.0000 43.4087 108331.0000 75.3443 34.2124 59.1553
Temperature C 30.0000 30.6548 30.8119 150.0000 25.0000 174.2000 200.0000 165.2305 200.0000 100.0000 30.0000 87.0727 87.3135 -43.3864 103.9483
Pressure bar 1.2000 1.2000 3.0000 2.6500 1.0133 3.0000 2.6500 2.6500 2.6500 1.5000 1.5000 1.5000 1.5000 1.5000 1.5000
Vapor Frac 0.0000 0.0000 0.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 0.0000 1.0000 0.0000 0.0000 0.0000
Liquid Frac 1.0000 1.0000 1.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 1.0000 0.0000 1.0000 1.0000 1.0000
Solid Frac 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
17

Discussion
We unable to solve the material for block DIST1 which is a rigorous distillation column
calculation. This is because the method used unable to model the behaviour of formaldehyde that
is provided by our reference. In Turton, formaldehyde is assume to follow the water but our
simulation method assume formaldehyde has very weak solubility in water and very volatile. K-
Value for formaldehyde/water/methanol system is provided in the Turtons reference, however
aspen does not feature that allow the use of this data. Furthermore, distillate of this block
supposedly to contain mostly methanol is recycled back which further complicate the calculation.
The complexities lead to the program unable to solve the calculation under a maximum 200
iteration.
From Turton reference, formaldehyde is able to be nearly fully absorbed by water with 99%
recovery at stream 13. However in our simulation, 47.07% of the formaldehyde is wasted at
stream 12 which is an off-gas stream. This suggests that the NRTL-HOC thermodynamic method
model the formaldehyde properties as more volatile and less soluble in water than it should in
experiment. We have tried more other thermodynamic properties such as NRTL-NTH, UNIFAC,
UNIQUAC but the result remains roughly the same.
Therefore, we recommend that aspen tech should add a feature whereby user is able to key in
experimental K-value data and the program is able to use the data to model the separation process.

18

4.0 CONCLUSION & RECOMMENDATION
Conclusion
We use ASPEN plus V8.0 to plan our operation. We specify the reaction kinetics and NRTL-
HOC as our thermodynamic property method. The raw material we used is methanol and air and
the product is 37 %wt formaldehyde in water also known as formalin. The unit operator that we
used is mixer, compressor, heater, chiller, PFR reactor, absorber and distillation column. Finally,
we obtained the production of 50,000MT/yr of formalin.
Recommendation
To improve the energy efficiency of the plant, the hot stream of the reactor outlet can be used to
preheat the inlet of the reactor since the reaction is exothermic which require cooling and the
reactant require preheating. Basically design heat exchanger network to save on energy cost.
Furthermore, this process can be further optimize by perform economic analysis to find the
process condition where less operating cost is needed. According to the Ott et al.,(2005),
UNIFAC method is used to produce formalin. The reason we not use this method is because we
are lacking the binary parameter for formalin-methanol system.

19

References
Gerberich, H.R., and G.C. Seaman (2004). Formaldehyde, Kirk-Othmer Encyclopedia of
Chemical Technology, on-line version (New York: John Wiley & Sons).
H. Renon and J.M. Prausnitz, (1968). "Local Compositions in Thermodynamic Excess Functions
for Liquid Mixtures," AIChE J., Vol. 14, No. 1, pp. 135 144.
Ott, M., Schoenmakers, H. and Hasse, H. (2005). Distillation of formaldehyde containing
mixtures: laboratory experiments, equilibrium stage modeling and simulation. Chemical
Engineering and Processing: Process Intensification, 44(6), pp. 687--694.
Turton, R., Bailie, R., Whiting, W. and Shaeiwitz, J. (2009). Analysis, synthesis, and design of
chemical processes. 3rd ed. Upper Saddle River, N.J.: Prentice Hall PTR.