.

A PLANT DESIGN REPORT ON THE

PRODUCTION OF 40,000 BPD OF S15 (ULSD)
FROM RAW DIESEL

SUBMITTED BY:

HAFIZ MUNEEB AHMAD CE-M10-50

MUHAMMAD NOUMAN CE-M10-08
ADNAN ALI CE-M10-40
MUHAMMAD TAUSEEF PG-M10-07

SESSION 2010-2014

SUPERVISORS:

PROF. DR. MAHMOOD SALEEM

ENGR. SYED ZOHAIB JAVEED ZAIDI
Institute of Chemical Engineering & Technology,
University of The Punjab
Quaid-e-Azam Campus, Lahore-54590
 A Plant Design Report
On
The Production Of 40,000 Bpd Of S-15 From Raw Diesel By
Ultra Hydrodesulfurization

SUBMITTED TO

INSTITUTE OF CHEMICAL ENGINEERING & TECHNOLOGY,

UNIVERSITY OF THE PUNJAB, LAHORE

IN PARTIAL FULFILLMENT FOR THE REQUIREMENTS OF

THE DEGREE OF
B.Sc. (Engg.) CHEMICAL ENGINEERING
BY
HAFIZ MUNEEB AHMAD CE-M10-50
MUHAMMAD NOUMAN CE-M10-08
ADNAN ALI CE-M10-40
MUHAMMAD TAUSEEF PG-M10-07
SESSION-2010-2014

SUPERVISORS
DR. MAHMOOD SALEEM
ENGR.SYED ZOHAIB JAVEED ZAIDI
November 2014

Institute of Chemical Engineering & Technology,

Faculty of Engineering & Technology,
University of The Punjab,
Quaid-e-Azam Campus, Lahore-54590
This page is intentionally left blank.

2014

Tauseef Ahmad Awan

All Rights Reserved

 To Almighty Allah, For His Daily
Blessings, Make All Our Work Possible.

To Our Parents Who Are Full Of

Sympathy And Everlasting Love.

To Prof. Dr. Mahmood Saleem; For His

Fatherly Behavior And Inspiring
Guidance

To Our Dearest Homeland, Pakistan

 All Praises To

Almighty ALLAH

WHO Gave Us Ability And Strength To Complete The Project,

And All Respects For

HIS Prophet

Muhammad (PBUH, On Whom Be ALLAHS Blessings And Salutations).

We All Owe Special Thanks To Our

Project Supervisor

Prof. Dr. Mahmood Saleem

Who Helped Us Throughout The Compilation Of This Design Project His Motivation,

Guidance And Kind Words Always Encouraged Us To Work With Commitment.

Whenever We Found Ourselves In Any Sort Of Trouble, We Always Found

Him Available To Cater The Issue.

We Also Take Immense Pleasure In Thanking Our

Project Co-Supervisor

Mr. Zohaib Javeed Zaidi

For Their Valuable Help Regarding Our Plant Design Project.

This Sort Of Generosity And Favor Is Highly Commendable

We Are Grateful To

Our Parents

For Their Special Prayers That Helped Us Achieve

This Tedious Task In The Compilation Of This Design Project.

We dont inherit the earth from our ancestors; we borrow it from our children. (David
Brower). The present work is purely an effort to protect the environment and upcoming
generations of this planet along with the development of Ultra clean fuels, keeping a sharp
eye on economics.

Sulfur is one of the major contents present in the fuel which continuously deteriorating the
environment since the beginning of times and its emission needs to be minimized as low as
possible by the use of new technology.

Raw diesel currently using in Pakistan contains almost 2000ppm to 500ppm of sulfur i.e.
diesel produced by the front end of the NRL refinery and DIESELMAX unit of the PARCO
refinery respectively. The present modifications in the process, limit the sulfur contents in the
processed diesel upto15ppm, which meets the EURO-VI standards. That is the beauty of
Hydrodesulfurization. ULSD (Ultra-Low-Sulfur Diesel) is a diesel fuel with a maximum of
15 ppm sulfur content.

Hydrodesulfurization is basically a purification process which removes sulfur, nitrogen,

heavy metal and other impurities. In this process raw diesel is subjected to a purification
process which takes place in the presence of hydrogen and a suitable catalyst, around at
355oC and 60kg/cm2. Trickle bed reactor is used for this process with intermediate quenching
of hydrogen gas due to overall exothermic nature of the reaction. Desulfurized diesel is
subsequently subjected to different separation steps to get end product with 15ppm sulfur. A
large amount of hydrogen is require for this process which renders the economics of this
process infeasible and hence increase the per liter cost of the diesel available to the
customers. Here in this project we try our best to make this project as economical as possible.
Production of hydrogen gas from the reforming process keeps the expenses to a minimum
level. Payback period with the present process is just 2.5 years which indicates the feasibility
of the process also the Net present value and profitability index of the project is positive
which also favors the project implementation on the large scale.
 Table of Contents
1: INTRODUCTION TO ULSD ........................................................................................... 20

1.1: Introduction to ULSD ................................................................................................... 20

1.2: Need of Ultra-Low Sulfur Diesel .................................................................................. 21

1.2.1: Diesel Exhaust ........................................................................................................ 21

1.2.2: Transport and Fate of Diesel Exhaust in the Environment..................................... 23

1.2.3: Health Effects of Diesel Exhaust ............................................................................ 24

1.3: Diesel Exhaust Exposure Pathways .............................................................................. 25

1.4: Strategies for Preventing or Controlling Exposures to Diesel Exhaust ........................ 28

1.5: Progress towards ULSD ................................................................................................ 29

1.5.1: Leading Europe ...................................................................................................... 29

1.5.2: Following USA ....................................................................................................... 30

1.5.3: Emerging Asia ........................................................................................................ 32

1.6: Pakistan Moving to Euro-2 (500-ppm Sulfur) Standards for Diesel Fuel .................... 33

2: DESULFURIZATION TECHNOLOGIES..................................................................... 35

2.1: Introduction ................................................................................................................... 35

2.2: ULSD Production Technologies ................................................................................... 36

2.3: Hydrotreating ................................................................................................................ 38

2.4: Developing Technologies and Ultra-Low-Sulfur Alternatives ..................................... 41

2.4.1: Sulfur Adsorption ................................................................................................... 41

2.4.2: Biodesulfurization .................................................................................................. 41

2.4.3: Sulfur Oxidation ..................................................................................................... 41

2.4.4: Fischer-Tropsch Diesel and Biodiesel .................................................................... 42

2.5: NEMS Approach to Diesel Desulfurization Technology ............................................. 43

2.6: Individual refinery Analysis Approach to Diesel Desulfurization Technology............ 44

2.7: Conclusion..................................................................................................................... 45
3: PROCESS DESCRIPTION & CAPACITY SELECTION ........................................... 47

3.1: Hydrodesulphurization [13] .......................................................................................... 47

3.1.1: Sulfur ...................................................................................................................... 48

3.1.2: Nitrogen .................................................................................................................. 48

3.1.3: Oxygen ................................................................................................................... 48

3.1.4: Olefins .................................................................................................................... 48

3.1.5: Metals ..................................................................................................................... 48

3.2: Operating Variables ...................................................................................................... 48

3.2.1: Temperature ............................................................................................................ 49

3.2.2: Pressure................................................................................................................... 49

3.2.3: Space Velocity ........................................................................................................ 49

3.2.4: Recycle Rate ........................................................................................................... 50

3.2.5: Makeup Hydrogen .................................................................................................. 50

3.2.6: Purge Ratio ............................................................................................................. 50

3.3: Catalysts ........................................................................................................................ 50

3.4: Diesel Hydrodesulfurization ......................................................................................... 51

3.4.1: Process Flow Diagram ............................................................................................ 51

3.4.2: Description of Flow Diagram ................................................................................. 55

3.4.3: Detailed process description of hydrodesulfurization ............................................ 55

3.5: Chemistry of the Process ............................................................................................... 57

3.6: Ultra-Low Sulfur Diesels [14] ...................................................................................... 58

3.7: Capacity Selection ......................................................................................................... 59

4: MATERIAL BALANCE:- ................................................................................................ 61

4.1: Reaction occurring in the reactor .................................................................................. 61

4.1.1: Reactions of sulfur compounds: ............................................................................. 61

4.1.2: Reactions of nitrogen removal: .............................................................................. 62

4.1.3: Reactions of olefins saturation: .............................................................................. 62

 4.1.4: Reaction of Aromatic Saturation ............................................................................ 63

4.1.5: Reactions of Halide removal: ................................................................................. 63

4.2: Material Balance Sheet along with Schematic Diagram ............................................... 63

5: ENERGY BALANCE ....................................................................................................... 66

5.1: Introduction: .................................................................................................................. 66

5.2: Conservation of Energy: ............................................................................................... 67

5.3: Forms of Energy:........................................................................................................... 67

5.3.1: Potential energy: ..................................................................................................... 67

5.3.2: Kinetin energy: ....................................................................................................... 68

5.3.3: Internal energy: ....................................................................................................... 68

5.3.4: Work: ...................................................................................................................... 68

5.3.5: Heat: ....................................................................................................................... 68

5.3.6: Electrical energy: .................................................................................................... 68

5.4: Energy Balance Sheet along with Schematic Diagram ................................................. 68

6: EQUIPMENT DESIGN .................................................................................................... 72

6.1: Reactor .......................................................................................................................... 72

6.1.1: Importance of Reactor in Hydrodesulfurization Unit ............................................. 72

6.1.2: Selection of the Reactor.......................................................................................... 72

6.1.2.1: Trickle Bed Reactors ............................................................................................... 73

6.1.2.2: Slurry Bed Reactors: ............................................................................................... 73

6.1.2.3: Up-Flow versus Down-Flow Co-Current Fixed Bed Reactors ............................... 75

6.1.2.4: Co-Current Operation versus Counter-Current Operation: ..................................... 76

6.1.3: Design of the Reactor ............................................................................................. 76

6.1.3.1: Thermodynamic Parameters ................................................................................ 77

6.1.3.1.1: Temperature ...................................................................................................... 77

6.1.3.1.2: Pressure............................................................................................................. 77

6.1.3.2: Calculation of Quench Gas Required .................................................................. 78

 6.1.3.3: Volume of the Reactor......................................................................................... 78

6.1.3.4: Length and Diameter of Reactor ......................................................................... 79

6.1.3.6: Pressure drop across the Reactor ......................................................................... 81

6.1.3.6.1: Calculations for Pressure drop.......................................................................... 82

6.1.3.7: Mechanical Design of the Reactor .......................................................................... 83

6.1.3.7.1: Material of construction ................................................................................... 83

6.1.3.7.2: Wall thickness .................................................................................................. 83

6.1.3.8: Column Internals ................................................................................................. 84

6.1.4: Specification Sheet for Reactor .............................................................................. 86

6.2: Heat Exchanger Design ................................................................................................. 87

6.2.1: Fluid Allocation ...................................................................................................... 87

6.2.2: Design Inputs: ......................................................................................................... 87

6.2.3: Available Data and Property estimation ................................................................. 87

6.2.4: Calculations:-.......................................................................................................... 88

6.3: Furnace (14) .................................................................................................................. 93

6.3.1: Classification of Furnace ........................................................................................ 93

6.3.2: Parts of Furnace ...................................................................................................... 93

6.3.3: Significance of Furnace in Overall Process............................................................ 94

6.3.4: Selection Criteria of Furnace .................................................................................. 94

6.3.5: Selection ................................................................................................................. 95

6.3.6: Selected Furnace ..................................................................................................... 96

6.3.7: Problems Faced in Industry during Operation........................................................ 96

6.3.7.1: Solution of these problem .................................................................................... 96

6.3.7.1.1: Pigg Decoking .................................................................................................. 96

6.3.8: Methods of Designing ............................................................................................ 96

6.3.9: Furnace Design Calculation by Method of Lobo and Evans .................................. 97

6.3.10: Specification Sheet ............................................................................................. 107

6.4: Make-up Gas Compressor ........................................................................................... 108

6.4.1: Types of Compressor ............................................................................................ 108

6.4.2: Compressor selection............................................................................................ 109

6.4.3: Operating Conditions............................................................................................ 110

6.4.4: Calculations .......................................................................................................... 110

6.4.5: Specification Sheet of Feed Gas Compressor ...................................................... 112

6.5: Recycle Gas Booster Compressor ............................................................................... 112

6.5.1: Operating Conditions............................................................................................ 112

6.5.2: Booster Compressor Specification Sheet ............................................................. 113

6.6: Pump (22) .................................................................................................................... 113

6.6.1: Two Basic Types of Pumps .................................................................................. 113

6.6.2: Comparison between Centrifugal Pump and Reciprocating Pump ...................... 114

6.6.3: Pump Selection Procedure .................................................................................... 114

6.6.4: Selection Criteria for Pumps ................................................................................ 115

6.6.5: Selection of Diesel Feed Pump and design Calculations ..................................... 116

6.6.6: Specification Sheet ............................................................................................... 117

6.7: Two Phase (Gas-Liquid) Separator ............................................................................. 118

6.7.1: Design Calculations (22) ...................................................................................... 118

6.7.1.2: Internals of Two Phase Separator ......................................................................... 122

6.7.2: Specification Sheets.............................................................................................. 124

6.8: Steam Stripper ............................................................................................................. 124

6.8.1: Design Calculations .............................................................................................. 124

6.8.2: Specification Sheet ............................................................................................... 135

6.9: Absorber design .......................................................................................................... 136

6.9.1: Specification Sheet ............................................................................................... 140

7: INSTRUMENTATION AND CONTROL .................................................................... 142

7.1: Introduction to Instrumentation................................................................................... 142

7.2: Analysis of Measurement ............................................................................................ 143

7.2.1: Variables to be measured...................................................................................... 143

7.3: Final Control Elements ............................................................................................... 152

7.4: Controller (5)............................................................................................................... 152

7.4.1: Modes of Control (5) ............................................................................................ 152

7.5: Transmitter .................................................................................................................. 153

7.6: Sensors ........................................................................................................................ 153

7.7: Typical Control Systems (6) ....................................................................................... 153

7.7.1: Temperature measurement and control ................................................................ 153

7.7.2: Pressure measurement & control .......................................................................... 153

7.7.3: Level measurement & Control ............................................................................. 154

7.7.4: Flow measurement and control ............................................................................ 154

7.8: Control Loops.............................................................................................................. 154

7.8.1: Cascade Control Loop of Furnace ........................................................................ 155

7.8.2: Feed Forward Control Loop of Heat Exchanger .................................................. 156

7.8.3: Selective Control for Reactor ............................................................................... 157

7.8.4: Ratio Control for Absorber ................................................................................... 158

7.8.5: Separator ............................................................................................................... 159

8: COST ESTIMATION & PROJECT EVALUATION ................................................. 161

8.1: Plant Cost Estimation .................................................................................................. 161

8.2: Capital Investments ..................................................................................................... 162

8.2.1: Working Capital Investment................................................................................. 162

8.2.2: Fixed Capital Investment ...................................................................................... 162

8.3: Methods Of Estimating Capital Investment ................................................................ 163

8.3.1: Summary Of The Factorial Method ..................................................................... 164

 8.3.2: Capital Cost Calculation ....................................................................................... 164

8.4: OPERATING COSTS................................................................................................. 169

8.4.1: Fixed operating costs: ........................................................................................... 170

8.4.2: Variable operating costs: ...................................................................................... 170

8.5: Estimation of operating cost........................................................................................ 171

8.5.1: Raw materials ....................................................................................................... 171

8.5.2: Miscellaneous materials (plant supplies).............................................................. 171

8.5.3: Utilities (services) ................................................................................................. 171

8.5.4: Shipping and packaging ....................................................................................... 172

8.5.5: Maintenance ......................................................................................................... 172

8.5.6: Operating labour ................................................................................................... 172

8.5.7: Supervision ........................................................................................................... 172

8.5.8: Laboratory costs ................................................................................................... 173

8.5.9: Plant overheads ..................................................................................................... 173

8.5.10: Capital charges ................................................................................................... 173

8.5.11: Local taxes .......................................................................................................... 174

8.5.12: Insurance............................................................................................................. 174

8.5.13: Royalties and licence fees .................................................................................. 174

8.6: Summary of production costs...................................................................................... 174

8.6.1: Variable costs ....................................................................................................... 174

8.6.2: Fixed costs ............................................................................................................ 175

8.7: Total Production Cost Calculation .............................................................................. 176

8.7.1: Variable cost ......................................................................................................... 176

8.7.2: Fixed Costs ........................................................................................................... 176

8.8: Project Evaluation ....................................................................................................... 178

8.8.1: Processing cost per liter ........................................................................................ 178

8.8.2: Profit Per liter ....................................................................................................... 178

 8.8.3: Total Profit Annually............................................................................................ 179

8.8.4: Cash Flow Diagram ............................................................................................. 179

8.8.5: Pay Back Period ................................................................................................... 179

8.8.6: Discounted Pay Back Period ................................................................................ 179

8.8.7: Net positive value ................................................................................................. 180

8.8.8: Profitability index ................................................................................................. 180

8.8.9: Book value of the plant......................................................................................... 180

9: ENVIRONMENTAL IMPACT ASSESSMENT .......................................................... 183

9.1: Purpose of This Document .......................................................................................... 183

9.2: Project Overview ......................................................................................................... 183

9.3: Key Areas of Environmental Concern ........................................................................ 186

9.4: Organization of the Document .................................................................................... 186

9.4.1: Summary of Environmental Impacts: ................................................................... 186

9.4.2: Environmental Settings, Impacts and Mitigation Measures: ................................ 186

9.4.3: Alternatives........................................................................................................... 186

9.5: Summary of Environmental Impacts .......................................................................... 187

9.5.1: Summary of Impacts of the Proposed Project ...................................................... 187

9.5.2: Review of Proposed Project Impacts .................................................................... 187

9.6: Environmental Setting, Impacts and Mitigation ......................................................... 192

9.6.1: Project Variables .................................................................................................. 192

9.6.2: Project Impact Analysis ........................................................................................ 193

9.7: Project Alternatives ..................................................................................................... 194

9.7.1: Development and Selection of Alternatives ......................................................... 194

9.7.2: Proposed Alternatives to the Project .................................................................... 195

10: HAZOP ANALYSIS ...................................................................................................... 200

10.1: Potential Hazard and Operability Problems .............................................................. 200

10.2: Deviation from Design Intent.................................................................................... 201

 10.3: The Basic Concept .................................................................................................... 201

10.4: The HAZOP Team .................................................................................................... 201

10.5: Hydrogen Sulfide Poisoning ..................................................................................... 203

10.5.1: Acute Hydrogen Sulfide Poisoning .................................................................... 203

10.5.2: Sub-acute Hydrogen Sulfide Poisoning.............................................................. 204

10.5.3: Prevention of Hydrogen Sulfide Poisoning ........................................................ 205

10.5.4: Further Information ............................................................................................ 205

10.6: Safety Precautions for Entering a Contaminated Atmosphere .................................. 206

APPENDICES

Material Balance Detail Calculations:- .................................................................................. 209

Energy Balance Detail Calculations ...................................................................................... 224

References:............................................................................................................................. 234
 List of Tables & Figures
Figure 1: Schematic Diagram along with the complete material Balance sheet. .................................. 64
Figure 2:Schematic Diagram along with the complete energy Balance sheet. ..................................... 69
Figure 3: Partial wetting of the catalyst ................................................................................................ 79
Figure 4: Hydrodynamics of the reactor i.e. flow regimes ................................................................... 80
Figure 5: Furnace (fired heater) ............................................................................................................ 93
Figure 6: Furnaces Used in Petroleum Refineries................................................................................. 95
Figure 7: Selection of compressor on the base of flow rate& discharge pressure .............................. 109
Figure 8: Vertical type separator with vertox breaker ....................................................................... 123
Figure 9: Cascade loop for furnace ..................................................................................................... 155
Figure 10: Feed Forward Control for Heat Exchanger ....................................................................... 156
Figure 11: Control Configuration for Reactor .................................................................................... 157
Figure 12: Ratio control for absorber .................................................................................................. 158
Figure 13: Control configuration of separator .................................................................................... 159
Figure 14: Cash flow diagrm .............................................................................................................. 179

Table 1: Ranges of occupational exposure to DPM by job category. [5] ............................................. 26

Table 2: Annual average nationwide DPM exposure estimates (g/m). [5] ......................................... 26
Table 3: Major components of gas-phase diesel engine emissions, their known atmospheric
transformation products, and the biological impact of the reactants and products [5] ......................... 27
Table 4: Major components of particle-phase diesel engine emissions, atmospheric transformation
products, and the biological impact of the reactants and products [5] .................................................. 28
Table 5: Effective Dates for Highway ULSD Fuel [9] ......................................................................... 31
Table 6: Non road Diesel Fuel Standards [10] ...................................................................................... 31
Table 7: Timing: What are countries doing?......................................................................................... 32
Table 8: Purge Requirements of HDS Processes .................................................................................. 50
Table 9: Typical reactions in desulfurization ........................................................................................ 57
Table 10: Typical Diesel HDS Operating Conditions........................................................................... 58
Table 11: Material balance sheet (All values are in kg/hr) .................................................................. 64
Table 12: Energy Balance Sheet ( All values are in kJ/hr). .................................................................. 69
Table 13: Comparison of Trickle bed reactor And Ebullated bed reactor ............................................ 74
Table 14: Reactor specification sheet ................................................................................................... 86
Table 15: Available date for heat exchanger design ............................................................................. 87
Table 16: Temperature differences at two ends of the exchangers ....................................................... 88
Table 17: Composition of natural gas ................................................................................................. 100
Table 18: Heat generated through natural gas burning ....................................................................... 100
Table 19: Enthalpies of flue gases at flue gas temperature ................................................................. 102
Table 20: Specification sheet of furnace ............................................................................................. 107
Table 21: General Compression and Vacuum Limits (22) ................................................................. 108
Table 22: Specific heat capacity of gas ............................................................................................... 111
Table 23: Specification sheet of feed compressor............................................................................... 112
Table 24: Specification sheet of booster compressor .......................................................................... 113
Table 25: Comparison of different type of pump................................................................................ 114
Table 26: Specification sheet of pump ................................................................................................ 117
Table 27: Data required for the design of separating vessel ............................................................... 118
Table 28: Specification sheet of separating vessel .............................................................................. 124
Table 29: Design variables.................................................................................................................. 124
Table 30: Design Specification sheet for Stripper .............................................................................. 135
Table 31: Design Specification sheet for absorber ............................................................................. 140
Table 32: Approximate Pressure Ranges for Pressure-Sensing Devices ............................................ 144
Table 33: Temperature ranges and accuracy of temperature sensors.................................................. 145
Table 34: Summary of Flow Meter Characteristics ............................................................................ 151
 Chapter # 01

1: Introduction to ULSD

1.1: Introduction to ULSD

. S15 (ULSD) is defined by the U.S. Environmental Protection Agency (EPA) as U.S. Diesel
. . . . . . . . . . . . . . . . .

. fuel with a sulfur content not to exceed 15 ppm (parts per million). S15, S500, and S5000
. . . . . . . . . . . . . . . . . . .

. are designations for diesel fuels that meet 15 ppm, 500 ppm, and 5, 000 ppm maximum
. . . . . . . . . . . . . . . . . .

. sulfur content, respectively, as defined in the American Society for Testing and Materials
. . . . . . . . . . . . . . .

(ASTM) standard D975 .In different regions of the world ULSD may refer to different
. . . . . . . . . . . . . . . .

. maximum sulfur content values, but ULSD and S15 are often used interchangeably in North
. . . . . . . . . . . . . .

. America (U. S. and Canada).

. . . . . . . .
1.2: Need of Ultra-Low Sulfur Diesel

1.2.1: Diesel Exhaust

. Diesel exhaust is a common contaminant of air in urban and rural environments. Many
. . . . . . . . . . . . . .

. people find the sight and smell of diesel exhaust to be objectionable and several agencies
. . . . . . . . . . . . . .

. believe that it causes cancer. It is generated by many sources including buses, semi- trucks,
. . . . . . . . . . . . . . . . . .

. electricity generators, and earth moving and farming equipment. The chemical compounds
. . . . . . . . . . . .

. that diesel exhaust is composed of depend on the fuel and engine used the presence of
. . . . . . . . . . . . . . .

. emissions control equipment, and how the engine is maintained and operated. The following
. . . . . . . . . . . . . .

. sections describe the characteristics of diesel exhaust, how it is transported and transformed
. . . . . . . . . . . . .

. in the environment, the routes by which humans may be exposed to diesel exhaust, its
. . . . . . . . . . . . . . . .

. constituents in the environment, and ways to prevent or control diesel exhaust generation
. . . . . . . . . . . . .

. and human exposure.

. . .

1.2.1.1: Characteristics of Diesel Exhaust

. The diesel engine was patented in 1892 and conceived to provide improved fuel efficiency . . . . . . . . .

. compared to gasoline engines. The diesel engine is used in trucks, ships, buses, trains,
. . . . . . . . . . . . . . . . . .

. agricultural and non- road equipment. Diesel engines emit more particulate matter (PM) than
. . . . . . . . . . . . . . . .

. gasoline engines. The diesel engine compresses air to high temperature and pressure. Fuel is
. . . . . . . . . . . . . . .

. then injected into this compressed air and auto - ignites releasing chemical energy. The gases
. . . . . . . . . . . . . . .

. expand and move the pistons before being released into the atmosphere. Diesel fuel is a
. . . . . . . . . . . . . . .

. mixture of many different hydrocarbon molecules. The combustion, both complete and
. . . . . . . . . . . .

. incomplete, of diesel fuel forms a complex mixture of hundreds of organic and inorganic
. . . . . . . . . . . . . .

. compounds in the gas and particle phases [1]. . . . . . . . .

1.2.1.2: Gaseous Components of Diesel Exhaust:

a) Carbon dioxide
b) Oxygen
c) Nitrogen
d) Water vapor
e) Carbon monoxide
f) Nitrogen compounds
g) Sulfur compounds
h) Low-molecular-weight hydrocarbons
1.2.1.3: Toxicologically Relevant Gaseous Components:
a) Aldehydes (formaldehyde, acetaldehyde, acrolein)
b) Benzene
c) 1,3-butadiene
d) Polycyclic aromatic hydrocarbons (PAHs)
e) Nitro-PAHs

1.2.1.4: Particulate Component of Diesel Exhaust (Diesel Particulate

Matter - DPM):
a) Elemental carbon
b) Adsorbed organic compounds
c) Small amounts of sulfate, nitrate, metals, and other trace elements

1.2.1.5: Toxicologically Relevant Compounds Adsorbed on DPM surfaces:

a) Polycyclic Aromatic Hydrocarbons
b) Nitro-PAHs
c) Oxidized PAH Derivatives

. The components of diesel exhaust (DE) emissions are a public concern for the following
. . . . . . . . . . . . . .

. reasons:
.

a) Emissions from diesel engines include over 40 substances that are listed by the EPA
. . . . . . . . . . . . . .

. as hazardous air pollutants.

. . . .

b) Components of DE contain potential cancer causing substances such as arsenic,

. . . . . . . . . . . .

. benzene, formaldehyde, nickel, and PAHs.

. . . . . . .

c) The diesel particulate matter (DPM) is very small (90% are less than 1um by mass),
. . . . . . . . . . . . . . . . . . . .

. making DPM easy to respire into the deep lung.

. . . . . . . . .

d) DPM has hundreds of chemicals adsorbed to their surfaces, including many known or
. . . . . . . . . . . . . .

. suspected carcinogens. . .

e) There are many irritants and toxic chemicals in the gaseous phase of DE.
. . . . . . . . . . . .

f) Oxides of nitrogen, component of urban smog, are in the gaseous phase of DE.
. . . . . . . . . . . . . . .

g) There is likelihood that people in both ambient and occupational settings can be
. . . . . . . . . . . . .

. exposed to DE. . ..

h) DE has the potential to cause adverse health effects including cancer, pulmonary and
. . . . . . . . . . . . . .

. cardiovascular diseases. .
 i) Studies show workers exposed to higher levels of DE are more likely to develop lung
. . . . . . . . . . . . . . .

. cancer. .

j) In 1990, the state of California identified DE as a chemical known to cause cancer.

. . . . . . . . . . . . . . . .

k) The International Agency for Research on Cancer has concluded that DE probably
. . . . . . . . . . . .

. causes cancer in humans. . . .

l) The EPA has proposed classifying DE as a probable human carcinogen [1].

. . . . . . . . . . . .

1.2.2: Transport and Fate of Diesel Exhaust in the Environment .

. Since there are so many compounds in diesel exhaust, it is complicated to discuss each
. . . . . . . . . . . . . . .

. chemicals fate and transport in the environment. . . . . . . .

1.2.2.1: Carbon Dioxide

. Carbon dioxide is a natural component of air. Excess carbon dioxide produced by diesel
. . . . . . . . . . . . . .

. exhaust and other fuel burning activities create an accumulation of carbon dioxide, which
. . . . . . . . . . . . .

. contributes to the greenhouse effect. During the day, sunlight penetrates the atmosphere and
. . . . . . . . . . . . . .

. heats the earth. CO2 and other greenhouse gases absorb the heat (infrared radiation) that the
. . . . . . . . . . . . . . . . .

. earth that normally escapes from the atmosphere. Excessive amounts of greenhouse gases
. . . . . . . . . . . .

. have caused the earths temperature to rise.

. . . . . .

1.2.2.2: Nitrogen dioxide

. Nitrogen dioxide reacts in air to form nitric acid and other organic nitrates, which are
. . . . . . . . . . . . . . .

. corrosive to buildings and sculptures and contribute to the formation of acid rain. Acid rain
. . . . . . . . . . . . . . .

. causes increased acidity in lakes and in the soil, which can kill fish and lead to
. . . . . . . . . . . . . . . .

. eutrophication. Acidic soil causes leaching of nutrients and can damage root filaments of . . . . . . . . . . . . .

. plants, hindering water uptake. Nitrogen oxides have secondary reactions produce ground-
. . . . . . . . . . . . .

. level ozone, which creates smog, and can damage crops and forests.
. . . . . . . . . . .. .

1.2.2.3: Sulfur Dioxide .

. Sulfur dioxide reacts to form sulfates, which contribute to acid rain, resulting in the
. . . . . . . . . . . . . . .

. corrosion of buildings such as the Taj Majal and the Mayan Temples and can lead to the
. . . . . . . . . . . . . . . .

. eutrophication of lakes. Sulfur dioxide is also a precursor to particulate matter. . . . . . . . . . . . .

1.2.2.4: Hydrogen Sulfide

. Hydrogen sulfide breaks down to form sulfur dioxide and sulfuric acid. . . . . . . . . . .
1.2.2.5: Particulate matter 2.5
. Particulate matter 2.5 is fine particles that linger in the air and causes reduced visibility and . . . . . . . . . . . . . . .

. haze. Humidity can increase the effects of particulate matter. Eventually PM 2.5 settles out
. . . . . . . . . . . . . . .

. as dust.
.

1.2.2.6: Benzene
. In the air, benzene breaks down in a couple of days . It can attach to rain, which brings it to
. . . . . . . . . . . . . . . . . . . . . .

. the ground. In the soil, benzene can dissolve in ground water or degrades by microbes.
. . . . . . . . . . . . . . . . .

. Benzene does not build up in plants or animals. . . . . . . . .

1.2.2.7: Formaldehyde
. This constituent of diesel exhaust breaks down during the day in the air. One of its by-
. . . . . . . . . . . . . . . . .

. products is carbon monoxide. It dissolves very quickly in water, but does not remain in
. . . . . . . . . . . . . . . .

. water for long. [2] . . .

1.2.3: Health Effects of Diesel Exhaust

. Diesel engines are used in automobiles, generators, light- duty and heavy- duty vehicles as
. . . . . . . . . . . . . . . . .

. well as railroad locomotives. When diesel fuel burns in an engine, the resulting exhaust is
. . . . . . . . . . . . . . . .

. made up of soot and gases representing thousands of different chemical substances. 90% of
. . . . . . . . . . . . . . .

. the soot consists of < 1 diameter particles that can be inhaled and deposited in the lungs.
. . . . . . . . . . . . . . . . .

. Diesel exhaust contains 20- 100 times more particles than gasoline exhaust. These particles
. . . . . . . . . . . . . .

. carry absorbed cancer causing substances known as poly- nuclear aromatic hydrocarbons
. . . . . . . . . . . .

(PAH)s. The gases in diesel exhaust can also create health problems. The top eight are
. . . . . . . . . . . . . . . . .

. listed here: . .

a) Nitrous oxide
b) Nitrogen dioxide
c) Formaldehyde
d) Benzene
e) Sulfur dioxide
f) Hydrogen sulfide
g) Carbon dioxide
h) Carbon monoxide.
Those most likely to be occupationally exposed to diesel exhaust include bridge, tunnel and
. . . . . . . . . . . . . .

. loading dock workers, auto mechanics, toll booth collectors, truck and forklift drivers and
. . . . . . . . . . . . . . .

. people who work near areas where diesel powered vehicles are used, stored and maintained.
. . . . . . . . . . . . . . .

. Workers exposed to high concentrations of diesel exhaust have reported these short- term
. . . . . . . . . . . . .

. symptoms: .

a) Irritation of the eyes, nose and throat

b) Lightheadedness
c) Feeling high
d) Heartburn
e) Headache
f) Weakness, numbness and tingling in the extremities
g) Chest tightness
h) Wheezing
i) Vomiting

. The chronic effects of exposure to diesel exhaust include those shown below. Few studies
. . . . . . . . . . . . . .

. have been done, however, to establish chronic effects. In terms of cancer risk, no consistent
. . . . . . . . . . . . . . . . . .

. evidence suggests that diesel emissions induce cancer in rats at sites other than the lung.
. . . . . . . . . . . . . . .

. Prolonged exposure to diesel emissions does not produce lung tumors in hamsters, and the . . . . . . . . . . . . . .

. results in mice are equivocal, which suggests that species- specific factors play a critical role
. . . . . . . . . . . . . . . .

. in the induction of lung tumors by diesel emissions. In addition, few epidemiologic studies
. . . . . . . . . . . . . . .

. have considered the effects of confounding by non- diesel particulates , cigarette smoke,
. . . . . . . . . . . . . .

. asbestos exposure, diet and socioeconomic factors. However, those studies that have been
. . . . . . . . . . . . . .

. done consistently show a weak association of 1.2 - 1.5 relative risk increase in lung cancer.
. . . . . . . . . . . . . .

. Thus the EPA, the ACGIH , NIOSH and IARC agree that diesel exhaust is a human
. . . . . . . . . . . . . . . .

. carcinogen. Other respiratory disorders caused or exacerbated by diesel exhaust include . . . . . . . . . . .

. asthma and chronic bronchitis [3]. . . .. .

1.3: Diesel Exhaust Exposure Pathways

. Diesel exhaust particles and gases are suspended in the air, so exposure to this pollutant
. . . . . . . . . . . . . . .

. occurs whenever a person breathes air that contains these substances. Although diesel
. . . . . . . . . . . .

. exhaust most easily enters the body by breathing, there are some occupations where the
. . . . . . . . . . . . .

. exhaust may cling to skin or hair and there after possibly be ingested as a consequence of
. . . . . . . . . . . . . . . . .

. hand- to- mouth activity. By far, the major exposure pathway is from breathing. [4]
. . . . . . . . . . . . . . . . .
. The prevalence of diesel - powered engines makes it almost impossible to avoid exposure to
. . . . . . . . . . . . . .

. diesel exhaust or its byproducts, regardless of whether you live in a rural or urban setting.
. . . . . . . . . . . . . . . . .

. However, people living and working in urban and industrial areas are more likely to be
. . . . . . . . . . . . . . .

. exposed to this pollutant. Those spending time on or near roads and freeways, truck loading
. . . . . . . . . . . . . . . .

. and unloading operations, operating diesel- powered machinery or working near diesel
. . . . . . . . . . . .

. equipment face exposures to higher levels of diesel exhaust and face higher health risks. The
. . . . . . . . . . . . . . .

. following tables illustrate the exposure to diesel particulate matter (DPM) in occupational
. . . . . . . . . . . . .

. and non- occupational settings.

. . . . .

Table 1: Ranges of occupational exposure to DPM by job category. [5]

Year of Sampling Occupational DPM,

Occupations
g/m
1980s and 1990s Miners 10-1,280
1980's Railroad Workers 39-191
1985 and later Firefighters 4-748
NA Airport crew, public transit workers 7-98
1990 Dockworkers, mechanics 5-61
1990 Long-and short-haul truckers 2-7

Table 2: Annual average nationwide DPM exposure estimates (g/m). [5]

Demographic group 1990 1996

50-State population 0.8 0.7

Rural population 0.5 0.3

Urban population 0.9 0.7

Urban outdoor workers 1.1 0.8

Urban children (0-17) 0.9 0.7

Exposure to diesel exhaust can have immediate health effects. Diesel exhaust can irritate the
eyes, nose, throat and lungs, and it can cause coughs, headaches, light-headedness and
nausea. In studies with human volunteers, diesel exhaust particles made people with allergies
more susceptible to the materials to which they are allergic, such as dust and pollen.
Exposure to diesel exhaust also causes inflammation in the lungs, which may aggravate
chronic respiratory symptoms and increase the frequency or intensity of asthma attacks.
. Diesel exhaust is a major source of fine- particle pollution. The elderly and people with
. . . . . . . . . . . . . . . .

. emphysema, asthma, and chronic heart and lung disease are especially sensitive to fine-
. . . . . . . . . . . . . . .

. particle pollution. Because childrens lungs and respiratory systems are still developing, they
. . . . . . . . . . . . .

. are also more susceptible than healthy adults to fine particles. Like all fuel- burning
. . . . . . . . . . . . . . .

. equipment, diesel exhaust contains nitrogen oxides. Nitrogen oxides can damage lung tissue,
. . . . . . . . . . . . . .

. lower the bodys resistance to respiratory infection and worsen chronic lung diseases, such
. . . . . . . . . . . . .

. as asthma. They also react with other pollutants in the atmosphere to form ozone, a major
. . . . . . . . . . . . . . . .

. component of smog. The tables below show the biological impact of the gas phase and
. . . . . . . . . . . . . . . .

. particulate phase of diesel engine emissions [4].

. . . . . .

Table 3: Major components of gas-phase diesel engine emissions, their known atmospheric
transformation products, and the biological impact of the reactants and products [5]
Gas-Phase Atmospheric Reaction
Biological Impact
Emission Component Products
Major contributor to global
Carbon dioxide --
warming
Highly toxic to humans,
Carbon monoxide --
blocks
Nitrogen dioxide is a
respiratory tract irritant and
Oxides of nitrogen Nitric acid, ozine major ozone precursor. Nitric
acid contributes
to acid rain.
Respiratory tract irritation.
Sulfur dioxide Sulfuric acid
Contributor to acid rain.
Hydrocarbons:
Respiratory tract irritation.
Aldehydes, alkyl nitrates, Reaction products are ozone
Alkanes (C18)
ketones precursors (in the presence of
NOx).
Respiratory tract irritation.
Some alkenes are mutagenic
Alkenes (C4) and carcinogenic. Reaction
Aldehydes, ketones
(e.g., 1,3-butadiene) products are ozone
precursors (in the presence of
NOx).
Aldehydes:
Formaldehyde is a probable
Carbon monoxide, human carcinogen and an
Formaldehyde
hydroperoxyl radicals ozone precursor (in the
presence of NOx).
Respiratory tract and eye
Higher aldehydes (e.g.,
Peroxyacyl nitrates irritation;
acetaldehyde, acrolein
causes plant damage
Monocyclic aromatic Hydroxylated and Benzene is toxic and
compounds (e.g., benzene, hydroxylated-nitro carcinogenic in humans.
toluene) derivatives
Some of these PAHs and
Benzene is toxic and
Nitro-PAHs (4 rings) nitro-PAHs are known
carcinogenic in humans.
mutagens and carcinogens.
Table 4: Major components of particle-phase diesel engine emissions, atmospheric
transformation products, and the biological impact of the reactants and products [5]
Particle-phase Atmospheric reaction
Biological impact
emission component products
Nuclei adsorb organic
Elemental carbon ---
compounds
Inorganic sulfate and
--- Respiratory tract irritation
Nitrate
Little information; possibly
Hydrocarbons (C14-C35) aldehydes, ketones, and alkyl Unknown
nitrates
Larger PAHs are major
contributors of carcinogens
PAHs (4 rings) (e.g., Nitro-PAHs (4 rings) Nitro-
in combustion emissions.
pyrene, benzo[a] pyrene) PAH lactones
Many nitro-PAHs are potent
mutagens and carcinogens.

1.4: Strategies for Preventing or Controlling Exposures to

Diesel Exhaust
. The best option for preventing exposure to diesel exhaust is to prevent it from being
. . . . . . . . . . . . . .

. generated. This can be accomplished through several different means. First diesel engines
. . . . . . . . . . . . .

. can be replaced with engines that use alternative fuels such as liquid propane or compressed
. . . . . . . . . . . . . . .

. natural gas. Second, diesel fuels can be reformulated to reduce the amount of sulfur and
. . . . . . . . . . . . . . . .

. other contaminant generating compounds that they contain. Third, diesel engines can be
. . . . . . . . . . . . . .

. redesigned to reduce the amount of pollutants that they generate. Finally, emissions control
. . . . . . . . . . . . . .

. equipment can be added to existing diesel engines. These engines emit far fewer pollutants
. . . . . . . . . . . . .

. than diesel engines, particularly diesel exhaust.

. . . . . . . .

. Diesel fuel reformulation can be a relatively simple and straightforward process. The
. . . . . . . . . . . .

. reformulation most commonly used today and required by the EPA for On Road diesel . . . . . . . . . . . . .

. engines in 2007 is to reduce the sulfur content of diesel fuel from as high as 3000 ppm to
. . . . . . . . . . . . . . . . . .

. less than 15 ppm. Diesel fuel reformulation may allow better emissions control technology
. . . . . . . . . . . . .

. such as particulate traps and catalytic converters to be used. The particulate traps can remove
. . . . . . . . . . . . . . .

. up to 95% of the particulates that are present in diesel exhaust. Traps that have a catalytic
. . . . . . . . . . . . . . . . . . .
. action can remove up to 90% of carbon monoxide, 90% of hydrocarbons, and 10 % of
. . . . . . . . . . . . . . . . . . .

. nitrogen oxides present in diesel exhaust. Oxidation catalysts can be used light in light trucks
. . . . . . . . . . . . . . .

. and cars in addition to heavy- duty vehicles. These catalysts are able to remove up to 90% of
. . . . . . . . . . . . . . . . . . . .

. carbon monoxide, 90% of hydrocarbons, and 25- 50% of particulate matter in diesel exhausts
. . . . . . . . . . . . . . . . . . .

[6].

1.5: Progress towards ULSD

1.5.1: Leading Europe

. Very- low- sulfur diesel products have been available commercially in some European
. . . . . . . . . . . . .

. countries and in California on a limited basis. Sweden was the first to impose very strict . . . . . . . . . . . . . . . .

. quality specifications for diesel fuel, requiring a minimum 50 cetane, a maximum of 10 ppm
. . . . . . . . . . . . . . . .

. on sulfur content, and a maximum 5 percent on aromatics content. To meet these

. . . . . . . . . . . . . . .

. specifications the refinery at Scanraff, Sweden, installed a hydro treating facility based on . . . . . . . . . . . . . .

. SynTechnology. The Scanraffhydrotreating unit consists of an integrated two- stage reactor . . . . . . . . . . . .

. system with an interstage high- pressure gas stripper. The unit processes a light gas oil
. . . . . . . . . . . . . . . . . .

(LGO) to produce a diesel product with less than 1- ppm sulfur and 2. 4 percent aromatics by
. . . . . . . . . . . . . . . . . . . . .

. volume. It is important to note that the Scanraff plant is highly selective of its feedstock to
. . . . . . . . . . . . . . . . .

. achieve the ultra- low sulfur content, which may not be generalized to most U. S. refineries.
. . . . . . . . . . . . . . . . . . . . .

. In addition to Sweden, other European countries are encouraging the early introduction of
. . . . . . . . . . . . .

. very- low- sulfur diesel fuel ahead of the shift to a European requirement for 50- ppm diesel in
. . . . . . . . . . . . . . . . . . . .

. 2005. The United Kingdom and Germany have structured tax incentives for the early
. . . . . . . . . . . . .

. introduction of 50- ppm diesel fuel and have discussed incentives for introduction of a 10 - . . . . . . . . . . . . . . . . . .

. ppm diesel fuel. An example of a European refinery capable of producing diesel fuel for
. . . . . . . . . . . . . . .

. these markets is BPs refinery at Grangemouth, United Kingdom, which has a 35, 000barrel
. . . . . . . . . . . . . . . .

. per stream day unit originally designed for 500 ppm sulfur in 1995. The hydrotreater at
. . . . . . . . . . . . . . .

. Grangemouth has a two - bed reactor, no quench, and operates at about 950 pounds per . . . . . . . . . . . . . . . . .

. square inch gauge (psig). Operating at a space velocity of 1. 5 and using a new higher
. . . . . . . . . . . . . . . . . . .

. activity AK30 Nobel catalyst (KF757 ), the unit is producing 10 to 20 ppm sulfur diesel
. . . . . . . . . . . . . . . . .

. product. The feed is primary LGO with a sulfur content of about 1, 800 ppm, derived from
. . . . . . . . . . . . . . . . . . .

. low- sulfur crude. BP reported that on several occasions the feed had included a small
. . . . . . . . . . . . . . . .

fraction of cycle oil, which resulted in a noticeable increase in catalyst deactivation rate [7].
. . . . . . . . . . . . . . .
1.5.2: Following USA
. Americans took early steps towards ULSD but not as early as Europeans. In 1999 Arco . . . . . . . . . . . . . . .

. announced that it would produce a premium diesel fuel which Arco termed EC Diesel at . . . . . . . . . . . . . . . .

. its Carson, California, refinery. EC Diesel was a super clean diesel designed to meet the
. . . . . . . . . . . . . . . . .

. needs of fleets and buses in urban areas. The reported quality attributes included less than 10
. . . . . . . . . . . . . . . .

. ppm sulfur, less than 10 percent aromatics, and 60cetane, among others. Arco indicated that
. . . . . . . . . . . . . . . . .

. the crude slates of the Carson refinery would remain unchanged , with only the operating
. . . . . . . . . . . . . .

. conditions modified. The refinery selectively took out sulfurous, aromatic cycle oil feed . . . . . . . . . . . .

. stream to the diesel unit and repeated this every few days for batches. In April 2000, Equilon
. . . . . . . . . . . . . . . . . .

. also announced that its Martinez refinery in Northern California could provide ULSD for
. . . . . . . . . . . .

. fleet use in that region of the State.

. . . . . . . .

. The challenge of producing ULSD from feedstocks that were difficult to desulfurize was
. . . . . . . . . . . .

. well represented by the experience of Lyondell - Citgo Refining (LCR) at its refinery in
. . . . . . . . . . . . . . . .

. Houston, Texas. In 1997 the refinery moved to a diet of 100 percent Venezuelan crude. The
. . . . . . . . . . . . . . . . . .

. gravity of the crude oil was less than 20 oAPI, and it was highly aromatic. To produce
. . . . . . . . . . . . . . . . . .

. suitable quality low- sulfur diesel product the refinery revamped a hydrotreater to SynSat . . . . . . . . . . . . .

. operation in 1996 and then converted to SynShift in 1998. The revamped hydrotreater has a . . . . . . . . . . . . . . . .

. capacity of 50, 000 barrels per day and consists of a first- stage reactor operating at 675 psig
. . . . . . . . . . . . . . . . . . .

. pressure, a high - pressure stripper, and a second- stage reactor that uses a noble metal
. . . . . . . . . . . . . . . . . .

. catalyst. The feed to the unit is a blend of light cycle oil (LCO), coker distillate, and
. . . . . . . . . . . . . . . . . . . .

. straight- run distillate (approximately equal volumes) with 1. 4 percent sulfur by weight, 70
. . . . . . . . . . . . . . . . . .

. percent aromatics, and a cetane number of 30. The product has about 40 percent aromatics, a
. . . . . . . . . . . . . . . . . .

. cetane number of 38 . 5, and sulfur content less than 140 ppm.

. . . . . . . . . . . . .. . .

. Citgo reported that the LCR hydrotreating unit was the largest reactor of its type when
. . . . . . . . . . . . . .

. installed in 1996 and that the volume of catalyst in the unit, which had been 40, 000 pounds . . . . . . . . . . . . . . . . . . .

. in the old unit, increased to 1. 7 million pounds in the revamped unit. The diesel sulfur level
. . . . . . . . . . . . . . . . . . .

. produced in the unit reportedly met the 15 ppm sulfur cap at initial conditions at start of run, . . . . . . . . . . . . . . . . . .

. but as the desulfurization catalyst aged, the reactor temperature had to be revised to achieve
. . . . . . . . . . . . .

. target sulfur levels. If the revamped unit had to consistently meet a 15 ppm diesel sulfur
. . . . . . . . . . . . . . .

. limit, the cycle life greatly reduced from current operation , causing frequent catalyst
. . . . . . . . . . . . .

. replacement and more frequent shutdowns. Under the current mode of operation, the . . . . . . . . . . . . .

. frequency of catalyst change out was managed by reducing the cracked stocks in the feed to . . . . . . . . . . . . . .
. the unit. More frequent catalyst change outs to meet a 15 ppm sulfur cap reportedly could
. . . . . . . . . . . . . . . .

. raise the cost of diesel production. The American government enforced the U. S. refiners to
. . . . . . . . . . . . . . . . .

. make the transition towards ULSD according to the following road maps which are for
. . . . . . . . . . . . .

. highway and non- road ULSD fuel respectively [8].

. . . . . . . .

Table 5: Effective Dates for Highway ULSD Fuel [9]

Who What U.S. California

Import/produce at least 80% ULSD for on

6/01/06 ---
Refiners & highway use
Importers Import/produce at least 100% ULSD for on
6/01/10 6/01/06
highway use
Downstream Facilities that choose to carry ULSD must meet
from 15 ppm 9/01/06 ---
Refineries sulfur specification
Through
All highway diesel must be ULSD 10/01/10 7/15/06
Fuel Terminals
Facilities that choose to carry ULSD must meet
10/15/06 ---
15 ppm sulfur specification
Retail Outlets
All highway diesel must be ULSD 12/01/10 9/01/06

Table 6: Non road Diesel Fuel Standards [10]

Covered
Who 2006 2007 2008 2009 2010 2011 2012 2013 2014
Fuel

Large
500+ 500 500 500 15 15 15 15 15
Refiners & Non-Road
ppm ppm ppm ppm ppm ppm ppm ppm ppm
Importers
Large
Locomotive 500+ 500 500 500 500 500 15 15 15
Refiners &
& Marine ppm ppm ppm ppm ppm ppm ppm ppm ppm
Importers
Small
Non-Road,
Refiners and 500+ 500+ 500+ 500+ 500 500 500 500 15
Locomotive
other ppm ppm ppm ppm ppm ppm ppm ppm ppm
And Marine
exceptions
 1.5.3: Emerging Asia
. In Asian region there is an Emerging trend among high and middle income countries in
. . . . . . . . . . . . . .

. moving aggressively towards sulfur levels of 50 ppm and below. The following table
. . . . . . . . . . . . .

. indicates the progress of different Asian countries towards cleaner fuel in comparison with
. . . . . . . . . . . .

. America and Europe. . .

Table 7: Timing: What are countries doing?

Country
1996 1998 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011
/City

Bangladesh 5000

Cambodia 2000

India 5000 2500 500 350

Indonesia 5000

Japan 500 100 50/10 10

Malaysia 5000 3000 500

Pakistan 10000 5000

Philippines 5000 2000 500

Korea 500 430 30 10

Singapore 3000 500 50

Sri Lanka 10000 3000

Thailand 2500 500 50

Viet Nam 10000 2500 500

Europe 350 50/10 10

United states 500 15

Color
Indication >500ppm <51-500ppm <50ppm

. As the table depicts, apart from some exceptions like China, Singapore, Korea and Japan ,
. . . . . . . . . . . . . . . . .

. who have already achieved the bench mark value of 50 ppm, the most of the developing
. . . . . . . . . . . . . . . .

. Asian countries are still lagging far behind this minimum standard which is being
. . . . . . . . . . . . .

. implemented in the world. Still a lot of efforts need to be put in by these countries to catch . . . . . . . . . . . . . . . . . .

. up the ever increasing demand of cleaner fuels standards. In this regard Indian government is
. . . . . . . . . . . . . . .

. also taking some serious steps as illustrated in the above table. In march 2001, the Tata
. . . . . . . . . . . . . . . .

. Energy Research Institute (TERI) expressed skepticism over the feasibility of conversion of
. . . . . . . . . . . . .

. the entire bus fleet in the capital into the CNG mode and instead favored ultra low sulfur
. . . . . . . . . . . . . . . .

. diesel (ULSD) as the fuel of choice to drastically reduce levels of vehicular pollution in the
. . . . . . . . . . . . . . . . .

. city. On the other hand Pakistan is still lagging far behind in this regard.
. . . . . . . . . . . . ..
1.6: Pakistan Moving to Euro-2 (500-ppm Sulfur)
Standards for Diesel Fuel
. At present Pakistan is lingering around mere value of 5000 ppm sulfur. But now the
. . . . . . . . . . . . . . .

. situation is changing and the Pakistani government is also taking initial steps to participate in . . . . . . . . . . . . .

. the race of cleaner fuels and hence cleaner and better environment. Government is
. . . . . . . . . . . . .

. encouraging the refiners to shift towards low sulfur diesel. As a result of these steps Pakistan . . . . . . . . . . . . . . .

. Refinery Limited (PRL), countrys leading refinery decided in 2006 to invest US $ 182. 5
. . . . . . . . . . . . . . . . .

. million in the next three years for the upgrading of the refinery to meet the future product
. . . . . . . . . . . . . . . .

. specification as specified by the petroleum ministry. The additional units include diesel . . . . . . . . . . .

. hydrotreater, visbreaker, hydrogen generating plant, deasphalting unit, sulfur recovery unit, . . . . . . . . . . . . . .

. amino treatment unit and vacuum distillation. These units will produce premium quality
. . . . . . . . . . .

. products for the local market as per the Euro- 2 specifications and will also produce
. . . . . . . . . . . . . . .

. exportable surplus. Meantime, according to a report from Gulf News (UAE), Pakistan's . . . . . . . . . . . . . . . .

. diesel demand is forecast to jump 70% cent in a decade to 15. 07 million tones, as the overall
. . . . . . . . . . . . . . . . . . . . .

. fuel consumption almost doubles, forcing the country to boost imports [11].
. . . . . . . . . .

. PARCO introduced environment friendly 90 Octane fuel in Pakistan. Now it further aims to
. . . . . . . . . . . . . .

. make environment even cleaner by reducing Sulphur content from refined diesel and meet
. . . . . . . . . . . .

. the revised country specifications for sulphur contents. To achieve this objective, PARCO
. . . . . . . . . . . . .

. installed a US$ 132 million Hydro Desulphurization Plant at its Mid- Country Refinery at
. . . . . . . . . . . . . . .

. Mahmood Kot near Multan and is completed and is working since mid 2010. . . . . . . . . . . . . . .

. NRL is presently producing HSD of around 1. 0 % sulfur content. In view of clean fuel
. . . . . . . . . . . . . . . . . .

. quality requirements, NRL is planning up gradation of its facilities to enable production of

. . . . . . . . . . . . . .

. HSD of 0. 05 wt. % Sulfur content. Ultimate aim is to reduce sulfur further to 50 parts per
. . . . . . . . . . . . . . . . . . . .

. million. UOP, an international process designer & licensor, is carrying out techno economic
. . . . . . . . . . . . . . .

. feasibility for conversion of redundant KeroHydrobon unit to Diesel service. After project . . . . . . . . . . . .

. completion, NRL will be the first refinery in Pakistan to produce diesel of low sulfur up to . . . . . . . . . . . . . . . . .

. 500 ppm and further to less than 50 ppm ULSD, i. e. Euro IV Specification [12].
. . . . . . .. . . . . . . . . . . .
DESULFURIZATION
TECHNOLOGIES
 Chapter # 02

2: Desulfurization Technologies
.

. The availability of technologies for producing ultra- low- sulfur diesel fuel (ULSD) is one of
. . . . . . . . . . . . . . . . . .

. the issues to be raised. First, do adequate and cost- effective technologies exist to meet the
. . . . . . . . . . . . . . . . . .

. ULSD standard? Second, are technologies being developed that could reduce the costs in the
. . . . . . . . . . . . . . .

. future? [7]

2.1: Introduction
. A review of the technologies reveals that current technologies can be modified to produce
. . . . . . . . . . . . .

. diesel with less than 10 parts per million (ppm) sulfur. A small number of refineries
. . . . . . . . . . . . . . . . .

. currently produce diesel with sulfur in the 10 ppm range on a limited basis. Widespread
. . . . . . . . . . . . . . .

. production of ULSD will require many refineries to invest in major revamps or construction
. . . . . . . . . . . . .

. of new units.
. .. . .

. Refineries are characterized by a wide range of size, complexity, and quality of crude oil
. . . . . . . . . . . . . . . .

. inputs. Upgrades at a given refinery depend on individual circumstances, including the

. . . . . . . . . . . . .

. refinerys existing configuration, its inputs, its access to capital, and its perception of the
. . . . . . . . . . . . . . . .

. market. The sulfur in petroleum products comes from the crude oil processed by the refinery.
. . . . . . . . . . . . . . . .
. Refiners can reduce the sulfur content of their diesel fuel to a limited extent by switching to
. . . . . . . . . . . . . . . .

. crude oil containing less sulfur; however, sulfur reduction from a switch in crude oil would
. . . . . . . . . . . . . . . .

. fall well short of the new ULSD standard. Refineries will require substantial equipment
. . . . . . . . . . . . .

. upgrades to produce diesel with such limited sulfur. . . . . . . . . .

. In order to allow for some margin of error and product contamination in the distribution
. . . . . . . . . . . . . .

. system, refineries will be required to produce highway diesel with sulfur somewhat below 15
. . . . . . . . . . . . . .

. ppm. Due to limited experience with such low- sulfur products, the exact sulfur level that
. . . . . . . . . . . . . . . . .

. will be required by refineries is not certain. In the Regulatory Impact Analysis for the ULSD
. . . . . . . . . . . . . . . .

. Rule, the EPA (America) assumed highway diesel production with an average of 7 ppm.
. . . . . . . . . . . . . . . . .

. Whether production is at 10 ppm or 7 ppm, the same technology would be used. In general,
. . . . . . . . . . . . . . . . . . .

. relatively lower sulfur content would be achieved with more severe operating conditions at a . . . . . . . . . . . . .

. higher cost. Considerable development in reactor design and catalyst improvement has
. . . . . . . . . . .

. already been made to achieve ULSD levels near or below 10 ppm. In some cases low sulfur
. . . . . . . . . . . . . . . . .

. levels are the consequence of refiners efforts to meet other specifications, such as low
. . . . . . . . . . . . . .

. aromatic levels required . In other cases refiners have decided to produce a premium low- . . . . . . . . . . . . . . .

. sulfur diesel product, as in the United Kingdom, Germany, and California. These
. . . . . . . . . . . . . . .

. experiences, though limited, provide evidence for both the feasibility of and potential . . . . . . . . . . . . .

. difficulties in producing ULSD on a widespread basis. . . . . . . .

. Refineries currently producing ULSD in limited quantities rely on enhanced hydrotreating . . . . . . . . . .

. technology. Technology vendors expect that this will also be the case for widespread . . . . . . . . . . . . . .

. production of ULSD . The following section focuses on hydrotreating as the primary means . . . . . . . . . . . . .

. to achieve ULSD levels . A few emerging and unconventional desulfurization technologies

. . . . . . . . . . .

. are also discussed, which if proven cost- effective eventually may expand refiners options
. . . . . . . . . . . . . .

. for producing ULSD.

. .

2.2: ULSD Production Technologies

. Very- low- sulfur diesel products have been available commercially in some European
. . . . . . . . . . . . .

. countries and in California on a limited basis. Sweden was the first to impose very strict . . . . . . . . . . . . . . . .

. quality specifications for diesel fuel, requiring a minimum 50 cetane, a maximum of 10 ppm
. . . . . . . . . . . . . . . .

. on sulfur content, and a maximum 5 percent on aromatics content. To meet these

. . . . . . . . . . . . . . .

. specifications the refinery at Scanraff, Sweden, installed a hydrotreating facility based on . . . . . . . . . . . . .

. SynTechnology. The Scanraff hydrotreating unit consists of an integrated two- stage reactor . . . . . . . . . . . . .

. system with an inter- stage high- pressure gas stripper. The unit processes light gas oil
. . . . . . . . . . . . . . . . . .
(LGO) to produce a diesel product with less than 1 ppm sulfur and 2. 4 percent aromatics by
. . . . . . . . . . . . . . . . . . . .

. volume. . .

It is important to note that the Scanraff plant is highly selective of its feedstock to achieve
. . . . . . . . . . . . . . . .

. the ultra- low sulfur content which may not be generalized to most refineries. In addition to
. . . . . . . . . . . . . . . . .

. Sweden, other European countries are encouraging the early introduction of very- low- sulfur
. . . . . . . . . . . . . . .

. diesel fuel ahead of the shift to a European requirement for 50 ppm diesel in 2005. The
. . . . . . . . . . . . . . . . .

. United Kingdom and Germany have structured tax incentives for the early introduction of 50
. . . . . . . . . . . . .

. ppm diesel fuel and have discussed incentives for introduction of a 10 ppm diesel fuel. An
. . . . . . . . . . . . . . .

. example of a European refinery capable of producing diesel fuel for these markets, is BPs . . . . . . . . . . . . . . . .

. refinery at Grangemouth , United Kingdom, which has a 35, 000- barrel - per-stream- day unit . . . . . . . . . . . . . . . . . . . .

. originally designed for 500 ppm sulfur in 1995. The hydrotreater at Grangemouth has a two- . . . . . . . . . . . . . . .

. bed reactor, no quench, and operates at about 950 pounds per square inch gauge (psig).
. . . . . . . . . . . . . . . . . .

. Operating at a space velocity of 1. 5 and using a new higher activity AK30 Nobel catalyst . . . . . . . . . . . . . . . . . .

(KF757), the unit is producing 10 to 20 ppm sulfur diesel product. The feed is primary LGO
. . . . . . . . . . . . . . . . . . .

. with a sulfur content of about 1, 800 ppm, derived from a low- sulfur crude. BP reported that
. . . . . . . . . . . . . . . . . . . . .

. on several occasions the feed had included a small fraction of cycle oil, which resulted in a
. . . . . . . . . . . . . . . . .

. noticeable increase in catalyst deactivation rate. . . . . . . .

. In 1999 Arco announced that it would produce a premium diesel fuel which Arco termed
. . . . . . . . . . . . . . . .

EC Diesel at its Carson, California, refinery. EC Diesel is a super clean diesel

. . . . . . . . . . . . . . . . . . .

. designed to meet the needs of fleets and buses in urban areas. The reported quality attributes . . . . . . . . . . . . . . . .

. include less than 10 ppm sulfur, less than 10 percent aromatics, and 60 cetane, among . . . . . . . . . . . . . . . . .

. others. Arco indicated that the crude slates of the Carson refinery would remain unchanged,
. . . . . . . . . . . . . . .

. with only the operating conditions modified. The refinery had to selectively take out a
. . . . . . . . . . . . . .

. sulfurous, aromatic cycle oil feed stream to the diesel unit and repeat this every few days for . . . . . . . . . . . . . . . . .

. batches. If continuous production were required, a major capital investment would have to
. . . . . . . . . . . . . .

. be made. In April 2000, Equilon also announced that its Martinez refinery in Northern
. . . . . . . . . . . . . . .

. California could provide ULSD for fleet use in that region of the State. The challenge of . . . . . . . . . . . . . . . .

. producing ULSD from feedstocks that are difficult to desulfurize is well represented by the . . . . . . . . . . . . .

. experience of Lyondell- Citgo Refining (LCR) at its refinery in Houston, Texas. In 1997 the . . . . . . . . . . . . . . . . . . .

. refinery moved to a diet of 100 percent Venezuelan crude. The gravity of the crude oil was . . . . . . . . . . . . . . . . .

. less than 20oAPI, and it was highly aromatic. To produce suitable quality low- sulfur diesel
. . . . . . . . . . . . . . . . .

. product the refinery had revamped a hydrotreater to SynSat operation in 1996 and then . . . . . . . . . . . . .

. converted to SynShift in 1998. The revamped hydrotreater has a capacity of 50, 000 barrels . . . . . . . . . . . . . . . .
. per day and consists of a first- stage reactor operating at 675 psig pressure, a high - pressure
. . . . . . . . . . . . . . . . . . .

. stripper, and a second - stage reactor that uses a noble metal catalyst. The feed to the unit is a
. . . . . . . . . . . . . . . . . . . . .

. blend of light cycle oil (LCO), coker distillate, and straight- run distillate (approximately
. . . . . . . . . . . . . . . . .

. equal volumes) with 1. 4 percent sulfur by weight, 70 percent aromatics, and a cetane
. . . . . . . . . . . . . . . . . .

. number of 30. The product has about 40 percent aromatics, a cetane number of 38. 5, and
. . . . . . . . . . . . . . . . . . . .

. sulfur content less than 140 ppm. Citgo reported that the LCR hydrotreating unit was the
. . . . . . . . . . . . . . .

. largest reactor of its type when installed in 1996 and that the volume of catalyst in the unit,
. . . . . . . . . . . . . . . . . .

. which had been 40, 000 pounds in the old unit, had increased to 1. 7 million pounds in the
. . . . . . . . . . . . . . . . . . . . .

. revamped unit. The diesel sulfur level produced in the unit reportedly met the 15 ppm sulfur . . . . . . . . . . . . . . .

. cap at initial conditions at start of run, but as the desulfurization catalyst aged, the reactor
. . . . . . . . . . . . . . . .

. temperature had to be revised to achieve target sulfur levels. If the revamped unit had to . . . . . . . . . . . . . . . .

. consistently meet a 15 ppm diesel sulfur limit, the cycle life could be greatly reduced from . . . . . . . . . . . . . . . .

. current operation, causing frequent catalyst replacement and more frequent shutdowns.
. . . . . . . . . . .

. Under the current mode of operation, the frequency of catalyst change out is managed by
. . . . . . . . . . . . .

reducing the cracked stocks in the feed to the unit. More frequent catalyst change outs to . . . . . . . . . . . . . . . .

. meet a 15 ppm sulfur cap reportedly could raise the cost of diesel production .
. . . . . . . . . . . . . ..

2.3: Hydrotreating
. Conventional hydrotreating is a commercially proven refining process that passes a mixture . . . . . . . . . . .

. of heated feedstock and hydrogen through a catalyst- laden reactor to remove sulfur and other
. . . . . . . . . . . . . . .

. undesirable impurities. Hydrotreating separates sulfur from hydrocarbon molecules; some . . . . . . . . . .

. developing technologies remove the molecules that contain sulfur. Refineries can desulfurize . . . . . . . . . . .

. distillate streams at many places in a refinery by hydrotreating straight- run streams . . . . . . . . . . . . . . .

. directly following crude distillation, hydrotreating streams coming out of the fluid catalytic
. . . . . . . . . . . .

. cracking . (FCC) unit, and/ or hydrotreating the heavier streams that go through a
. . . . . . . . . . . . . . .

. hydrocracker. Over half of the streams currently going into highway- grade diesel (500 ppm) . . . . . . . . . . . . . . . .

. are made up from straight- run distillate streams, which are the easiest and least expensive to
. . . . . . . . . . . . . . . .

. treat. . .

. Refineries with hydrotreaters are likely to achieve production of ULSD on straight runs by . . . . . . . . . . . . .

. modifying catalysts and operating conditions. Desulfurizing the remainder of the distillate . . . . . . . . . .

. streams is expected to pose the greatest challenge, requiring either substantial revamps to
. . . . . . . . . . . .

. equipment or construction of new units. In some refineries the heavier and less valuable . . . . . . . . . . . . . .

. streams, such as LCOs, are run through a hydrocracker. The distillates from the cracked
. . . . . . . . . . . . . . . .
. stocks contain a larger concentration of compounds with aromatic rings, making sulfur
. . . . . . . . . . .

. removal more difficult. The need for some refineries to desulfurize the cracked stocks in
. . . . . . . . . . . . . .

. addition to the straight- run streams may play a key role in the choice of technology.
. . . . . . . . . . . . . . . . . .

. When the 15 ppm ULSD specification takes effect in Pakistan, refiners will have to
. . . . . . . . . . . . . .

. desulfurize essentially all diesel blending components, especially cracked stocks, to provide . . . . . . . . . . . .

. for highway uses. It is generally believed that a two- stage deep desulfurization process will
. . . . . . . . . . . . . . .

. be required by most, if not all refiners, to achieve a diesel product with less than 10 ppm
. . . . . . . . . . . . . . . . . . .

. sulfur. The following discussion reviews a composite of the technological approaches of

. . . . . . . . . . . .

. UOP, Criterion Catalyst Haldor Topsoe, and MAKFining(a consortium effort of Mobil, . , . . . . . . . . . . .

. Akzo Nobel, Kellogg Brown & Root, and TotalFinaElf Research).

. . . . . . . . . .

. A design consistent with recent technology papers would include a first stage that reduces
. . . . . . . . . . . . .

. the sulfur content to around 250 ppm or lower and a second stage that completes the
. . . . . . . . . . . . . . .

. reduction to less than 10 ppm. In some cases the first stage could be a conventional . . . . . . . . . . . . . . . .

. hydrotreating unit with moderate adjustments to the operation parameters. Recent advances . . . . . . . . . . .

. in higher activity catalysts also help in achieving a higher sulfur removal rate. The second
. . . . . . . . . . . . . . .

. stage would require substantial modification of the desulfurization process, primarily

. . . . . . . . . .

. through using higher pressure, increasing hydrogen rate and purity, reducing space velocity,
. . . . . . . . . . . . . . .

. and choice of catalyst. To deep desulfurize cracked stocks, a higher reactor pressure is
. . . . . . . . . . . . . . .

. necessary. Pressure requirements would depend on the quality of the crude oil and the setup
. . . . . . . . . . . . . . .

. of the individual refinery.

. .. .

. The level of pressure required for deep desulfurization is a key uncertainty in assessing the
. . . . . . . . . . . . . .

. cost and availability of the technology. In its 2000 study, U. S. Petroleum Refining: Assuring
. . . . . . . . . . . .. . . . . . . .

. the Adequacy and Affordability of Cleaner Fuels, the National Petroleum Council (NPC)
. . . . . . . . . . . . . .

. suggested that in order to produce diesel at less than 30 ppm sulfur, new high - pressure . . . . . . . . . . . . . . . . .

. hydrotreaters would be required, operating at pressures between 1,100 and 1,200 psig. . . . . . . . . . . . . . .

. Pressures over 1000 psig are expected to require thick- walled reactors, which are produced . . . . . . . . . . . . . .

. by only a few suppliers and take longer to produce than reactors with thinner walls. In
. . . . . . . . . . . . . . . .

. contrast to NPCs expectations, EPAs cost analysis reflected vendor information for . . . . . . . . . .

. revamps of 650 psig and 900 psig units that would not require thick- walled reactors. The
. . . . . . . . . . . . . . . . .

. vendors indicated that an existing hydrotreating unit could be retrofitted with a number of
. . . . . . . . . . . . .

. different vessels, including: a reactor, a hydrogen compressor, a recycle scrubber, an . . . . . . . . . . . . . . .

. interstage stripper, and other associated process hardware. The amount of hydrogen required . . . . . . . . . . . . . .
. for desulfurization is also uncertain, because the industry has no experience with widespread
. . . . . . . . . . . . .

. desulfurization at ultra- low levels. . . . . . . .

. One of the primary determinants of cost is hydrogen consumption and the related investment
. . . . . . . . . . . . .

. in hydrogen - producing equipment. Hydrogen consumption is the largest operating cost in

. . . . . . . . . . . . .

. hydrotreating diesel, and minimizing hydrogen use is a key objective in hydrotreating for . . . . . . . . . . . . .

. sulfur removal. In general, 10 ppm sulfur diesel would require 25 to 45 percent more
. . . . . . . . . . . . . . . .

. hydrogen consumption than would 500 ppm diesel, in addition to improved catalysts. . . . . . . . . . . .

. Hydrogen requirements at lower sulfur levels rise in a nonlinear fashion. . . . . . . . . . . . .

. In addition to improvements in design and catalysts, other modifications to refinery

. . . . . . . . . . . . .

. operations can contribute to the production of ULSD. For example, high - sulfur compounds . . . . . . . . . . . . . . .

. in both straight runs and cracked stocks lie predominantly in the higher boiling range of the
. . . . . . . . . . . . . . . .

. materials. . .

. Thus, reducing the final boiling point for the streams and cutting off the heaviest boiling
. . . . . . . . . . . . . . .

. segment can reduce the difficulty of the desulfurization task. If a refiner has hydrocracking . . . . . . . . . . . . .

. capability, the hydrocracker would be an ideal disposition for these streams. Some refiners . . . . . . . . . . . . . .

. making both high- and low- sulfur distillate products may be able to allocate the more . . . . . . . . . . . . . . . .

. difficult distillate blend streams to the high- sulfur product. . . . . . . . . . .

. A processing scheme that has been promoted primarily in Asia and Europe employs a
. . . . . . . . . . . . .

. combination of partial hydrocracking and FCC to produce very- low- sulfur fuels. In this . . . . . . . . . . . . . . . .

. scheme a partial conversion hydrocracking unit is placed in front of the FCC unit to convert
. . . . . . . . . . . . . . .

. the vacuum gas oil to light products (distillate, kerosene, naphtha, and lighter) and FCC
. . . . . . . . . . . . . . . . . .

. feed. The distillate product is low in sulfur (less than 200 ppm) and has a cetane number of
. . . . . . . . . . . . . . . . . . . .

. about 50. The cracked stocks produced in the FCC unit are also lower in sulfur and higher in
. . . . . . . . . . . . . . . . . .

. cetane. The relatively greater demand for distillate relative to gasoline demand in Europe
. . . . . . . . . . . . . .

. and Asia and the higher diesel cetane requirement are more in keeping with the strengths of
. . . . . . . . . . . . . .

. this process option than is the case for most U. S. refineries.

. . .. . . . . . . . . . . .

. A few new technologies that may reduce the cost of diesel desulfurization sulfur adsorption
. . . . . . . . . . . , . . ,

. biodesulfurization and sulfur oxidation are in the experimental stages of development. In , . . . .. . . . . . . . .

. addition, methods have been developed to produce diesel fuel from natural gas and organic
. . . . . . . . . . . . . .

. fats, but they still are costly

. . . . . . .
2.4: Developing Technologies and Ultra-Low-Sulfur
Alternatives

2.4.1: Sulfur Adsorption

. One new technology on the horizon is the S Zorb processing under development by
. . . . . . . . . . . . .

. Phillips Petroleum. S Zorb has been promoted for gasoline desulfurization to meet EPAs
. . . . . . . . . . . . .

. Tier 2 requirements. The major distinction of this process from conventional hydrotreating is
. . . . . . . . . . . . .

. that the sulfur in the sulfur- containing compounds adsorbs to the catalyst after the feedstock -
. . . . . . . . . . . . . . . ..

. hydrogen mixture interacts with the catalyst. Thus the catalyst needs to be regenerated . . . . . . . . . . . .

. constantly. Phillips is promoting the S Zorb process for highway diesel as potentially having
. . . . . . . . . . . . . .

. lower capital cost than conventional hydrotreating options and reportedly is on the fast track
. . . . . . . . . . . . .

. to demonstrate the process in a pilot plant in 2001. Phillips estimates on- site capital costs at
. . . . . . . . . . . . . . . . . .

. $ 1, 000 to $ 1, 400 per barrel per day.

. . . . . . . . . . . . .

2.4.2: Biodesulfurization
. Biodesulfurization is another innovative technology, which uses bacteria as the catalyst to . . . . . . . . . . . .

. remove sulfur from the feedstock. In the biodesulfurization process, organosulfur

. . . . . . . . . . .

. compounds, such as dibenzothiophenes and its alkylated homologs, are oxidized with . . . . . . . . . . . .

. genetically engineered microbes, and sulfur is removed as a water- soluble sulfate salt. . . . . . . . . . . . . . .

. Several factors may limit the application of this technology, however. Many ancillary
. . . . . . . . . . . . .

. processes novel to petroleum refining would be needed, including a biocatalyst fermentor to

. . . . . . . . . . . . .

. regenerate the bacteria . The process is also sensitive to environmental conditions such as . . . . . . . . . . . . .

. sterilization, temperature, and residence time of the biocatalyst. Finally, the process requires . . . . . . . . . . . . . . .

. the existing hydrotreater to continue in operation to provide a lower sulfur feedstock to the
. . . . . . . . . . . . .

. unit and is more costly than conventional hydrotreating. Biodesulfurization has been tested
. . . . . . . . . . . .

. in the laboratory, but detailed engineering designs and cost estimates have not been
. . . . . . . . . . . . .

. developed. . .

. Sulfur Oxidation . .

. The latest entry in unconventional desulfurization involves sulfur oxidization. This process
. . . . . . . . . . .

. creates a petroleum and water emulsion in which hydrogen peroxide or another oxidizer is
. . . . . . . . . . . . .

. used to convert the sulfur in sulfur- containing compounds to sulfone. The oxidized sulfone
. . . . . . . . . . . . . . .

. is then separated from the hydrocarbons for post-processing. Most of the peroxide can be
. . . . . . . . . . . . . .
. recovered and recycled. The major advantages of this new technology include low cost, . . . . . . . . . . . . .

. lower reactor temperatures and pressures, short residence time, no emissions, and no
. . . . . . . . . . . . .

. hydrogen requirement. . .

. Advocates for the sulfur oxidation technology estimate capital costs at $ 1, 000 per barrel of . . . . . . . . . . . . . . . .

. daily installed capacity less than half the cost of a new high- pressure hydrotreater. The
. . . . . . . . . . . . . . . . .

. technology preferentially treats dibenzothiophenes, one of streams that is most difficult to . . . . . . . . . . . .

. desulfurize, but it does not work as well on straight- run distillate. Because the process . . . . . . . . . . . . . . . . .

. removes molecules containing sulfur, some volume losses also occur. One company working . . . . . . . . . . . . .

. on the technology has proposed installation of 1,000 to 5,000 barrel per day units at
. . . . . . . . . . . . .

. distribution terminals to polish material that might otherwise be downgraded. Construction . . . . . . . . . . . . .

. of a pilot plant is planned, but to date there has been no real- world demonstration of the
. . . . . . . . . . . . . . . . . . . .

. process.

2.4.3: Fischer-Tropsch Diesel and Biodiesel

. One way to add to ULSD supply without desulfurization is to rely on a non- oil- based diesel.
. . . . . . . . . . . . . . . . . . . .

. The Fischer- Tropsch process, for example, can be used to convert natural gas to a synthetic,
. . . . . . . . . . . . . . . . . . .

. sulfur- free diesel fuel. Two gas- to- liquids (GTL ) facilities have operated commercially: the
. . . . . . . . . . . . . . . . . . . .

. Mossgas plant in South Africa with output capacity of 23, 000 barrels per day and the Shell . . . . . . . . . . . . . . .

. Bintulu plant in Malaysia at 12, 500 barrels per day. Other plants are in the planning stages.
. . . .. . . . . . . . . . . . . .

. Commercial viability of GTL projects depends on capital costs, the market for petroleum . . . . . . . . . . . .

. products and possible price premiums for GTL fuels, the value of byproducts such as heat . . . . . . . . . . . . . .

. and water, the cost of feedstock gas, the availability of infrastructure, the quality of the local
. . . . . . . . . . . . . . . . . .

. workforce, and potential government subsidies . . . . . . .. .

. Capital costs for GTL projects are currently less than $ 25, 000 per daily barrel of capacity.
. . . . . . . . . . . . . . . . . .

. An EIA analysis of a hypothetical GTL project estimated the cost of GTL fuel at almost $ 25
. . . . . . . . . . . . . . . . .

. per barrel in 1999 dollars. Thus, a GTL project with present technology could be cost
. . . . . . . . . . . . . . . .

. competitive only if investors were confident that crude oil prices would stay in the range of . . . . . . . . . . . . . . .

. $ 25 to $ 30 per barrel and natural gas feedstock prices would remain at 50 cents per thousand
. . . . . . . . . . . . . . . . . .

. cubic feet.

. A second way to avoid desulfurization is with biodiesel made from vegetable oil or animal
. . . . . . . . . . . . . .

. fats. Although other processes are available, most biodiesel is made with a base- catalyzed
. . . . . . . . . . . . . . . .

. reaction. A fat or oil is reacted with an alcohol, such as methanol, in the presence of a
. . . . . . . . . . . . . . . . . . . .
. catalyst to produce glycerin and methyl esters or biodiesel. The methanol is charged in
. . . . . . . . . . . . .

. excess to assist in quick conversion and recovered for reuse. The catalyst, usually sodium or
. . . . . . . . . . . . . . . .

. potassium hydroxide, is mixed with the methanol. Increased production of biodiesel could . . . . . . . . . . . .

. create more surfactants than the market would be able to absorb. Biodiesel is a strong
. . . . . . . . . . . . . . .

. solvent and can dissolve paint as well as deposits left in fuel lines by petroleum- based
. . . . . . . . . . . . . . . .

. diesel, sometimes leading to engine problems. Biodiesel also freezes at a higher temperature
. . . . . . . . . . . . . .

. than petroleum- based diesel. Biodiesel advocates claim that a 1 - percent blend of biodiesel
. . . . . . . . . . . . . . . .

. can improve lubricity by as much as 65 percent.

. . . . . . . . .

. At least eight companies are marketing biodiesel in all parts of the United States, according
. . . . . . . . . . . . . . .

. to the National Biodiesel Board.

. . . . .

2.5: NEMS Approach to Diesel Desulfurization .

Technology
. The Petroleum Market Module (PMM) in the National Energy Modeling System (NEMS)
. . . . . . . . . . . . . . .

. projects petroleum product prices, refining activities, and movements of petroleum into the
. . . . . . . . . . . . .

. United States and among domestic regions. In addition, the PMM estimates capacity
. . . . . . . . . . . . .

. expansion and fuel consumption in the refining industry. The PMM is also revised on a . . . . . . . . . . . . . . .

. regular basis to incorporate current regulations that may affect the domestic petroleum
. . . . . . . . . . .

. market. . .

. The PMM optimizes the operation of petroleum refineries in the United States, including the
. . . . . . . . . . . . . .

supply and transportation of crude oil to refineries, the regional processing of these raw
. . . . . . . . . . . . . .

. materials into petroleum products, and the distribution of petroleum products to meet . . . . . . . . . . . .

. regional demands. The production of natural gas liquids from gas processing plants is also
. . . . . . . . . . . . . .

. represented. The essential outputs of the model are product prices, a petroleum supply/ . . . . . . . . . . . . . . .

. demand balance, demands for refinery fuel use, and capacity expansion. The PMM employs
. . . . . . . . . . . . . .

. a modified two- stage distillate deep desulfurization process based on proven technologies.
. . . . . . . . . . . . .

. The first stage consists of a choice of two distinct units, which accept feedstocks of various
. . . . . . . . . . . . . . .

. sulfur contents and desulfurize to a range of 20 to 30 ppm. The second stage also includes a
. . . . . . . . . . . . . . . . . .

. choice of two processing units, which further deep desulfurize the first- stage streams to a
. . . . . . . . . . . . . . . .

. level below 10 ppm. The purpose of reducing the sulfur level to 20 to 30 ppm in the first
. . . . . . . . . . . . . . . . . .

. stage, rather than the common goal of 250 ppm or less, is to enable a more accurate
. . . . . . . . . . . . . . .

. representation of costs for processing streams. The PMM retains the option of conventional . . . . . . . . . . . . .
. distillate desulfurization when 500 ppm sulfur diesel can still be produced. Because the
. . . . . . . . . . .

. PMM models an aggregation of refinery capacities in each of the refinery regions, the above
. . . . . . . . . . . . . .

. representation of multiple processing options is possible, although in reality individual . . . . . . . . . . .

. refineries may choose one process over the other on the basis of strategic and economic . . . . . . . . . . . . . .

. evaluations. .

2.6: Individual refinery Analysis Approach to Diesel

Desulfurization Technology
. To assess the supply situation during the transition to ULSD in 2006 in USA, industry- level
. . . . . . . . . . . . . . . . .

. cost curves were constructed for this study and matched against assumed demand and
. . . . . . . . . . . .

. imports. The cost curves are the result of a refinery- by- refinery analysis of investment
. . . . . . . . . . . . . . . . .

. requirements and operating costs for refineries in Petroleum Administration for Defense . . . . . . . . . .

. Districts (PADDs) I through IV. The ULSD production costs were estimated for different
. . . . . . . . . . . . . . .

. groups of refineries based on their size, the sulfur content of the feeds, the fraction of
. . . . . . . . . . . . . . . . .

. cracked stocks in the feed, the boiling range of the feed, and the fraction of highway diesel
. . . . . . . . . . . . . . . . . .

. produced. The capital and operating costs for the different groups were developed for EIA
. . . . . . . . . . . . . .

. by the staff of the National Energy Technology Laboratory (NETL).

. . . . .. . . . . . . .

. For the study, a semi- empirical model was developed to size and cost new and retrofitted
. . . . . . . . . . . . . . . . .

. distillate hydrotreating plants for production of ULSD. Sulfur removal was predicted using a
. . . . . . . . . . . . .

kinetic model tuned to match the limited literature data available on deep distillate
. . . . . . . . . . .

. desulfurization. Correlations were used in the model to relate hydrogen consumption, utility . . . . . . . . . . . . .

. usage, etc., to the three major constituents of the distillate pool: straight- run distillate, cat-
. . . . . . . . . . . . . . . . . . . .

. cracker light cycle oil, and coker gas oil. . . . . . . .

. Capital costs ranged from $ 592 to $ 1, 807 per barrel per day, depending on the size of the
. . . . . . . . . . . . . . . . . . . . .

. unit, whether it was new or retrofitted, and the percentage of straight run feedstock. A large
. . . . . . . . . . . . . . . . .

. hydrotreater using only straight- run distillate derived from high - sulfur crude had the least . . . . . . . . . . . . . .

. cost for both new and retrofitted units. The most expensive units were small hydrotreaters
. . . . . . . . . . .

. running 32 percent cracked stocked, about the average proportion of cracked feedstocks in
. . . . . . . . . . . .

PADD II.
2.7: Conclusion
. Technology for reduction of sulfur in diesel fuel to 15 ppm is currently available and new
. . . . . . . . . . . . . .

. technologies are under development that could reduce the cost of desulfurization. Variations
. . . . . . . . . .

. in feedstock sulfur content and the amount of cracked stock may be very influential in the
. . . . . . . . . . . .

choice of process option and cost of desulfurization. Estimates of investment costs related to
. . . . . . . . . . . . .

. ULSD production range from $ 3 billion to $ 13 billion. The ability and willingness of
. . . . . . . . . . . . . .

. refiners to invest depends on an assessment of market economics. The availability of

. . . . . . . . . .

. personnel, thick- walled reactors, and reciprocating compressors may delay some
. . . . . . . . . .

. construction. .
PROCESS DESCRIPTION

&

CAPACITY SELECTION
 Chapter # 03

3: Process Description & Capacity Selection .

3.1: Hydrodesulphurization [13]

. Hydrodesulfurization processes aim at the removal of impurities such as sulfur and nitrogen
. . . . . . . . . . . . .

. from distillate fuels naphtha, kerosene, and diesel by treating the feed with hydrogen at
. . . . . . . . . . . . . . . . .

. elevated temperature and pressure in the presence of a catalyst. Hydrodesulfurization has

. . . . . . . . . . . .

. been extended in recent years to atmospheric residues to reduce the sulfur and metal content
. . . . . . . . . . . . . .

. of residues for producing low- sulfur fuel oils. The operating conditions of treatment are a
. . . . . . . . . . . . . . . .

. function of type of feed and the desulfurization levels desired in the treated product. The
. . . . . . . . . . . . . . .

. principal impurities to be removed are

. . . . .

a) Sulfur.
b) Nitrogen.
c) Oxygen.
d) Olefins.
e) Metals.
. The basic reactions involved in hydrodesulphurization are outlined in the Table: 02.
. . . . . . . .

3.1.1: Sulfur
. The sulfur- containing compounds are mainly mercaptans, sulfides, disulfides, polysulfide,
. . . . . . . . . . . . . .

. and thiophenes. The thiophenes are more difficult to eliminate than most other types of
. . . . . . . . . . . . . .

. sulfur.

3.1.2: Nitrogen
. The nitrogen compounds inhibit the acidic function of the catalyst considerably. These are
. . . . . . . . . . . . .

. transformed into ammonia by reaction with hydrogen. . . . . . .

3.1.3: Oxygen
. The oxygen dissolved or present in the form of compounds such as phenols or peroxides is
. . . . . . . . . . . . . . .

. eliminated in the form of water after reacting with hydrogen. . . . . . . . . . .

3.1.4: Olefins
. The olefinic hydrocarbons at high temperature can cause formation of coke deposits on the
. . . . . . . . . . . . .

. catalyst or in the furnaces. These are easily transformed into stable paraffinic hydrocarbons.
. . . . . . . . . . . . . .

. Such reactions are highly exothermic. Straight run feeds from the crude unit usually contain
. . . . . . . . . . . . . .

. no olefins. If, however, the feed contains a significant amount of olefins, a liquid quench
. . . . . . . . . . . . . . . . . .

. stream is used in the reactor to control the reactor outlet temperature within the design
. . . . . . . . . . . . . .

. operating range. . . .

3.1.5: Metals
. The metals contained in the naphtha feed are arsenic, lead, and to a lesser degree copper and
. . . . . . . . . . . . . . . . . .

. nickel, which damage the reforming catalyst permanently. Vacuum diesels and residue feeds
. . . . . . . . . . . . .

. can contain a significant amount of vanadium and nickel. During the hydrodesulfurization
. . . . . . . . . . . .

. process, the compounds that contain these metals are destroyed and the metals get deposited
. . . . . . . . . . . . . .

. on the hydrodesulfurization catalyst.

. . . .

3.2: Operating Variables

. The principal variables for hydrodesulfurization (HDS) reactions are temperature, the total
. . . . . . . . . . . . .

. reactor pressure and partial pressure (PP H2) of hydrogen, the hydrogen recycle rate, and the
. . . . . . . . . . . . . . . . . .

. space velocity ( VVH). . . .. .

3.2.1: Temperature
. The HDS reactions are favored by an increase in temperature, but at the same time, high
. . . . . . . . . . . . . . . . .

. temperature causes coking reactions, diminishing the activity of the catalyst. The . . . . . . . . . . . .

. desulfurization reactions are exothermic and the heat of reaction is approximately 22- 30 Btu/ . . . . . . . . . . . . . .

. mole hydrogen . It is necessary to find a compromise between the reaction rate and the
. . . . . . . . . . . . . . .

. overall catalyst life. The operating temperature (start of run/ end of run) is approximately
. . . . . . . . . . . . . . . . .

. 325- 355C according to the nature of the charge. During the course of a run, the temperature
. . . . . . . . . . . . . . . . . . . .

. of the catalyst is gradually raised to compensate for the fall in activity due to coke deposits
. . . . . . . . . . . . . . . .

. until the maximum permissible temperature limit (EOR) for the HDS catalyst is reached. At
. . . . . . . . . . . . . . .

. this stage, the catalyst must be regenerated or discarded .

. . . . . . . .

3.2.2: Pressure
. The increase in partial pressure of hydrogen increases the HDS rate and diminishes the coke
. . . . . . . . . . . . . .

. deposits on the catalyst, thereby reducing the catalyst fouling rate and increasing the catalyst
. . . . . . . . . . . . . .

. life. Also, many unstable compounds are converted to stable compounds. Operation at
. . . . . . . . . . . . . .

. higher pressure increases the hydrodesulfurization rate because of higher hydrogen partial
. . . . . . . . . .

. pressure in the reactor, requiring a smaller quantity of catalyst for a given desulfurization
. . . . . . . . . . . . .

service. In an operating unit, higher- pressure operation can increase the feed throughput of
. . . . . . . . . . . . . . . .

. the unit while maintaining the given desulfurization rate.

. . . . . . . .

3.2.3: Space Velocity

. The liquid hourly space velocity (LHSV) is defined as
. . . . . . . . . . .

Volumetric Feed Rate m3

LHSV=
Catalyst Volume hour.m3catalyst
. Hydrodesulfurization reactions are favored by a reduction in VVH. The rate of . . . . . . . . . . . .

. desulfurization is a function of (PP H2/ VVH) or the ratio of partial pressure of hydrogen in . . . . . . . . . . . . . . . . . . .

. the reactor to liquid hourly space velocity. For a given desulfurization rate (at constant
. . . . . . . . . . . . . .

. temperature), the ratio PP H2 / VVH is fixed. Fixing the total reactor pressure automatically . . . . . . . . . . . . . . .

. fixes the partial pressure and the required hydrogen recycle rate. In general, the total reactor
. . . . . . . . . . . . . . . .

. pressure is fixed from the available hydrogen pressure, the hydrogen partial pressure, and. . . . . . . . . . . . .

. other variables such as VVH are adjusted until these falls within the acceptable limits.
. . . . . . . . . . . . . .
3.2.4: Recycle Rate
. In an HDS process, the hydrogen separated in a high- pressure (HP) separator drum is
. . . . . . . . . . . . . . . . . . .

. recycled to the reactor via a recycle compressor and furnace. This stream joins the incoming
. . . . . . . . . . . . . . .

. fresh feed, which has been heated in the feed furnace. The recycle rate is the ratio of volume
. . . . . . . . . . . . . . . .

. of hydrogen at 1atm and 25 C to the volume of fresh liquid feed at 25 C [14].

. . . . . . . . . . . . . . .. . .

3.2.5: Makeup Hydrogen

. While the hydrogen recycling assures the requisite partial pressure of hydrogen in the
. . . . . . . . . . . .

. reactor, makeup hydrogen is required to replace the hydrogen consumed in HDS reactions.
. . . . . . . . . . . . .

. The hydrogen is lost through solution losses in the liquid phase and purges for regulating
. . . . . . . . . . . . . .

. unit pressure and maintaining recycle gas purity [14].

. . . . . .

3.2.6: Purge Ratio

. A purge ratio is the ratio of the volume of hydrogen in the purged gas to the volume of
. . . . . . . . . . . . . . . . . .

. hydrogen in the makeup gas. Purging is required to prevent the buildup of inert gases and
. . . . . . . . . . . . . . . .

. light hydrocarbons in the recycle gas. The quantity of purge directly influences the purity of
. . . . . . . . . . . . . .

. the hydrogen in the recycle gas. For low- sulfur feeds such as naphtha, the purge ratio
. . . . . . . . . . . . . . . . . .

. required is small. For heavy, high- sulfur feeds the purge ratio required to maintain the purity
. . . . . . . . . . . . . . . . .

. of recycled hydrogen is quite high. Typical purge values used in hydrodesulfurization

. . . . . . . . . . . .

. process are shown in Table 3.1 [14] . . . .

Table 8: Purge Requirements of HDS Processes

Hydrogen in purge / Hydrogen
Process
in makeup gas
Naphtha HDS 10%
Kerosene HDS 15%
Diesel HDS 20%
VGO HDS 30%

3.3: Catalysts
. The catalyst consists of two parts, the catalyst support and the active elements. The support
. . . . . . . . . . . . . . . .

. consists of solid substances with high porosity and able to withstand the temperature,
. . . . . . . . . . . . .

. pressure, and the environment encountered in HDS reactors. The support utilized by the
. . . . . . . . . . . . .
. HDS catalyst is alumina in the form of balls or extrudates. The active elements are the
. . . . . . . . . . . . . . . .

. metals deposited on the support in form of oxides. Before operation, the catalyst is sulfided
. . . . . . . . . . . . . . .

. in order to moderate activity. The principal types of catalyst used in the HDS service are
. . . . . . . . . . . . . . .

a) Cobalt (molybdenum on alumina support). This is the general catalyst for HDS
. . . . . . . . . . . . .

. service.
b) Nickel (molybdenum on alumina support). This is used especially for denitrification.
c) Cobalt (molybdenum and other metals on neutral support). The neutral support
. . . . . . . . . . . . .

. prevents the polymerization of the olefins. This catalyst is employed in conjunction . . . . . . . . . . .

. with other catalysts for olefinic feeds [14]. . . . . ..

3.4: Diesel Hydrodesulfurization

. Diesel hydrodesulfurization is designed to reduce the sulfur and other impurities (e. g.,
. . . . . . . . . . . . . . .

. nitrogen ) present in the raw diesel cuts. The feed to the unit may be a straight run diesel cut
. . . . . . . . . . . . . . . . . . . .

. from the crude distillation unit or secondary units such as FCCU (light cycle diesel). The
. . . . . . . . . . . . . . . .

. feed from these secondary units may contain significant amount of olefinic hydrocarbons,
. . . . . . . . . .

which must be converted to saturate in the diesel hydrodesulfurization unit to improve the
. . . . . . . . . . .

. storage stability of these products. . . . . . .

. The primary improvement in product quality is with respect to sulfur and conradson carbon.
. . . . . . . . . . . . . .

. The raw diesel cut from most Middle Eastern crudes, for example, may contain as much as
. . . . . . . . . . . . . . . .

. 1- 2% sulfur. Because of atmospheric pollution concerns, the sulfur content of saleable diesel
. . . . . . . . . . . . . . .

. grades allowable in most countries has fallen very rapidly. Until a few years ago 1. 0% sulfur
. . . . . . . . . . . . . . . .

. was acceptable. But, because of very rapid increase in the number of vehicles using diesel
. . . . . . . . . . . . .

. worldwide, the pollution level has risen exponentially. To curb this increasing atmospheric
. . . . . . . . . . .

. pollution, sulfur specifications in most developed countries have fallen to 0. 005 wt % or

. . . . . . . . . . . . . . .

. lower. The average sulfur decline is often pushed by vehicle and engine manufacturers
. . . . . . . . . . .

. aiming at lower particulate emissions [13]. . . . .

3.4.1: Process Flow Diagram

Flow sheet of our process prepared on MS visio is shown in following page.
 F-4 F-17
Start

F-16
Start

E-4 F-5 F-18 E-10

E-9
F-6 F-8

F-15
END

E-5 F-13

E-3
F-7

Start

F-3 F-9 F-12 E-8

F-11 F-14
END

E-2
E-7
F-22
END
F-10 E-6

F-2

F-19 E-11
F-24
END

F-1
Start
F-20 F-23
END
Process flow sheet diagram

E-1 E-12
Sr. No. Description
E-1 Pump
E-2 Heat Exchanger
E-3 Furnace
E-4 Compressor
E-5 Trickle Bed Reactor
E-6 High Pressure Hot Separator
E-7 Cooler
E-8 High Pressure Cold Separator
E-9 Absorber
E-10 Recycled Gas Booster
E-11 Steam Stripper
E-12 Dryer
F-1 Raw Diesel entering to pump(E-1)
F-2 Raw Diesel leaving the pump(E-1) and entering the heat exchanger(E-2)
F-3 Raw Diesel leaving the heat exchanger(E-2) and mixing with compressed H2
coming from compressor(E-4) and recycled gas booster(E-10)
F-4 H2 entering to compressor(E-4)
F-5 H2 leaving the compressor(E4) and mixing with stream (F-18) coming from recycle
gas booster(E-10)
F-6 Combined stream of H2 from compressor(E-4) and recycle gas booster(E-10)
F-7 Stream entering to furnace(E3) containing raw diesel coming from heat
exchanger(E-2) and H2 (F-6)
F-8 Stream coming out from furnace(E-3) and entering to reactor(E-5)
F-9 Stream coming out from reactor(E-5) and entering to heat exchanger(E-2) for heat
exchange with raw diesel
F-10 Stream coming out from heat exchanger(E-2) after exchanging heat with raw diesel
and entering the high pressure hot separator(E-6)
F-11 Stream leaving at the top of HP hot separator(E-6) and entering the cooler(E-7)
F-12 Stream leaving the cooler(E-7) and entering to HP cold separator(E-8)
F-13 Stream leaving the from top of HP cold separator(E-8) and entering the bottom of
absorber(E-9) for H2S absorption with DEA
F-14 Stream leaving the HP cold separator(E-8)
F-15 Rich DEA stream leaving the absorber(E-9)
F-16 Lean DEA stream entering the absorber(E-9)
F-17 Stream leaving from the top of absorber(E-9) containing mostly H2 and entering to
recycle gas booster(E-10)
F-18 Stream leaving the recycle gas booster(E-10) and mixing with compressed H2
coming from compressor(E-4)
F-19 Stream leaving the bottom of HP hot separator(E-6) and entering the steam
stripper(E-11) for removal of H2S and light ends
F-20 Stream leaving the bottom of steam stripper(E-11) and entering to dryer for H2O
removal from hydrotreated diesel
F-22 Stream leaving the top of steam stripper(E-11) containing H2S and light ends
F-23 Hydrotreated diesel stream leaving the dryer(E-12) after removal of H2O
F-24 H2O steam leaving the dryer(E-12)
3.4.2: Description of Flow Diagram
. A typical flow diagram for distillate hydrodesulfurization is shown in the figure. The diesel
. . . . . . . . . . . . . .

. feed is mixed with fresh and recycled hydrogen and heated under pressure to the proper
. . . . . . . . . . . . . .

. reactor temperature and pressure (325- 355oC & 60 kg/cm2). The diesel hydrogen mixture is
. . . . . . . . . . . . . . . . .

. charged to the reactor, passing down flow through the catalyst. In the reactor, fresh feed is
. . . . . . . . . . . . . . . . .

. hydrotreated and a limited amount of hydrogenation, isomerization and cracking occurs to . . . . . . . . . . .

. produce a small amount of C1 to C5 paraffin. In addition, sulfur compounds are converted to

. . . . . . . . . . . . . . .

. hydrogen sulfide and nitrogen compounds are converted to ammonia . Olefins are also
. . . . . . . . . . .

. saturated. These reactions are exothermic and, in the cases of vacuum gas oils or unsaturated
. . . . . . . . . . . . .

. feedstocks, reactor temperature rise is regulated by the use of cold recycle gas quench.. . . . . . . . . . . . . .

. .Reactor effluents are cooled in heat exchanger and enter the high pressure separator where
. . . . . . . . . . .

the diesel is separated from the hydrogen sulfide and hydrogen rich gas. Hydrogen sulfide is
. . . . . . . . . . . .

. scrubbed from the gas with the help of absorber by using 20% DEA solution and the
. . . . . . . . . . . .

. hydrogen- rich gas is recycled. The liquid is passed through stripper to remove the remaining
. . . . . . . . . . . . . . .

. . light ends and dissolved hydrogen sulfide. Fractionation of the liquid product is sometimes
. . . . . . . . . . . .

. employed , especially on heavier charge stocks. . . . .. ..

3.4.3: Detailed process description of hydrodesulfurization

3.4.3.1: Feed Pump

. Product diesel from distillation unit passes through series of exchangers by feed pump where
. . . . . . . . . . . .

. temperature if increases from 50oC to 60oC and then sent to furnace. A flow rate of about . . . . . . . . . . . . . . . .

. 40000bbl/ day is handled by this pump. . .. . . . .

3.4.3.2: Furnace
. When feed passes through furnace it is heated from 117oC to 325oC by using natural gas
. . . . . . . . . . . . . . .

. having calorific value of 361364. 638 Btu/ lbmole.

. . . . . . . . . . .

. Natural gas is used for linear heating purposes and easily control because reactor is very
. . . . . . . . . . . . . .

. sensitive towards the changes of the temperature another advantage is its low price and
. . . . . . . . . . . .

. availability. .
3.4.3.3: Reactor
. Feed enter the reactor from the top at the temperature of 325oC and hydrogen gas from side,
. . . . . . . . . . . . . . . .

. so that there may be intimate contact between diesel and hydrogen gas. The reaction takes
. . . . . . . . . . . . . . .

. place 325oC, temperature increases because major reactions involves are exothermic in
. . . . . . . . . . .

. nature. In the reactor sulfur compounds react with hydrogen and produces H2S. Nitrogen
. . . . . . . . . . . . .

. compounds react and form NH3, salts like Chlorides react to form HCl. Phenol in Diesel . . . . . . . . . . . . . .

. reacts to form water and saturated Hydrocarbons . All chemical reactions are involved here,
. . . . . . . . . . . .

. after that only physical separation occurs which is as follows

. . . . . . . . . .

3.4.3.4: High Pressure Hot separator

. All the components from the bottom of reactor enter in the high pressure hot separator by
. . . . . . . . . . . . . . .

. passing through heat exchanger where heat is recovered. High pressure hot separator . . . . . . . . . . . .

. operates at 240oC temperature and 54. 9 kg/ cm2 pressure. In HP hot separator H2 and light . . . . . . . . . . . . . . . . . .

. gases like NH4Cl, H2S, H2 gas and excess NH3 which are less condensed even at high
. . . . . . . . . . . . . .

pressure are separated from top and sent to the absorber to recover H2S. The condensate is . . . . . . . . . . . . . .

. diesel which is about 99. 9 % and water 60 % are separated from bottom and sent to stripper
. . . . . . . . . . . . . . . . . .

. feed. .

3.4.3.5: High pressure cold separator

. The top product of high pressure hot separator is sent to high pressure cold separator where
. . . . . . . . . . . . . . .

. temperature is decreased by exchanging heat through heat exchanger. Water is also injected . . . . . . . . . . . . .

. before high pressure cold separator to dissolve NH4Cl acid to separate it by condensing the
. . . . . . . . . . . .

. vapors and condensable gases at high pressure. Solution of NH4Cl in water is about 560gm/
. . . . . . . . . . . . . .

. liter of water and is separated by dissolving it in water. The incondensable H2S is sent to
. . . . . . . . . . . . . . . . .

. absorber to recover it by absorbing it in DEA (diethanol Amine) solution. . . . . . . . . . . .

3.4.3.6: Absorber
. The top product containing H2S and H2 gas as major constituent and traces of light
. . . . . . . . . . . . . .

. hydrocarbons is sent to absorber where it is absorb in 20% DEA solution while light . . . . . . . . . . . . . .

. hydrocarbons and H2 gas acts as inert. Hydrocarbons and waste gases are sent to flare from . . . . . . . . . . . . .

. the top of the absorber while hydrogen gas is recycled. DEA solution is shower from the top
. . . . . . . . . . . . . . . .

. at 45oC while feed gas is injected from the bottom at 40oC, for maximum absorptions and
. . . . . . . . . . . . . .

. contact time at this temperature solubility if H2S in DEA is 0. 3 kg/ liter of DEA solution. The
. . . . . . . . . . . . . . . . . .

absorption column is plate tower because suspended solid may be present in the feed and . . . . . . . . . . .
. fluctuation in flow rate is anticipated. The temperature of the column is about 40oC while the . . . . . . . . . . . . . . . .

. pressure is 53 kg/ cm2. The bottom contains rich DEA solution containing H2S, this stream is
. . . . . . . . . . . . . . .

. sent to amine regeneration tower.

. . . . .

3.4.3.7: Stripper
. From the bottom of the HP hot separator product is sent to stripper. Stripper operating
. . . . . . . . . . . . .

. conditions are 237oC temperature and the atmospheric pressure. At these conditions 80 % of . . . . . . . . . . . .

. water, 90 % NH4Cl and almost all the NH3 gas is stripped out of feed gas and 0 .1 % of C5+
. . . . . . . . . . . . . . . . . . . . .

. which is unstabilized naphtha is also stripped out from top of stripper. Some amount of water
. . . .. . . . . . . .

. along with C5+ are separated from bottom of the stripper and sent to dryer to remover the . . . . . . . . . . . . .

. water contents present in C5+. In stripper temperature is maintained by using MP steam

. . . . . . . . .

(medium pressure steam).

. . .

3.4.3.8: Vacuum dryer

. The product desulfurized diesel obtained from the bottom of the stripper is sent to the
. . . . . . . . . . . . . .

. product dryer from nearly top of the column and hydrogen gas is entered from the bottom
. . . . . . . . . . . . . .

. and drying of the product is done at temperature of about 100oC and a vacuum of 45torr. The
. . . . . . . . . . . . . . . .

. bottom product of dryer is the final product of Hydrodesulfurization unit containing about
. . . . . . . . .

. 99. 96 % diesel hydrocarbons, less than 200 ppm sulfur and minute amount of water and
. . . . . . . . . . . . .

. salts. . .

3.5: Chemistry of the Process

. Catalytic hydrodesulfurization can be accomplishing more than just desulfurization. . . . . . . . . .

. Denitrogenation and olefin saturation can occur as well as the removal of oxygen in certain . . . . . . . . . . . . . .

. applications. Different types of sulfur compounds found in the light hydrocarbons streams . . . . . . . . . . . .

. and the basic desulfurization reactions for which type are listed below. These reaction
. . . . . . . . . . . .

equations show that desulfurization us accomplished by the cleavage of C-S bonds, these . . . . . . . . . . . .

. bonds are replaced by C- H and S- H bonds [15].

. . . . . . . . . . .

Table 9: Typical reactions in desulfurization

Types of Sulfur Compounds Desulfurization Reactions
a.(Mercaptans) a.(Mercaptans)
R-SH R-SH + H2 R-H + H2S
b.(Sulfide) b.(Sulfide)
R-S-R R-S-R + 2H2 2R-R + H2S
c. (Di-sulfide) c. (Di-sulfide)
R-S-S-R R-S-S-R + 3H2 2R-R + 2H2S

3.6: Ultra-Low Sulfur Diesels [14]

. The production of diesel with ultra- low sulfur
. . . . . . . . . (<500ppm) requires a high- severity
. . . . . . .

. operation. Small fluctuations in feedstock properties, unit operating parameters, and catalyst
. . . . . . . . . . . . .

. activity significantly affect the required operating conditions, catalyst deactivation, and cycle
. . . . . . . . . . . .

. length. Essential to deep HDS is good contacting efficiency between the catalyst and the
. . . . . . . . . . . . . .

. liquid. Homogeneous gas and liquid distribution over the entire cross section of the top of
. . . . . . . . . . . . . . .

. the catalyst bed is essential. Dense loading of catalyst is essential to ensure more
. . . . . . . . . . . . .

. homogenous catalyst loading, minimizing the risk of preferential flow through regions with . . . . . . . . . . .

. lower catalyst loading density. The pressure drop at the start of the run is higher than that for
. . . . . . . . . . . . . . . . .

. sock loading but more stable during the cycle. Hydrogen sulfide in the recycle gas inhibits
. . . . . . . . . . . . . .

. the desulfurization activity of the catalyst. At 5 vol% H2S, about 25-30% catalyst activity is
. . . . . . . . . . . . . . . . . . .

. lost. For deep HDS operations, H2S scrubbing of the recycled gas is justified. Feedstock
. . . . . . . . . . . . . . . .

properties greatly affect the degree of desulfurization. Most of the sulfur in the middle . . . . . . . . . . . . . .

. distillates is present only as few types of alkyl substituted benzothiophenes . . . . . . . . . . (BT) and. . .

. dibenzothiophenes (DBT). These compounds differ greatly in their refractivity toward HDS. . . . . . . . . . . . .

. In the straight run diesels, the sulfur concentration increases gradually over the boiling
. . . . . . . . . . . . .

. range, peaking at 350 C, followed by a decline . The Light Cycle Diesel (LCO) containing
. . . . . . . . . . . . . . . . . .

. feed shows a double peak structure consistent with sulfur existing predominantly as
. . . . . . . . . . .

. benzothiophenes and dibenzothiophenes. The . . . . . .effect of feed distillation on color is . . . .

. significant. The color bodies are concentrated in the tail end of the boiling range. A
. . . . . . . . . . . .

. significant improvement in color can be obtained if the end point of the feedstock is reduced . . . . . . . . . . . . . .

slightly. Also, the color of product increases with time, due to higher reactor temperatures.
. . . . . . . . . . . . . . . . .

. Operating conditions of a diesel HDS unit are shown in Table 10. . . . . . . .

Table 10: Typical Diesel HDS Operating Conditions

Operating parameter UNITS Value

Reactor inlet temperature C 325

Reactor T C 20

Reactor inlet pressure kg/cm2 60

Reactor pressure drop kPa 34.5

LHSV* hr -1 11.42

H2/oil ratio SCF/bbl 4575

Recycled gas/feed ratio SCF/bbl 5065

Quench gas/feed ratio SCF/bbl 971

H2 chemical consumption SCF/bbl 422.3

% Desulfurization 98.9

% Denitrification 73.9

* Ni-Mo on Alumina Base Catalyst.

3.7: Capacity Selection

. The capacity of the plant is based on diesel production at PARCO Mid- Country Refinery.
. . . . . . . . . . . . . . . .

. Now, diesel produced at PARCO Mid- Country Refinery at 100 % capacity is 1. 56 MMTY.
. . . . . . . . . . . . . . . . . . .

. Based on 330 days of plant operation,

. . . . . . . .

Daily diesel produced at PARCO = 4522 MTD

Density of diesel = 53.71 lb/ft3

= 861.5 kg/m3

Keeping in view this density of diesel the conversion factor is calculated as follows

Hence, the required capacity of the unit = 4522 7.30

= 33,008bbl/day

Now we have selected plant capacity by keeping eye on the increasing demand of diesel
= 40,000bbl/day
MATERIAL BALANCE
 Chapter# 04

4: Material Balance:-
4.1: Reaction occurring in the reactor
4.1.1: Reactions of sulfur compounds:
4.1.1.1: Mercaptans
C-C-C-C-SH + H2 C-C-C-C-H + H2S

4.1.1.2: Sulfide
C-C-S-C-C + 2H2 2C-C + H2S

4.1.1.3: Di-sulfide
C-C-S-S-C-C + 3H2 2C-C + 2H2S

4.1.1.4: Cyclic sulfide

C
+ 2H2 C-C-C-C and C-C-C + H2S
4.1.1.5: Thiophene
C
+ 4H2 C-C-C-C and C-C-C + H2S

4.1.2: Reactions of nitrogen removal:

4.1.2.1: Pyridine C
C

+ 5H2 C-C-C-C and C-C-C + NH3

4.1.2.2: Quinoline

+ 4H2 + NH3

4.1.2.3: Pyrrole
C

+ 4H2 C-C-C-C and C-C-C + NH3

4.1.3: Reactions of olefins saturation:

4.1.3.1: Linear olefins

C-C-C-C=C-C-C + H2 C-C-C-C-C-C-C

4.1.3.2: Cyclic olefins (Having two double bonds)

+ 2H2
4.1.4: Reaction of Aromatic Saturation

+ 3H2

4.1.5: Reactions of Halide removal:

C-C-C-Cl C-C-C

+ H2 + HCl

HCl + NH3 NH4Cl

4.2: Material Balance Sheet along with Schematic

Diagram
See the very next page.
 F-4 F-17
Start

F-16
Start

E-4 F-5 F-18 E-10

E-9
F-6 F-8

F-15
END

E-5 F-13

E-3
F-7

Start

F-3 F-9 F-12 E-8

F-11 F-14
END

E-2
E-7
F-22
END
F-10 E-6

F-2

F-19 E-11
F-24
END

F-1
Start
F-20 F-23
END
E-1 E-12

Figure 1: Schematic Diagram along with the complete material Balance sheet.
Table 11: Material balance sheet (All values are in kg/hr)
Components F-4 F-6 F-8 F-9 F-11 F-13 F-14 F-15 F-16 F-18 F-19 F-20 F-22 F-23 F-24

Mercaptans --- --- 651.03 --- --- --- --- --- --- --- --- --- --- --- ---

Sulphide --- --- 651.03 --- --- --- --- --- --- --- --- --- --- --- ---

Disulphide --- --- 651.03 --- --- --- --- --- --- --- --- --- --- --- ---

Cyclic Sulphide --- --- 651.03 --- --- --- --- --- --- --- --- --- --- --- ---

Thiophene --- --- 651.03 --- --- --- --- --- --- --- --- --- --- --- ---

Pyridine --- --- 1910.3 --- --- --- --- --- --- --- --- --- --- --- ---

Quinoline --- --- 1910.3 --- --- --- --- --- --- --- --- --- --- --- ---

Pyrrole --- --- 1910.3 --- --- --- --- --- --- --- --- --- --- --- ---

Linear Olefins --- --- 4584.7 --- --- --- --- --- --- --- --- --- --- --- ---

Cyclic Olefins --- --- 4584.7 --- --- --- --- --- --- --- --- --- --- --- ---

Aromatics --- --- 29800 --- --- --- --- --- --- --- --- --- --- --- ---

Phenol --- --- 29800 --- --- --- --- --- --- --- --- --- --- --- ---

Halides --- --- 5731 --- --- --- --- --- --- --- --- --- --- --- ---

H2 5879 8818 --- 2939.5 2939.5 2939.5 --- --- --- 2939.5 --- --- --- --- ---

H2 S --- --- --- 1369.7 1164.4 1152.7 11.643 1152.7 --- --- 205.47 --- 205.5 --- ---

NH3 --- --- --- 517 465.3 --- 465.3 --- --- --- 51.7 --- 51.7 --- ---

HCl --- --- --- --- --- --- --- --- --- --- --- --- --- --- ---

NH4Cl --- --- --- 1984.2 1785.8 --- 1785.8 --- --- --- 198.42 19.842 178.6 2.976 16.864

C2 --- 13.6 --- 754.2 754.2 22.63 731.6 9.05 --- 13.6 --- --- --- --- ---

C4 --- 5.313 --- 2951.9 2656.7 26.57 2630.1 21.3 --- 5.313 295.2 --- --- --- ---

C5+ --- --- 145749 221832 221.9 --- 221.83 --- --- --- 221610 220502 220393 220.53

H2 O --- --- --- 5706 285.3 --- 285.3 --- --- --- 5420.7 1084.2 4336.6 108.41 975.7

DAE 20% solution --- --- --- --- --- --- --- 19211 19211 --- --- --- --- --- ---
ENERGY BALANCE
 Chapter # 05

5: Energy Balance .

5.1: Introduction:
. . As with mass, energy can be considered to be separately conserved in all but nuclear
. . . . . . . . . . . . . .

. process. The conservation of energy, however differ from that of mass in that energy can be
. . . . . . . . . . . . . . . . .

. generated (or consumed ) in a chemical process. Material can change form, new molecular
. . . . . . . . . . . .

. species can be formed by chemical process, but total mass flow into a process unit must be
. . . . . . . . . . . . . . . . .

. equal to flow out at the steady state. The same is not true of energy. The total enthalpy of
. . . . . . . . . . . . . . . . . . .

. outlet streams will not equal to that of inlet streams if energy is generated or consumed in
. . . . . . . . . . . . . . . . .

. the process; such as that due to heat of reaction . Energy can exist in several forms: heat,
. . . . . . . . . . . . . . . . . . . .

. Mechanical energy, electrical energy, and these are the total energy that is conserved. In
. . . . . . . . . . . . . . . .

. process design, energy balance are made to determine the energy requirements of the
. . . . . . . . . . . . .

. process: heating, cooling and power required. In plant operation, energy balance (energy
. . . . . . . . . . . . . . . .

. audit) on the plant will show the pattern of the energy usage, suggest areas for conservation
. . . . . . . . . . . . . . . . .

. and savings.
.
5.2: Conservation of Energy:
. As for material, a general equation can be written for the conservation of energy:
. . . . . . . . . . . . . .

Energy out = energy in + generation consumption accumulation

. It is the statement of first law of thermodynamics . An energy balance can be written for any
. . . . . . . . . . . . . . . . .

. process step. Chemical reaction will evolve energy

. . . . . . . . (exothermic) or consume energy
. . . . . .

(endothermic). For steady state processes, the accumulation of both mass and energy will be
. . . . . . . . . . . . . . . .

. zero. Energy can exist in many forms and this, to some extent, makes an energy balance
. . . . . . . . . . . . . . . . .

. more complex than material balance.

. . . .

In our project we are using the steady state energy balance i.e

Amount of heat in = Amount of heat out

As we are using the relation given below for the calculation of heat

Where

Q = Amount of heat

m = mass

CP = Specific heat capacity

T = Given Temperature Reference temperature

5.3: Forms of Energy:

5.3.1: Potential energy:

. Energy possess by the body due to its position relative to datum is known as potential energy
. . . . . . . . . . . . . . . .

. of the body. Mathematically it is expressed as

.. . . . . . .

Where
h = height above some arbitrary datum, m
g = gravitational acceleration (9.8 m/s2)
m = mass of the body
5.3.2: Kinetin energy:
. Energy possessed by the the body due to motion is known as kinetic energy of the body.
. . . . . . . . . . . . . . . . .

. Mathematically it is defined as . . . .

Where
u = velocity, m/s
m= mass of the body.

5.3.3: Internal energy:

. The energy associated with molecular motion is known as internal energy. The temperature
. . . . . . . . . . . . .

. T of the material is a measure of its internal energy U.

. . . . . . . . . . .

U = f(T)

5.3.4: Work:
. Work is done when a force acts through a distance. Mathematically it is defined as
. . . . . . . . . . . . . .

Where
F = force
D = Distance covered

5.3.5: Heat:
. Energy is transferred either as heat or work. A system does not contain Heat but the
. . . . . . . . . . . . . . . . . .

. transfer of heat or work to a system changes its internal energy. Heat taken in by a system
. . . . . . . . . . . . . . . . . .

. from its surrounding is conventionally taken as positive and that given out as negative.
. . . . . . . . . . . . . .

5.3.6: Electrical energy:

. Electrical and mechanical forms of energy are included in the work term in an energy
. . . . . . . . . . . . . . .

. balance. Electrical energy will only be significant in an energy balance on electrochemical

. . . . . . . . . . . . .

. processes.

5.4: Energy Balance Sheet along with Schematic Diagram

See the next page.
 F-4 F-17
Start

F-16
Start

E-4 F-5 F-18 E-10

E-9
F-6 F-8

F-15
END

E-5 F-13

E-3
F-7

Start

F-3 F-9 F-12 E-8

F-11 F-14
END

E-2
E-7
F-22
END
F-10 E-6

F-2

F-19 E-11
F-24
END

F-1
Start
F-20 F-23
END
E-1 E-12

Figure 2:Schematic Diagram along with the complete energy Balance sheet.
Table 12: Energy Balance Sheet ( All values are in kJ/hr).
Equipment Furnace (E-3) Reactor (E-5) Absorber (E-9) Heat exchanger (E-2) Stripper (E-11)

Components Qin Qout Qin Qout Qin Qout Qin Qout Qin Qout

H2 3152590.155 17872260.64 17872260.64 5957420.21 1721358.31 1721358.31 --- --- --- ---

H2 S --- --- --- 1373099.68 48412.47 48412.47 --- --- 20578.67 23786.6

NH3 --- --- --- 378109.478 --- --- --- --- 378109.478 368989.381

NH4Cl --- --- --- 1073662.19 --- --- --- --- 1073662.19 1073662.19

C2 --- --- --- 324917.973 1665.27 1665.27 --- --- --- ---

C4 --- --- --- 5467268.24 193 1955.32 --- --- 5060358.5 5130398.7

C5+ --- --- --- 224587604 --- --- --- --- 224587604 237898678

H2 O --- --- --- 6557940.55 --- --- --- --- 6557940.55 6557940.55

Raw Diesel 88829376.25 260757201.3 260757201.3 --- --- --- 38511833 80232985 --- ---

Desulfurized
--- --- --- --- --- --- 329586983 287865831 --- ---
Diesel

DEA 20% --- --- --- --- 2689582 2459046.4 --- --- --- ---

Fuel (CH4) + Air 209758906.9 --- --- --- --- --- --- --- --- ---

Flue Gases --- 231117771 --- --- --- --- --- --- --- ---

Steam --- --- --- --- --- --- --- --- 154342.6 ---
EQUIPMENT DESIGN
 Chapter # 06

6: Equipment Design
.

6.1: Reactor

6.1.1: Importance of Reactor in Hydrodesulfurization Unit

. Catalytic hydrodesulfurization process brings about change in sulfur and nitrogen contents of
. . . . . . . . . . .

. diesel oil by hydro - desulphurization of the sulfur compounds and hydro - denitrogenation of
. . . . . . . . . . . . . .

. nitrogen compounds in presence of Ni/ Mo catalyst and simultaneously hydrogenating the

. . . . . . . . . . . .

. aromatics by the hydrogenation sites of the catalyst, so that the cetane number of the diesel
. . . . . . . . . . . . . . . .

. fuel is increased and it becomes more environment friendly. Thus, the reactor is the
. . . . . . . . . . . . . . .

. indispensable component in the hydrodesulfurization unit. . . . . .

6.1.2: Selection of the Reactor

. For hydrodesulfurization, usually two types of reactors are employed, each having its own
. . . . . . . . . . . . . .

. merits and demerits;. . .

a) Trickle bed reactor

. . .

b) Ebullated bed (slurry) reactor

6.1.2.1: Trickle Bed Reactors (1)

6.1.2.1.1: Advantages
a) Flow is close to plug flow, allowing high conversion to be achieved in a single
. . . . . . . . . . . . . . . . .

. reactor. . .

b) Liquid- to- solid ratio is small, minimizing the homogeneous side reactions if possible.
. . . . . . . . . . . . . . . . .

c) Liquid flows as a film, thus offering very small resistance to the diffusion of the
. . . . . . . . . . . . . . . .

. gaseous reactant to the catalyst surface. . . .. . .

d) Flooding is not a problem

. . . .

e) Pressure drop is lower than in cocurrent- upflow and countercurrent - flow reactors.
. . . . . . . . . . . . . ..

f) If temperature rise is significant, it may be controlled by recycling the liquid product

. . . . . . . . . . . . . . .

. or by the addition of the quenches to the side of the reactor. The recycle of the liquid
. . . . . . . . . . . . . . . . . .

. would cause the reactor to behave more like a CSTR; hence, recycling will not be
. . . . . . . . . . . . . . . .

. possible when high conversions are desired. . . . . .

g) Can be operated as a partially or completely vapor- phase reactor. A trickle bed

. . . . . . . . . . . . . . . .

. reactor minimized the energy costs associated with reactant vaporization.

. . . . . . . .

h) Lower pressure drop will allow an essentially uniform partial pressure of reactant
. . . . . . . . . . . .

. across the length of the reactor. . . . . .

i) In the commercial reactor, uniform distribution of gas and liquid are achieved. The
. . . . . . . . . . . . . .

. catalyst is uniformly and effectively wetted by the liquid. . . . . . . .

6.1.2.1.2: Disadvantages
a) Poor radial mixing of heat.
. . . . .

b) At low liquid flow rates, flow mal distributions such as channeling, bypassing and
. . . . . . . . . . . . . . .

. incomplete catalyst wetting may occur. This adversely affects the reactor . . . . . . . . . .

. performance.
c) The catalyst particles cannot be very small. The intra-particle diffusion effects can be
. . . . . . . . . . . . . .

.. significant. The catalyst pore- mouth plugging can cause rapid deactivation. . . . . . . . . . . ..

6.1.2.2: Slurry Bed Reactors:

6.1.2.2.1: Advantages
a) High heat capacity providing good temperature control.
. . . . . . ..

b) Potentially high reaction rate per unit volume of reactor if the catalyst is highly
. . . . . . . . . . . . . .

. active.
 c) Ease of heat recovery.
. . . . .

d) Can be easily used as a batch (slurry) reactor or continuous flow (fluidized-bed)

. . . . . . . . . . . . . . .

reactor.
e) The catalyst can be easily removed and replaced if it decays rapidly. Steady- state
. . . . . . . . . . . . . . . .

. operation can be achieved even in a rapidly decaying system. . . . . . . . . .

f) It allows the use of very fine catalyst particles, which can give an effectiveness factor
. . . . . . . . . . . . . . . .

. approaching unity. This is especially important if diffusion limitations cause rapid . . . . . . . . . . .

. catalytic deactivation or poorer selectively. . . .

g) It allows three phase gas- liquid- solid reactions to operate in the presence of a solid
. . . . . . . . . . . . . . . . .

. catalyst without plugging of the reactor. . . . . .

h) It allows more flexibility for mixing, e. g., agitated slurry reactor.

. . . . . . . . . . . . . .

6.1.2.2.2: Disadvantages
a) High degree of axial mixing reduces conversion. High degree of conversion is
. . . . . . . . . . . . .

. obtained only by staging several reactors in series. . . . . . . .

b) Catalyst separation from the product mixture by filtration may pose problems of
. . . . . . . . . . . .

. plugging the filters. . .

c) The cost of separation of catalyst and product mixture may be very high.
. . . . . . . . . . . .. .

d) The high ratio of liquid to solid may allow homogeneous side reactions to become
. . . . . . . . . . . . . .

. important, if they are possible. . . . . .

e) High liquid hold up may cause the liquid- phase diffusional resistance to the gaseous
. . . . . . . . . . . . . . .

. reactant to be an important factor affecting the global rate of reaction.

. . . . . . . . . . .

Table 13: Comparison of Trickle bed reactor And Ebullated bed reactor
Characteristics Trickle Bed Reactor Ebullated Bed Reactor
Channeling at low flow rates
No liquid flow
Liquid flow of fluid may occur resulting
maldistributions are there.
in flow maldistributions.
High conversion can be
achieved owing to plug flow Conversion is less because of
Conversion
behavior of fluid in the axial mixing.
reactor
Mixing Poor radial mixing. Good mixing is achieved.
Relatively difficult, usually
Heat control is easier owing
Heat control provided by additional
to fluidized system.
quench streams.
Liquid/solid ratio Ratio is less. Ratio is quite higher.
Partial wetting is a serious
Catalyst wetting Complete wetting is possible.
shortcoming.
Separation is required which
Not required as fixed beds of
Catalyst separation makes handling difficult and
catalysts are used.
costly.
Pressure drop It is higher. It is low or medium.
Not a problem, as catalyst
Catalyst attrition It may be a problem.
particles are fixed.
Usually employed for
Used where Gas/liquid ratio
Application operations where high
is very high.
liquid/gas ratio is required.
3
Maximum volume 300 m 50 m3
Maximum working
Very high pressures possible. 10 MPa
pressure
Investment costs Low. High.
Operating costs Low. High.

As 445 SCF of hydrogen is required per barrel of oil, so the reactor flow regime is trickle
flow regime and Trickle flow reactor is selected for the service

6.1.2.3: Up-Flow versus Down-Flow Co-Current Fixed Bed Reactors (2)

a) Pressure drop is larger in an up- flow reactor.
. . . . . . . . . .

b) Better mixing in an up - flow reactor. This may give better heat transfer, but larger
. . . . . . . . . . . . . . . . . .

. axial mixing would give poorer conversion in an up- flow reactor.

. . . . . . . . . . .

c) At low flow rates up- flow behaves like a bubble column, i. e., gas as a dispersed
. . . . . . . . . . . . . . . . . . . . . .

. phase, liquid as a continuous phase. In down- flow trickle- bed operations, gas is a
. . . . . . . . . . . . . . . . . . .

. continuous phase and liquid flows as a film. . . . . . . ..

d) High pressure drop in an up- flow reactor would cause significant drop in the partial
. . . . . . . . . . . . . . . .

. pressure of the reactant across the length of the reactor.

. . . . . . . . .

e) Under similar flow conditions, a higher gas- liquid mass transfer coefficient is
. . . . . . . . . . . . . .

. obtained in an up- flow operation than in a down- flow operation.

. . . . . . . . . . . . .

f) High liquid hold up and liquid- to- solid ratio in an up- flow reactor . High liquid hold
. . . . . . . . . . . . . . . . . . . . .

. up will offer more liquid- phase resistance to the mass transfer of the gaseous reactant
. . . . . . . . . . . . . . .
 . to the catalyst surface. High liquid- to- solid ratio will give more importance to the
. . . . . . . . . . . . . . . . .

. role of possible homogeneous reactions. . . . . .

g) At low liquid flow rates, up- flow will provide better distribution of liquid and, thus,
. . . . . . . . . . . . . . . . . . .

. in many cases, better performance of the reactor than the down- flow reactor under
. . . . . . . . . . . . . . .

. similar operating conditions. . . . .

h) If reaction is rapid and highly exothermic, heat transfer between liquid and solid is
. . . . . . . . . . . . . .

more effective in an up- flow reactor. . . . . . . .

i) In an up- flow reactor, the catalyst must be kept in place by suitable mechanical
. . . . . . . . . . . . . . . . .

. methods; otherwise the bed will be fluidized. In a down- flow reactor, the catalyst is . . . . . . . . . . . . . . . . . .

. held in place tightly by the flow. This may cause undesired cementation of the soft
. . . . . . . . . . . . . . .

. catalyst particles. ..

j) In an up- flow reactor, the catalyst particles are more likely to fill completely with the
. . . . . . . . . . . . . . . . .

. liquid than in a down- flow reactor. The catalyst effectiveness factor is lower when
. . . . . . . . . . . . . . .

. the catalyst pores are completely filled with liquid compared to the case when they
. . . . . . . . . . . . .

. are only partially filed with the liquid.

. . . . . .

k) Better sweeping of the catalyst by liquid in an up- flow reactor may sometimes give
. . . . . . . . . . . . . . . . . .

. better aging of the catalyst. If a solid reactant is used, then an up- flow would cause
. . . . . . . . . . . . . . . . . . .

. less solids plugging problem than the down- flow operation.

.. . . . . . . . .

l) In an up-flow reactor, flooding may be a problem.

6.1.2.4: Co-Current Operation versus Counter-Current Operation:

.

a) The relative direction of flow of the liquid and gaseous phases is important.
. . . . . . . . . . . . .

b) Counter- current operation is mostly preferred for the gas - liquid- solid inert (GLSI)
. . . . . . . . . . . . . . .

. reactors. In these units, the solid is used as a packing to increase the contact of the . . . . . . . . . . . . . . . . . .

. liquid and gas phases, but it remains inert in the reaction. . . . . . . . . . . .

c) Co current mode of operation is best suited for the (GLSC) gas liquid- solid catalytic
. . . . . . . . . . . . . . . . . .

. reactors where the solid acts as a catalyst . . . . . . .

6.1.3: Design of the Reactor

. The design of the Trickle bed reactor is the application of various fields of Chemical
. . . . . . . . . . . . . .

. engineering, along with some chemical principles which do govern the nature of the process
. . . . . . . . . . . . .

. underway in a Trickle bed reactor. For design purposes, following important aspects are to
. . . . . . . . . . . . . . .

. be evaluated and their functioning understood to have a design which accomplishes the
. . . . . . . . . . . .

. purpose of installment of reactor fairly.

. . . . .
 a) Basic understanding of the hydrodesulfurization chemistry.
. . . . . .

b) Catalyst structure and properties.

. . . .

c) Estimation of product yield and Hydrogen required.

. . . . . . .

d) Thermodynamic parameters. . . .

e) Calculation of Quench gas required.

. . . . .

f) Residence time required for the reaction accomplishment.

. . . . . . .

g) Volume of reactor vessel. . . . .

h) Hydrodynamics of the reactor. . . .

i) Mechanical design. . . .

6.1.3.1: Thermodynamic Parameters

. The important . thermodynamic
. .parameters .that .significantly influence . . reactor
. performance are .

a) Temperature
b) Pressure

6.1.3.1.1: Temperature
. The hydrodesulfurization reactions are favored when the system temperature is about 325-
. . . . . . . . . . . .

. 355 C. However, the temperature of operation should not be as high as 420 C because at a
. . . . . . . . . . . . . . . . . . . . .

. temperature that much high thermal cracking starts along with catalytic cracking which . . . . . . . . . . .

. results in much coke formation which chokes the catalyst particles necessitating regeneration
. . . . . . . . . . .

. much before it is needed. Thus the catalyst aging properties are adversely affected and
. . . . . . . . . . . . . .

. operation has to be dismantled quite frequently if too high a temperature is maintained. Thus
. . . . . . . . . . . . . . .

. the optimum temperature is between 320- 400 C. In this process the operation is non-
. . . . . . . . . . . . . . . . . .

. isothermal and temperature inside varies from 325 C at the top to 355 C at the bottom. The
. . . . . . . . . . . . . . . . . . . .

. design temperature is usually the maximum working temperature possible in the reactor.
. . . . . . . . . . . .

. Allowing a provision of 10%, the design temperature is chosen to be 385 C.

. . . . . . . . . . . . .

6.1.3.1.2: Pressure
. The hydrodesulfurization reactions are heterogeneous in nature so pressure increases always
. . . . . . . . .

. favor better conversion. It is stated that pressure in excess of 1000 psi is quite suitable for
. . . . . . . . . . . . . . . . .

. smooth operation of this process, the upper limit being dictated by a compromise between
. . . . . . . . . . . . . .

. conversion and wall thickness cost. The pressure for Catalytic Hydrodesulfurization is
. . . . . . . . . . .

. chosen as 60 kg/ cm2. Allowing a provision of 15%, the design pressure is taken as 69
. . . . . . . . . . . . . . . . . . .

. kg/cm2.
.
6.1.3.2: Calculation of Quench Gas Required
. In the present case, the primary purpose of adding quench gas is to maintain the hydrogen
. . . . . . . . . . . . . . . .

. partial pressure inside the reactor and the secondary purpose is to maintain the temperature
. . . . . . . . . . . . .

. at about 325-355 C.
.

6.1.3.3: Volume of the Reactor (3)

Residence time of the reactor is reciprocal of the Liquid Hourly Space Velocity (hr-1). LHSV
can also be given by the formula

LHSV is calculated from the kinetics of a reaction. Here the primary reaction is
hydrodesulfurization and it must be at least 86.3 % completed. The kinetic equation is (4)

Where

k (4) = reaction rate constant = 97.65

n = order of reaction = (1.5-1.7), we will take 1.5.

Cf = sulfur content in feed = 0.0056 = 0.56(weight %)

Cp = sulfur content in product = 0.00029 = 0.029 (weight %)

Putting all the values in the above equation gives

LHSV = 1.3096hr-1

Since space time is the inverse of space velocity, therefore,

= 0.763575hr = 45.81451minutes.

The volume of the catalyst comes out to be 324m3. Using catalyst porosity equal to 0.5,
volume of the catalyst bed is 648.033 m3.
Usually, 2 to 5 catalyst beds are employed for hydrodesulfurization. Since the length of a
catalyst bed cant exceed a particular limit to avoid channeling, so five catalyst beds with two
gas quenches are used each having a volume of 129.60 m3.

One major problem that is encountered with trickle bed reactor is the partial wetting of the
catalyst which makes some of the catalyst surface ineffective. This is shown in the
accompanying diagram.

Plug flow

Many catalyst particles

get wetted partially

Figure 3: Partial wetting of the catalyst

To account for this maldistribution of the liquid Catalyst Effectiveness Factor is used. Here a
Catalyst Effectiveness Factor of 0.9 is assumed. Then

Corrected volume of catalyst bed = 144 m3

Assuming that 80% of the bed is occupied by catalyst and the rest is spare for distributors,
quench boxes and clearances at the top and bottom, so volume of the reactor

Final Volume of the reactor after applying all factors = 900 m3

6.1.3.4: Length and Diameter of Reactor

Usually, the L/D ratio used for designing a Trickle bed reactor is 10. Using the same ratio
Thus,

Volume of the reactor = ( )

( )*Volume of the reactor =

d=

d = 4.85m and as (L/d=10) L= 48.5m

Length of the reactor required = 48.5 m.

Diameter of the reactor required = 4.85 m.

6.1.3.5: Hydrodynamics of the reactor:

Gas superficial velocity = 0.0529 m/s Liquid superficial velocity = 0.24 m/s

At such low velocities, Trickle flow regime is the dominant one as can be seen

Figure 4: Hydrodynamics of the reactor i.e. flow regimes

6.1.3.6: Pressure drop across the Reactor (5)
For Trickle bed reactors, where Trickle flow regime prevails, the pressure drop in the catalyst
bed is calculated as follows

1. The liquid based Reynolds number is given by

2. An empirical factor is determined as a function of Reynolds number.

3. The modified Lockhart-Martinelli ratio is determined as

4. The Krischer-Kast hydraulic diameter is calculated.

5. Friction factor is calculated as

6. The pressure drop per unit length of the catalyst bed is given by
6.1.3.6.1: Calculations for Pressure drop
The values used in the pressure drop calculations are

Liquid density = L = 842.7 kg/m3

Liquid viscosity = L = 0.082 cP = 0.000082 Pa.sec

Particle size = dp = 0.003 m

Inside diameter of reactor = Di = 4.85 m

Superficial liquid velocity at inlet = UL = 0.24m/s

Superficial gas velocity at inlet = UG = 0.0529 m/s

Gas density = G = 37.01 kg/m3

Bed porosity = = 0.5

C = 200 D = 85

m = 1.2 n = -0.5

The results of the calculations are

Rel= 4765

= 69.030

XG= 0.0584

dK=0.001969 m

f= 1107.877

And

Pressure drop = 15.1944k Pa/m

But Length of each bed 9.7 m

So Pressure drop per bed = = 147.38 kPag

Total pressure drop = 736.92 kPag

6.1.3.7: Mechanical Design of the Reactor
Mechanical design covers the following essentials of the Reactor;

a) Material of construction.
b) Wall Thickness.
c) Column internals
d) They include
e) Catalyst bed support plates.
f) Feed distributors.
g) Liquid redistributors.
h) Quench gas distributors.
i) Wall wipers.
j) Type of head.
k) Type of supports.

6.1.3.7.1: Material of construction

Since the reactor is a high temperature and high pressure reactor, so the material of
construction needs be tolerant these severe conditions. The selected material of construction
is SS-347 because of the following properties;

a) Better tensile strength and stiffness.

b) Lesser creep rate.
c) Not much affected by temperature rise.
d) Resistant to corrosion.
e) Relatively cheaper.

6.1.3.7.2: Wall thickness

The wall thickness required is calculated by the formula (6);

Where P = operating pressure, N/mm2

ri = reactor radius, mm = (4850/2)mm

S = Design stress, N/mm2 = 230 N/mm2

 Ej = joint efficiency =1

C = corrosion allowance, mm =2 mm

Wall thickness = 64 mm.

6.1.3.7.3: Wall Thinness criteria

The wall is assumed to be very thin compared to the other dimensions of the vessel. If the
thickness is t and a characteristic dimension is R (for example, the radius of the cylinder or
sphere) we assume that

t/R << 1, or R/t >> 1

Usually

R/t > 10. As a result, we may assume that the stresses are uniform across the wall.

6.1.3.8: Column Internals

6.1.3.8.1: Catalyst bed support plates

The support plates selected for the desired operation is Multi beam support plates
because of the following characteristics relative to others;

Better load bearing ability as compared to plastic packing support plates.

Can withstand high temperature there in the reactor.
Have very low Pressure drop compared to perforated ceramic plates.
Not vulnerable to sagging in the middle of the plates.

6.1.3.8.2: Feed distributors

Feed distribution system used is feed distributing support plate that uses orifice deck
above the catalyst bed. Distribution points used per square feet are 10. This assembly
provides the following advantages;

More uniform feed distribution in the bed.

Wetted area compared to dry area in the column is minimum.
6.1.3.8.3: Liquid redistributors
With the multi beam support plates the liquid redistribution is mandatory. To get the
proper mixing of liquid on the next bed inlet and uniform flow of liquid to the next bed,
orifice deck liquid redistributors are used. 10 orifices per sq. ft. are used.

6.1.3.8.4: Quench gas distributors

For a vessel with a lesser diameter like the one being considered, vapor
maldistribution can easily be avoided by using gas orifices in each quench box where it mixes
with the incoming gas and liquid to get there temperature down. 16 distribution points per sq.
ft. are used.

6.1.3.8.5: Wall wipers

With a column having diameter of 1.06 m, approximately 10% of feed may flow down the
wall which needs be wiped away from the wall to make it available at the outlet of mass
transfer zone. For this purpose, Rosette wall wiper is used.

6.1.3.8.6: Liquid collector

A liquid collector is installed at the base of the vessel to get all the effluent directed to the
separation equipments located downstream.

6.1.3.8.7: Type of head

The type of head used with Trickle bed reactor designed for a pressure of approximately 52
bars is hemispherical head. Hemispherical head is used as it is most suitable for high pressure
duties. Torispherical and Ellipsoidal heads are not used because the pressure requirement in
the reactor is quite high.

It can be seen by examination of below given equations

That for equal stress in the cylindrical section and hemispherical head of a vessel the
thickness of the head need only be half that of the cylinder. However, as the dilation of the
two parts would then be different, discontinuity stresses would be set up at the head and
cylinder junction. For no difference in dilation between the two parts (equal diametrical
strain) it can be shown that for steels (Poissons ratio D = 0.3) the ratio of the hemispherical
head thickness to cylinder thickness should be 7/17. However, the stress in the head would
then be greater than that in the cylindrical section; and the optimum thickness ratio is
normally taken as 0.6; see Brownell and Young (1959).

6.1.3.8.8: Type of supports

Since L/D ratio is quite high for the reactor designed, so conical skirt supports are used for
the reactor because they can support heavy weight and tall equipments well.

6.1.4: Specification Sheet for Reactor

Table 14: Reactor specification sheet

Equipment Trickle-Bed Reactor

Hydro-desulfurization and hydro-

Function
denitrogenation of diesel feed

Height (m) 48.5 m

Inside Diameter (m) 4.85m

Wall Thickness (m) 6.4cm

No. of Gas Quenches 2

No. of Catalyst Beds 5

Design Temperature (C) 385

Operating Temperature (C) 325-355

Design Pressure (kg/cm2) 60

Operating Pressure (kg/cm2) 52

Catalyst Ni-Mo/Al2O3 containing Boron

Catalyst pore Size (mm) 3mm cylinders

Material of Construction SS-347

Head Hemispherical

Support Conical skirt

6.2: Heat Exchanger Design

6.2.1: Fluid Allocation

According to the rule of thumb high-pressure fluid should be kept on the tube side. This
usually minimizes exchanger cost. The smaller tube diameter has a higher pressure rating for
the same metal thickness compared to the larger diameter shell. Desulfurized diesel is at high
temperature and high pressure so we will keep it on tube side to minimize energy losses.

Shell Side: Cold Fluid, Tube Side: Hot Fluid

6.2.2: Design Inputs:

Fluid on Shell side (Cold Fluid) => Raw diesel

Fluid on Tube side (Hot Fluid) => Desulfurized diesel

6.2.3: Available Data and Property estimation

Table 15: Available date for heat exchanger design

Hot Fluid Cold Fluid

Property /Quantity
Symbol Value Symbol Value

Mass flow rate (lb/hr) W 523720.736 W 504321.62

Inlet Temperature (oF) T1 671 t1 140

Outlet Temperature (oF) T2 ? t2 257

Average Temperature (oF) Tavg 630.5 tavg 198.5

Specific Heat Capacity (Btu/lboF)

C 0.77 C 0.53
(7)

Specific Gravity (7) S 0.83 S 0.86

Allowable pressure drop (psi) [17] Pt 10 Ps 10

Viscosity (lb/ft.hr) (7) t 0.726 s 3.025
o
API (9) 37 33

6.2.4: Calculations:-

6.2.4.1: Heat Balance

Raw Diesel QC = w*c*(t2-t1) => QC = 504321.62*0.53*(257-140)

QC = 31272983.66 Btu/hr

Desulfurized oil QH = W*C*(T1-T2) => QH = 523720.736*0.77*(671-T2)

QC = QH = 31272983.66 Btu/hr

T2 = 593.45oF

6.2.4.2: True Temperature Difference

Table 16: Temperature differences at two ends of the exchangers

Hot Fluid Cold Fluid Difference

671 High Temperature 257 414

593.45 Low Temperature 140 453.45

77.55 Difference 117 39.45

6.2.4.3: LMTD:

= 433.42oF

Here

6.2.4.4: LMTD correction factor (FT)

 FT = 0.98

At these values of R & S, FT becomes equal to 0.98 for 1-2 Heat exchangers (10).

6.2.4.5: True temperature difference (t)

o
F

6.2.4.6: Caloric Temperature

Following formulas are used to find the caloric temperature of hot and cold streams
respectively

First of all we have to find out FC which is correction factor for caloric temperature. It can be

estimate from graph between dimensionless parameter KC and . Estimate KC = for

both streams and take larger value of KC because it will act as a controlling factor (11).

In our case

KC for Desulfurized diesel = 0.15

KC for Raw diesel = 0.32

So we will take KC = 0.32.

Now from graph between Kc and (7)

FC = 0.48

Now using this value of Fc

TC = 630.67oF

&

tC = 196.16 oF
6.2.4.7: Trail value of UD (7)
Select a value of UD between 40 -70 (Btu/hr.oF.ft2). Select a value of UD near the upper limit
because it will minimize the area requirement for that particular heat exchanger. (12)
UD= 60

6.2.4.8: Provisional Area

6.2.4.9: Selection of tube

Normally this selection is made on the basis of availability of tubes in the inventory storage.
Here we select the tube of 3/4inch OD and 16 BWG having 16ft length.

6.2.4.10: No. of tubes

Surface per linear ft (7) = a= 0.1963ft2/linear ft

6.2.4.11: Shell Diameter from tube count

Assume two tube passes as the large amount of flow will cause abnormal pressure drop if we
increase the number of tube side passes. (13)

For

n = 2 Nt = 390.69 OD = 3/4inch Pt= 1inch square tube pitch

The nearest tube count comes out to be

Nt= 394 tubes with 25inch internal diameter of the shell. (7)

Ds= 25 inch

6.2.4.12: Corrected Coefficient UD

New area = A = Nt*L*a=394*16*0.1963 = 1237.47ft2
6.2.4.13: Shell side and tube side film coefficients and pressure drop
First we will ensure calculations on tube side then we will proceed to the shell side

Cold Fluid Shell side Hot Fluid Tube Side

(i) Flow area (i) Flow area at (7)

Flow area per tube =at=0.302in2

N *a 394*0.302
t t
at=144*n = =0.4131ft2
144*2

(ii) Mass velocity

Baffle spacing (max) = B = IDs = 25inch
W 523720.736 lb
G= = =1267620
at 0.4131 hrft2

(iii) At Tc=630.67oF
(ii) Mass velocity

= 0.726 (7)

IDt = 0.62/12 = 0.0517ft

De = 0.95112in (iv) JH factor (7)

De= 0.0792ft

At Ret = 90269

JH= 200

From (7)
(v) For = 0.3cp & 37oAPI
JH= 60 = 0.12

For
= 464.21Btu/hr.ft2.oF
= 1.25cp and 33oAPI

Btu/hr.ft2.oF

Neglecting viscosity correction factor

Btu/hr.ft2.oF

Neglecting viscosity correction factor hio = 383.75 Btu/hr ft2 oF

(vi) Pressure drop on tube side

ho= Btu/hr.ft2.oF Ret= 90269

Pressure drop on shell side. S= 0.83

Res= 12168.85 f = 0.00015 (7)

S= 0.86

Gs= 464782.805lb/ft2 hr

De= 0.0792 ft
This pressure drop is within the limit of maximum
allowable pressure drop. [18]

Ds= 2.0833 ft
From graph (7)

f=0.002

6.3: Furnace (14)

Furnace is equipment in which chemical energy of fuel or electrical energy is converted into
heat which is then used to raise the temperature of material, called the burden or stock, placed
with in the furnace.

6.3.1: Classification of Furnace

Furnace can be classified on many bases, e.g.

a) Based on operations.
b) Based on the heat source.
c) Based on type of fuel used.
d) Based on draft control.

6.3.2: Parts of Furnace

a) Burner.
b) Radiant section. Furnace inlet
Furnace outlet
c) Convection section.
d) Breeching section.
e) Stack.
f) Dampers, Louvers.
g) Fans & Blowers.
Figure 5: Furnace (fired heater)
 h) Soot Blowers.
i) Air pre-heater.

6.3.3: Significance of Furnace in Overall Process

According to requirements furnace is placed just before reactor, where the required
temperature for reaction is 325 oC. Although we have used the heat exchangers but still 208
o
C rise in temperature is still needed. By preliminary analysis of the flow sheet we see that
there is no stream available at temperature higher than 325 oC so that heat may be recovered
from it. Therefore we have to use direct heating method. For this purpose furnace has been
used here to increase the temperature of the feed mixture up to 325 oC.

6.3.4: Selection Criteria of Furnace

The selection of a furnace is based upon the following points:

a) The required heat duty

b) Temperature to be achieved
c) Kind of fuel.
d) Firing temperature.
e) Location and infrastructure.
f) Economics is the final factor.
Figure 6: Furnaces Used in Petroleum Refineries

6.3.5: Selection
a) Stills a, b, c are suited for very high duties and required very tall stacks.
b) Still d is used for small heat duties and has a problem of overheating of shield tubes.
c) Still e is used for large capacities but with poor heat distribution.
d) Stills f, g, h are best suited for very low rates of heat absorption.
e) Still j is used for large capacities.
f) Stills i, k are used when there is need to control rate of heat transfer in high range of
temperature i.e. 1000-1500 0F. They are expensive due to large frameworks and
requirement of numerous burners respectively.
6.3.6: Selected Furnace
I have selected still vertical tube cylindrical type furnace, because of high heat duty.

Our conditions are:

a) Heat duty = 209758906.9 kJ/hr.

b) Inlet temperature = 125 oC.
c) Outlet temperature = 325 oC.
We have used 3 furnaces so above duty is divided equally to each

6.3.7: Problems Faced in Industry during Operation

Following are the major problems faced in a fired heater during operations:

a) Scaling, fouling and deposition of coke inside the tubes.

b) Rise of tube skin temperature.
c) Stack gases exit at a very high temperature.
d) Flame impingement.
e) Refractory material damage.
f) Loss of strength of tube material.
g) Maintenance of draft.

6.3.7.1: Solution of these problem

6.3.7.1.1: Pigg Decoking

A method of cleaning tubing in an operating heater: This phenomenon is applicable in the

shutdown period. This polymer Pigg is available in diameters from 16mm ("), to as large as
914mm (36"). These piggs are passed through tubes with water of high flowrate.
The selection of the appropriate Pigg determined by the following factors:

a) The deposit hardness.

b) The extent of coke build-up.
c) The location of the deposits.
d) The specific pipe material.

6.3.8: Methods of Designing

There are several methods:
 a) Method of Lobo and Evans.
b) Method of Wilson, Lobo and Hottel.
c) The Orrok-Hudson Equation.
d) Wohlenberg simplified Method.
I have selected Method of Lobo and Evans

Here we have taken vertical tube cylindrical furnace

6.3.9: Furnace Design Calculation by Method of Lobo and Evans

6.3.9.1: Average radiant heat flux:

First of all we shall assume radiant heat flux. In literature, permissible average radiant rate for
different types of feedstocks are available.

From table 19.2 (15)

For Heating Charge Heater charge heater

Average radiant heat flux= 10,000 Btu/(hr)(ft2 of circumferential tube area)

6.3.9.2: Find Q/Acp:

=2 x Average flux

=2 x 10000

=20,000 Btu/(hr)(ft2 of circumferential tube area)

Where,

Acp = Equivalent cold plane surface (ft2)

= effectiveness factor

Acp =effective cold plane surface (ft2)

Q = heat transferred to cold surface (Btu/hr)

6.3.9.3: Overall exchange factor ()

Assume overall exchange factor. Normally it is in the range of 0.55 to 0.65

Here lets take

 = 0.57

6.3.9.4: Actual heat transfer between hot and cold surfaces:

Q/Acp = 20000/0.57

= 35087.82 (Btu/ hr. ft2)

6.3.9.5: Tube surface temperature (Ts):

It is fixed depending upon the desired temperature of fluid in tubes.

Lets,

Ts = 800 oF

6.3.9.6: Evaluate temperature of the gases leaving the radiant section:

From fig. 19.14 (16)

Tg = 1625 oF

Or by substituting Q/Acp and Ts in the following heat transfer equation

Q/Acp =0.173[(Tg/100) 4-(Ts/100) 4]+7(Tg-Ts)

Where, all the terms have usual meaning as described.

6.3.9.7: Heat balance:

Heat balance is necessary for the solution of heat absorption problem. The heat balance is as
follows:

Q = Qf + Qa + Qr + Qs Qw Qg

Where,

Q = total radiant section duty, (Btu/hr)

Qa =Sensible heat above 60 oF in combustion air, (Btu/hr)

Qf = Heat liberated by fuel, (Btu/hr)

Qr =Sensible heat above 60 oF in recirculated flue gases, (Btu/hr)

 Qs =Sensible heat above 60 oF in steam used for oil atomization,

Qw =Heat loss through furnace walls, (Btu/hr)

Qg =Heat leaving the furnace radiant section in the flue gases,

(Btu/hr)

6.3.9.7.1: Total required heat duty (Q):

Q = 69919635.63 kJ 0.948 Btu

Hr kJ

Q = 66269830.65 Btu/ hr (from overall energy balance)

6.3.9.7.2: QF heat liberated by fuel (Btu/hr)

The Efficiency of furnace () is supposed

= 0.77

so heat liberated by fuel

Q/ = 66269830.65/ 0.77

= 86064715.13 Btu/hr.

6.3.9.7.3: Qa sensible heat above 60 oF in combustion air (Btu/hr)

As we have taken natural gases as fuel which exist naturally and contain fractions of methane
ethane, propane and butane and hydrogen.

L.H.V of Natural gases = 361364.638 Btu / lb.mol.

So amount of fuel consumed (qf) and material balance on fuel:

qf = Qf/L.H.V

= 86064715.13 / 361364.638

= 238.16 lbmole/ hr.

As the composition of Natural Gas is:

Table 17: Composition of natural gas

Components mol %

CH4 90.75

C2H6 5.25

C3H8 1.9

C4H10 0.95

H2 1.15

Reactions Involved:

CH4 + 202 C02 + 2H20

C2H6 + 3.502 2C02 + 3H20

C3H8 + 502 3C02 + 4H20

C4H10 + 6.502 4C02 + 5H20

H2 + 0.5O2 H2O

Table 18: Heat generated through natural gas burning

mol Mol lb mol of O2 CO2 H2O

Components % wt
lb/lb.mol
component Produced(lb.mol) Produced produced

CH4 90.75 16 14.52 216.1302 432.2604 216.1302 432.2604

C2H6 5.25 30 1.575 12.5034 43.7619 25.0068 37.5102

C3H8 1.9 44 0.836 4.52504 22.6252 13.57512 18.10016

C4H10 0.95 58 0.551 2.26252 14.70638 9.05008 11.3126

H2 1.15 2 0.023 2.73884 1.36942 0 2.73884

Total = 17.505 514.7233 263.7622 501.9222

Amount of fuel gas qf = 238.16 x 17.505

 = 4168.99 lbs/ hr

O2 Required = 514.7233 lbmole/hr

Or = 16471.11 lb/hr

Air is in 20% Excess:

Original O2 = 1.2 x 514.7233

= 617.66 lbmole/hr

Air Required = 514.7233 /.23

= 2237.92 lbmoles/hr

Or = 64899.89 lb/hr

20% Excess = 1.2 x 64899.89

= 77879.87 lb/hr

6.3.9.7.4: Sensible heat in combustion air (Qa):

Air Required qa = 77879.87 lb/hr

Air enter at ambient temperature = 77 oF

Enthalpy of air at this temperature Ha = 10.78 Btu/lbs.

Qa = qa x Ha

= 77879.87 x 10.78

= 839545.03 Btu/ hr.

6.3.9.7.5: Heat loss through wall ( Qw) :

Qw = 2% of Qf

= 0.02 x 86064715.13

= 1721294.30 Btu/ hr
6.3.9.7.6: Sensible heat in steam (Qs):
Since it is a gas fuel , no steam is required for atomization , so

qs. = 0 lbmole/hr

Qs = 0 lbmole/ hr

6.3.9.7.7: Heat in the flue gases (Qg):

Qg = Q(N2) +Q(O2) + Q(CO2) +Q(H2O)

O2 Required = 514.7233 lbmole/hr

Or = 16471.11 lb/hr

Air is in 20% Excess:

Original O2 = 1.2 x 514.7233

= 617.66 lb.mols/hr

N2 entered = 617.66 x (0.79/ 0.21)

= 2323.57 lbmole.

N2 leaving =N2 entering

O2 consumed = 514.7233 lbmole.

O2 unconverted = 617.66 514.7233

= 102.9367 lbmoles = O2 leaving

CO2 leaving = 263.7622 lbmole

H2O leaving = 501.9222 lbmole

Table 19: Enthalpies of flue gases at flue gas temperature

ENTHALPY OF COMPONENT AT Tg
COMPONENT OF FLUE GAS
(Btu/ lb.mol.)

N2 11364.7995

O2 12032.04
CO2 17918.5458

H2 O 13907.3642

So,

Q (N2) = 2323.57 x 11364.7995 = 26406907.17 Btu/ hr.

Q (O2) = 102.9367 x 12032.04 = 131590.8119 Btu/ hr.

Q (CO2) = 263.76 x 17918.5458 = 4726194.11 Btu/ hr.

Q (H2O) = 501.922 x 13907.3642 = 6980409.4 Btu/ hr.

Therefore,

Qg = Q(N2) +Q(O2) + Q(CO2) +Q(H2O)

= 38245102.78 Btu/ hr.

So overall heat balance is:

Q = Qf + Qa + Qr + Qs Qw Qg

= 46937863.79 Btu/hr

6.3.9.8: Establish the number and Sizes of tubes:

Fix tube length l = 50 ft

Fix outer diameter of tubes = 5 inch.

= 5/12

= 0.42 ft.

Area of tubes = xDx l

= x (5/12)x 50

= 65.45 ft.2

Heat transferred per tube = Average flux x surface area per tube
 = 10000 x 65.45

= 654500 Btu/ hr.

Number of tubes = total radiant section duty (Q)/ heat transferred per
tube

=46937863.79 / 654500

= 71.7 72 tubes

6.3.9.8.1: Arrangement of the tubes:

Height of furnace = 52 ft

Center to center distance = 8 inch

= 8 /12

= 0.708 ft

Tubes are vertically mounted in a single row along the wall of the cylindrical furnace about
one tube diameter away from wall.

Diameter of furnace (D) = (number of tubes x center to center distance)/

= (72 x 0.708)/ 3.14

= 16.24 ft 17 ft

6.3.9.9: Checking the performance of furnace

6.3.9.9.1: Evaluate effectiveness factor ():

For C-C distance / O.D = 1.6

& Arrangement of tubes is single row when only one is present

From fig 19.11 (17)

= 0.95
6.3.9.9.2: Evaluate equivalent cold plan surface area (Acp):
Acp = (number of tubes)x (length of each tube) x (C-C
distance)

= 2548.8 ft2

So,

Acp = 0.95 x 2548.8

= 2421.36 ft2

6.3.9.9.3: Evaluate the total area of furnace surface (At):

For cylindrical furnace,

At = xD xH

= 2777.16 ft2

6.3.9.9.4: Evaluate effective refractory surface (Ar):

Ar = At - Acp

= 355.80 ft2

6.3.9.9.5: Evaluate (Ar/ Acp):

Ar/ Acp = 0.128 (this would be used to evaluate exchange
factor)

6.3.9.9.6: Evaluate mean beam length (L):

It depends on the dimensions of the furnace & found from any suitable formula from table
19.1 (18)

Here, for cylindrical furnace whose dimensions are like Dx2D

L = 1 x diameter of furnace (D)

= 17 ft

6.3.9.9.7: Evaluate gas emissivity (g):

Evaluate partial pressure of (CO2+ H2O)
At 20% excess air

p(CO2 + H2O) = 0.24 atm. from fig. 1-7 (19)

Calculate pxL:

pxL = p (CO2+ H2O) xL

= 0.24 x 17

= 4.08 atm.ft.

At pxL = 4.08 atm.ft. & Tg = 1625 F

g = 0.53 from fig 1-8 (19)

6.3.9.9.8: Evaluate Overall exchange Factor ():

at g = 0.53

&

Ar/ Acp = 0.128

= 0.53 from fig. 19.15 (20)

6.3.9.9.9: Check flue gas temperature

Check of gas temperature (Tg) required affecting assumed duty on assumed surface)

Calculate Q/Acp using the above calculated value of

= 0.53

Q = 46937863.79 Btu/hr

Acp = 2421.36 ft2

Q/Acp = 36575.316 Btu/ hr. ft2

Evaluate Tg (actual) at calculated Q/Acp & Ts

Tg = 1650 F

We have,
 Tg = 1650F calculated from figure 19.14 (16)

Whereas assumed Tg was 1625 F that is round about equal to calculated one, So our
assumption is true.

Assumed Specified flux is our required flux, So

Specified flux =10000 Btu/hr.ft2

6.3.9.10: Final Results

Number of tubes = 72

Flue gas temperature = 1650 oF

Heat duty = 66269830.65 Btu / hr

Heat Flux = 10,000 Btu/ hr ft2

Dimension of furnace = Height x Diameter

= 52 ft x 17 ft

6.3.10: Specification Sheet

Table 20: Specification sheet of furnace

Equipment name Furnace

Use to increase 200 oC before reactor to

Function
achieve reaction temperature.

No. required 3

Total heat duty 209758906.9 kJ/hr

Fuel required 12506.97 lb/hr

Inlet Temperature 125 oC

Outlet Temperature 325 oC

O.D. of tubes 5 in

Tube length 50 ft

Center to center distance 8 in

No. of tubes 72
Diameter of furnace 17 ft

Height of furnace 52 ft

Beam length 17 ft

Material of construction Carbon Steel (Furnace), S.S 316 (Tubes)

Refractory material Fire Clay & kastolite

6.4: Make-up Gas Compressor

6.4.1: Types of Compressor

The several kinds of commercial compressors are:

1. Rotodynamic
a. Centrifugal (radial flow)
b. Axial Flow
2. Positive displacement
a. Reciprocating piston
b. Rotary (screws, blades, lobes, etc.).

Table 21: General Compression and Vacuum Limits (22)

Approximate
Maximum Approximate Approximate
Maximum Maximum
Compressor Type Commercially Used Compression Compression Ratio per
Discharge Ratio per Stage Case or Machine
Pressure, psia

Reciprocating 35,00050,000 10 as required

Centrifugal 3,000 5,000 34.5 810

Rotary
100 130 4 4
displacement

Axial flow 80 130 1.21.5 56.5

Figure 7: Selection of compressor on the base of flow rate& discharge pressure

6.4.2: Compressor selection

In selecting the appropriate compressor for our process condition, the volumetric capacity,
head and discharge pressure are useful parameters in making a preliminary choice. The figure
provides operating boundaries using these parameters for the three major types of
compressors namely, centrifugal, reciprocating and axial. In our process the discharge
pressure and inlet volumetric flow rate are 7865 kPa and 7009 ft3/min respectively. The
intersection of these values lies in the region of centrifugal compressor as shown in the figure
6.1. The centrifugal air compressor is a dynamic compressor which depends on transfer of
energy from a rotating impeller to the air. The rotor accomplishes this by changing the
momentum and pressure of the air. This momentum is converted to useful pressure by
slowing the air down in a stationary diffuser. The centrifugal air compressor is an oil free
compressor by design. The oil lubricated running gear is separated from the air by shaft seals
and atmospheric vents. The centrifugal is a continuous duty compressor, with few moving
parts, that is particularly suited to high volume applications, especially where oil free air is
required. Centrifugal air compressors are water cooled and may be packaged; typically the
package includes the after-cooler and all controls.
6.4.3: Operating Conditions
The operating conditions of make-up gas compressor are as follows

Inlet pressure = 517.1 kPa

Discharge Pressure = 7865 kPa (78.65 bar)

Inlet Flow-rate = 8818.433 Kg/hr (6.922 m3/min)

6.4.4: Calculations
After selecting the compressor, the work requirement and the number of stages are calculated
by following procedure. First of all, values of reduced temperature and reduced pressure are
calculated by using critical temperature and pressure of each component.

Tr1 = 2.924

Pr1 = 0.256

The compressibility factor z is obtained from graph against these reduced temperature and
reduced pressure.

z1 = 0.99

The efficiency of the centrifugal compressor is found from the graph against the volumetric
flow rate.

p = 0.725

Then (n-1) / n = (k-1) / k / p factor is calculated by using k values, which come outs to be
0.262. The work requirement assuming one stage of compression is calculated by

Wp = z R n T1/(n-1) [(P2/P1) (n-1)/n -1] = 11374332.2 J/kg mole

Wc1 = Wp1 / p=15581277.01

(k-1) / k = p(n-1)/n

(k-1)/k = 0.19126

Value of T2 is calculated by formula

T2 = (Wc1 (k-1/k) / 8314) + T1 = 706.4 K

Since T2 > 450 K, so we cannot use one stage. Now Assuming 2 stages of compression, work
is calculated by using the following formula

Wp2 = z R n T1 / (n-1) [(P2 / P1) (n-1)/n -1 + (P3/P2) (n-1)/n -1] = 9367685.266 J/kg mole

Wc2 = Wp2 / p

= 12832445.57 J/kgmole

Again TD is calculated by

TD = ((Wc2 (k-1/k))/8314) + T1

= 497.09 K

As the discharge temperature is less than 500 K, two stages are selected for our compressor.

6.4.4.1: Heat Duty of inter cooler

Table 22: Specific heat capacity of gas

Cp (inlet) 52.47 kJ / kgmole.C

Cp (outlet) 45.26 kJ / kgmole. C

Cp (avg) 48.865 kJ / kgmole. C

Gas molar flow rate, m 4409.217 kgmole/hr

The amount of heat required is calculated by

Q = m Cp (TD-T1)

= 32122393 kJ/hr

Total Power required for compressor is given by

 PT = ((m Wc2) / 1000) / 3600

= 15716.95 kJ/sec

Power required for one Stage

P = PT / n

= 7858.47 kW

6.4.5: Specification Sheet of Feed Gas Compressor

Table 23: Specification sheet of feed compressor

Type of compressor Centrifugal

Inlet flow-rate 8818.433 kg/hr

Inlet Temperature 348 K

Inlet Pressure 517.1 kPa

Discharge Temperature 497.7 K

Discharge Pressure 7865 kPa

Number of Stages 2

Compression Ratio (per stage) 3.9

Overall Compression Ratio 15.2

Heat Duty of inter cooler 32122393 kJ/hr

Power Required for Compressor 15716.95 kJ/hr

6.5: Recycle Gas Booster Compressor

A booster gas compressor is used for maintaining the pressure of the recycle gas, which is
coming from the H2S absorber. The selection of booster compressor is based on the very
same criteria as discussed in previous section.

6.5.1: Operating Conditions

Inlet pressure = 6205 kPa

Discharge Pressure = 7865 kPa

 Inlet Flow-rate = 2983.367 Kg/hr

The number of stages in this case comes out to be one because the check of temperature is
satisfied. The work of compression and the heat duty are calculated on the same parallel lines
as for make-up gas compressor in above section.

6.5.2: Booster Compressor Specification Sheet

Table 24: Specification sheet of booster compressor

Type of compressor Centrifugal Compressor

Equipment code Operational

Inlet flow-rate 2983.367 kg/hr

Inlet Temperature 306.3 K

Inlet Pressure 6205 kPa

Discharge Temperature 320.95 K

Discharge Pressure 7584 kPa

Number of Stages 1

Compression Ratio (per stage) 1.22

Overall Compression Ratio 1.22

Power Required for Compressor 1086 kW

6.6: Pump (22)

Pump is a mechanical device generally used for raising liquids from a lower level to a higher
level. This is achieved by creating a low pressure at the inlet and high pressure at the outlet of
the pump. Due to low inlet pressure, liquid raises from where it is available and the high
outlet pressure forces it up where it is to be stored or supplied.

6.6.1: Two Basic Types of Pumps

Two very basic types of pumps being most frequently used in chemical industry are

a) Rotodynamic pumps
b) Reciprocating Pumps
6.6.2: Comparison between Centrifugal Pump and Reciprocating
Pump
Table 25: Comparison of different type of pump
Centrifugal Pump Reciprocating Pumps

Steady flow. Pulsating flow.

Uniform torque. Non-uniform torque.

High efficiency for low head pumps. Low efficiency for low head pumps.

Usually preferred when large capacities Preferred for low capacities but large
are to be handled. developed heads.

It has high speed. It has low speed.

Handles all types of fluids. Causes trouble in handling viscous fluids.

High initial cost nearly four times that of
Low initial cost.
centrifugal pumps.
High maintenance cost. Valves require
Low maintenance cost.
special attention.

Compact design. Requires less floor Requires more floor space 6-8 times more
space. than centrifugal pump.

Gross weight is less. Gross weight is considerable.

It causes less noise. It causes more noise.

6.6.3: Pump Selection Procedure

Pump selection mainly depends upon the pumping system decided to be followed in a
project. Therefore, while specifying a pump, the engineer is required to determine the system
requirements and then select a pump-centrifugal or reciprocation, vertical or horizontal, and
then write the pump specification along with drive and other accessories, so that no supplier
finds any problem in offering the right type of pump. The steps involved in pump selection to
purchase the pump are:

Engineering of system requirements;

Selection criteria of pump set;
Specification of pump and drive;
Raising enquiry;
Evaluation of tenders, and
 Placement of order for supply and installation of pump set.

6.6.4: Selection Criteria for Pumps

Proper selection of pumping equipment that will provide satisfactory performance requires
good understanding of existing conditions. Design restrictions, operating conditions of the
plant, and required flexibility in system operation must be understood before an efficient
pump can be selected for a given system. Following factors need to be considered when
selecting a pump for particular job. These include

6.6.4.1: Capacity
Capacity of fluid being pumped is a dictating factor in selecting a pump. Centrifugal pumps
can handle higher capacities.

6.6.4.2: Head Developed

In selecting a pump, one should carefully consider the head that needs to be developed in
order to transport the fluid from one point to another point.

6.6.4.3: Specific Gravity

Specific gravity of liquid to be pumped must be considered while selecting a pump. Due to
change in specific gravity of liquid pressure developed, quantity by weight of fluid delivered,
power required and permissible suction lift will change.

6.6.4.4: Viscosity
Viscosity of liquid to be pumped has marked influence on pump selection. High viscosity
increases the capacity, lowers the head developed, increases the power required and reduces
the efficiency.

6.6.4.5: Net Positive Suction Head Available

This is a function of the system in which pump will operate. It is the available pressure head
at the inlet of the pump. That pump should be selected which has enough NPSH available.

6.6.4.6: NPSH Required

This is a function of pump design. This is the positive head required at the pump suction to
overcome pump internal losses and maintain the liquid above its vapor pressure. It varies
with speed and capacity within any pump. This should be greater than NPSH available for
satisfactory pump operation.
6.6.4.7: Vapor Pressure
Vapor pressure of the liquid must be considered in selection of a pump. If at operating
temperature, liquid exhibit high vapor pressure it may cause an increase in required NPSH.

6.6.4.8: Solid Contents

Solid contents need to be evaluated while selecting a pump because pump requires large flow
area in order to make passage for solids. Centrifugal pumps are incapable of handling solids
more than 10% by weights.

6.6.5: Selection of Diesel Feed Pump and design Calculations

The fluid that needs to be pumped is diesel. The specifications in this case are

Temperature 323 K

Suction pressure 101 kPa

Head Developed 6963 kPa

Viscosity 0.35 cP

Specific gravity 0.8612

Capacity 0.074 m3/sec

Pump type can be selected by evaluating specific speed which is a function of head, capacity
and speed of impeller, given by

Ns = Nr mv 0.5 / (gH) 0.75

Where

Nr = speed of impeller in rev/sec

mv = volumetric flow rate in m3/sec

H = head in m

= pressure / density change

Ns comes out to be
 Ns = 58.33 0.07361 0.5 /(10* 710.2)0.75

= 354

This specific speed suggests the use of four-stage radial flow centrifugal feed pump.

6.6.5.1: Power Requirements

Power required for driving this pump can be calculated by

P = H mv /

Where P = power in watts

H = head developed in Pa

mv = flow rate in m3/sec

= overall pump efficiency

Pump efficiency used in this case is 80 %. So the power required by the pump is

P = 6961135.1 0.0736 / 0.8

= 640 kW

6.6.6: Specification Sheet

Table 26: Specification sheet of pump

Type of pump Centrifugal

Inlet flow-rate 0.0736 m3/sec

Inlet Temperature 323 K

Inlet Pressure 101 kPa

Discharge Temperature 325 K

Discharge Pressure 6961.135 kPa

Number of Stages 1

Power Required for pump 640 kW

6.7: Two Phase (Gas-Liquid) Separator
Two phase separator is a high pressure vessel used to separate two phase inlet into pure gas
and pure liquid. Our aim in this case is to separate the diesel from lighter hydrocarbons and
gases so that they can be recycled back to the reactor. Major types of two phase separator are

1. Vertical two phase separator.

2. Horizontal two phase separator.
The function of the separator is to separate the oil from hydrogen sulfide and hydrogen rich
gas, for which we are using a horizontal separator.

In the design of a separator vessel diameter cannot be determined independently of its length.
The diameter and the length and the liquid level must be choosen to give the sufficient vapour
residence time for the liquid droplets to settle out, and for the required liquid hold up time to
be met.

6.7.1: Design Calculations (22)

The operating conditions and data required for the design of this vessel (V-103) are given
below
Table 27: Data required for the design of separating vessel

Operating temperature 40 oC

Operating pressure 5236 kPa

Liquid density, L 854 kg/m3

Vapor density, v 1.179 kg/m3

Liquid volumetric flow rate, VL 0.072 m3/s

Vapor volumetric flow rate, Vv 2.174 m3/s

Mist eliminator Yes

Generally, first the calculations are made for vertical type separator and if the checks on the
final result are not satisfied then we shift to horizontal type separator design.

Flow rate of diesel oil Goil = 221832.414 kg/hr

Flow rate of H2S GH2S = 1369.789 kg/hr

Flow rate of H2 GH2 = 2939.478 kg/hr

Density of oil oil = 854 kg/m3

Density of H2S H2S = 1.54 kg/m3

Density of H2 H2 = 0.0897 kg/m3

Volume flow rate of oil Qoil = Goil/ oil

= 221832.414/854

= 259.75 m3/hr

Fraction of H2 in gas phase = 2939.478/ (2939.478+1369.789)

= 0.682

Fraction of H2S in gas phase = 1-0.682

= 0.317

Avg density of the gas v = (0.317)(1.54)+ (0.682)(0.0897)

v = 0.5506 kg/m3

Total mass flow of the gas = 2939.478+1369.789

= 4309.267 kg/hr

Volume flow rate of the gas (vapors) Qv = 4309.267/ 0.5506

Qv = 7826.35 m3/hr

Settling velocity Ut = 0.07 (oil-v/v)1/2

 Ut = 0.07(854.1-0.5506/0.5506)1/2

Ut = 2.756 m/s

Us = 0.15 x Ut

Us = 0.15 x 2.756

Us = 0.4314 m/s

Qv = 7826.35 m3/hr

Qv = 2.174 m3/s

Length to dia ratio Lv/Dv = 5 (P > 35 bar)

Lv = 5 Dv

Height above liquid level Hv = Dv/2

Cross sectional area for vapour flow Av = /4 x (Dv2) x 0.5

Av = 0.3927 Dv2

Vapour velocity Uv = Qv/Av

= 2.174/0.3927 Dv2

Uv = 5.536 Dv-2

Vapour residence time required for vapour to settle down

= Hv/Us

= 0.5 Dv/0.4134

= 1.209 Dv

Actual residence time = vessel length / vapour velocity

= Lv/Uv

= 5 Dv/ 5.536 Dv-2

= 0.903Dv3
For satisfactory operation

Required residence time = Actual residence time

5.84 Dv = 0.903 Dv3

Dv = 2.543 m say 3 m

Liquid hold up time

Vol. flow rate of oil Qoil = 259.72 m3/hr

= 0.072 m3/s

Liquid cross-sec area Av = /4 x (Dv2) x 0.5

Av = /4 x (2.543)2 x 0.5

Av = 2.53 m2

Length Lv = 5 x Dv

Lv = 5 x 2.54

Lv = 12.667 m

Hold up volume = liq. cross-sec x length

= Av x Lv

= 2.53 x 12.667

= 32.04 m3

Hold up time t = Hold up vol./ liquid flow Rate

t = 32.04/0.072

= 445.13 sec

= 7.41 say 8 min

6.7.1.1: Wall Thickness
Wall thickness is calculated by following formula,

tw = [R P / (2 E S + 0.4P)]

Design pressure of vessel P is 1.5 times operating pressure = 7854 kPa.

Inner radius with corrosion allowance R is = 0.852 m.

Joint efficiency E is taken as = 0.9.

Allowable Stress S is = 119 MPa.

So, wall thickness comes out to be = 0.0307 m

6.7.1.2: Internals of Two Phase Separator

6.7.1.2.1: Mist Extractor (Mist Eliminator)

The function of the mist extractor is to remove the very fine liquid droplets from the gas
before it exist the separator. Several types of mist extractor are available:

6.7.1.2.2: Wire-Mesh Mist Extractor:

These are made of finely woven stainless-steel wire wrapped into a tightly packed cylinder of
about 6 in thickness. It is capable of removing about 99% of the 10 m and larger liquid
droplets but it is prone to plugging.

Plugging could be due to the deposition of paraffin or the entrainment of large liquid droplets
in the gas passing to the mist eliminator in such case we use vane type mist eliminator.

6.7.1.2.3: Vane Mist Extractor:

This type of extractor consists of series of closely spaced parallel, corrugated plates. As the
gas and entrained liquid droplets flowing between the plates change flow direction due to
corrugations, the liquid droplets impinge on the surface of the plates, where they coalesce and
fall down into the liquid collection section.
6.7.1.2.4: Centrifugal Mist Extractor:
This type of extractor uses centrifugal force to separate the liquid droplets from the gas.
Although it is more efficient and less susceptible to plugging than other extractors, it is not
commonly used because of its performance sensitivity to small changes in flow rate.

6.7.1.2.5: Inlet Diverters (Splash Plate)

Inlet diverters are used to cause the initial bulk separation of liquid and gas. The most
common type is baffle plate diverter, which could be in the shape of a flat plate, a spherical
dish, or a cone. Another type, is the centrifugal diverter; it is more efficient but more
expensive.

6.7.1.2.6: Advantages:
It provides a means to cause a sudden and rapid change of momentum (velocity and
direction) of the entering stream. If it is not present then the vapors will escape very rapidly
without contacting with liquid to establish equilibrium.

6.7.1.2.7: Vortex Breaker

A vortex breaker is normally installed on the liquid outlet to prevent formation of vortex
when the liquid outlet valve is open. The formation of a vortex at the liquid outlet may result
in withdrawal and entrainment of gas with the exiting liquid (gas blow by).

Figure 8: Vertical type separator with vertox breaker

6.7.2: Specification Sheets
Table 28: Specification sheet of separating vessel

Equipment name Gas liquid separator

Function To separate gas phase from liquid phase.
Type Vertical
Pressure 5314.6 kPa
Temperature 313 K
Diameter 3 m
Length 12.667 m
Material of construction Stainless steel 316

6.8: Steam Stripper

This equipment is used to separate dissolved gases and light ends present in the product
which could not be separated in separators. It is important to remove these light ends
otherwise they may disturb the flash point of our diesel product which may result in poor
ignition quality of fuel .Steam is being used for this purpose. The flow rate of steam is so
adjusted as to ensure complete removal of gases as well as any wild naphtha present. The
final product coming out of stripper is ultralow sulfur diesel which does not require any
further processing.

6.8.1: Design Calculations

Before proceeding towards design, we first have to specify certain decision variables which
are usually selected on the basis of experience keeping in view the properties and flow rates
of fluids. These variables are taken as
Table 29: Design variables

Tray spacing 0.900 m

% down comer area 20%

% of flooding velocity 85%

Hole diameter 3.5 mm

Weir height 70 mm

Hole to active area ratio 0.06

Turn down ratio 0.75

Standard Design Steps for Calculation

1) Theoretical number of stages.

2) Diameter of column.
3) Weeping point.
4) Pressure drop.
5) Downcomer design.
6) Entrainment calculations.
7) Residual time calculation
8) Perforated area calculation
9) Number of holes calculation

6.8.1.1: Calculation of theoretical number of stages (21):

The main component which we want to be stripped from diesel is H2S. So, we take it as a
reference.

Let us suppose that 100% of H2S is not stripped and very minute quantities remains in the
lean diesel coming out from Stripper.

Fraction of H2S stripped Esi = 0.998

Minimum V/L for H2S = ( )min =

Value of K depends on T & P.

So, average tower conditions for value of ki:

T = 237 C

P = 14.7 psia.

Ki (22) = 95

So, ( )min =

=
 = 0.01050

Operating ( ) = 1.25 (0.01050)

= 0.0131

Operating stripping factor

Si = ( ) . ki

= 0.0131 x 95

= 1.2475

Theoretical stages at operating conditions.

ESi = SiN+1 Si / SiN+1 1

0.998 = (1.2475)N+1 1.2475 / (1.2475)N+1 1

(N+1) log 1.2475 = log ( )

(N+ 1)(0.0955) = 2.0969

N = 20

It means 20 theoretical trays are needed.

If efficiency of process is 75%

Number of actual plates required = 26

6.8.1.2: Calculation of diameter of column:

Flooding velocity is given by

Uf = K1

Where,

Uf = Flooding vapor velocity in m/s , base on net column cross-sectional area.

K1 = Constant obtained from figure 11.27 (23)

 FLV =

Where,

Lw =Liquid mass Flow rate,

Vw = Vapour mass Flow rate,

In this Case,

Lw = 61.56

Vw = 1.715

v =1.47

L = 861.5

FLV =

= 1.484

We use Plate Spacing 900 mm.

K1 = 0.03

Then, UF = 0.03

= 0.724

We take actual velocity as 85% of flooding velocity

So, Uv = 0.85 x .724

= 0.616

Maximum volumetric vapor flow rate =

=1.163
Net area required An =

= 1.88 m2

We take downcomer area as 20% of total area

Column cross sectional area Ac =

= 2.36 m2

Down comer area Ad = 2.36 1.88

= 0.48 m2

Active area , bubbling area Aa = Ac 2 Ad

= 2.36 2(0.48)

= 1.40 m2

Total hole area as 6% of active area, so

Hole area AH = 0.06 x 1.40

= 0.084 m2

Column diameter Dc =

= 1.74 m.

6.8.1.3: Calculation of Weeping Point:

For the calculation of weeping point, hole diameter must be selected so that at lowest
operation rate, the vapor flow velocity is still above weeping point.

Maximum liquid flowrate = 61.56

Minimum liquid rate , at 70% turn down = 0.70 x 61.56

= 43.10
 x 100 = x 100

= 20%

From figure 11.31 (24)

= 0.86

lw = 0.86 x 1.74

= 1.50 m

We know

how = 750 * + 2/3

Lw = weir length, m

how = height over weir , mm liquid

Lw = liquid flow rate

Minimum how = 750 [ ] 2/3

= 98.7 mm.

We take, hw = 70 mm

hw + how = 98.70 + 70

= 168.70 mm.

From fig 11.30 (25)

K2 = 31

Uh(min) =[ ]

Uh = minimum vapor velocity through holes, m/s

Dh = hole diameter, mm
 Uh = ]

Uh = 9.296 m/s

Actual minimum vapor velocity =

= 9.7 m/s

So, minimum operating rate will be well above weeping point.

6.8.1.4: Calculation of Pressure drop:

= 9.81 x 10-3 ht PL

= total pressure drop, Pa (N/m2)

ht = total pressure drop , mm liquid

Total pressure drop is giver by

ht = hd + (hw + how) + hr

ht = total plate pressure drop

hd = dry plate pressure drop

hr = residual head

hw = height of weir

how = weir crest, mm liquid

hd = 51 [ ]2

Co = Orifice coefficient

Uh = Vapor velocity through holes , m/s

Uh = = 13.84 m/s.
We take carbon steel plate, so

Plate thickness = 4 mm

Hole diameter = 3.5 mm

So, .142

from figure 11.34 (26)

Co = 0.84

hd = 51 [ ]2 [ ]

= 14.70 mm

hr =

= 14.50 mm

ht = 14.70+168.70+14.50

= 197.70 mm liquid

= 9.81 x 10-3 x 197.70 x 861.5

= 1669.12 Pa

6.8.1.5: Downcomer Design:

The downcomer area and the plate spacing must be such that the level of the liquid and froth
in the downcomer is well below the top of outlet weir on the plate above. If the liquid rises
above the outlet weir the column will flood.

hb = (hw + how) + ht + hdc

Where,

hb = downcomer backup, measured from plate surface,

mm
 hdc = head loss in downcomer, mm

hdc = 166 [ ]2

Where,

hdc = head loss in downcomer, mm

Lwd = liquid flowrate in downcomer, kg/s

Am = Either downcomer area or clearance area under the downcomer Aop which is smaller.

Aop = hop Lw

Where hop = height of bottom edge of apron above

plate

Lw = length of weir

hop = hw 10

=70 10

= 60mm

So, Aop = 0.070 x 1.50 m

= 0.105 m

hdc = 166 [ ]2

= 112.90 mm

So, backup in downcomer hb =168.70+197.70+112.90

= 479.30 mm

= 0.479 m

Then, backup in downcomer < (pate spacing + weir height)

0.479 < (0.900 + 0.070)

0.479 < 0.485

So, plate efficiency is acceptable.

6.8.1.6: Entrainment Calculation:

For checking entrainment, we calculate

Uv =

Uv =

= 0.61 m/s

% flooding =

= = 85%

We already know FLV

FLV = 1.484

From figure 11.29 (27)

It is well below 0.1, so there is no chance of entrainment and process is satisfactory.

6.8.1.7: Check residual time

The sufficient resistance time must be allowed in the down comer for the entrained vapor to
disengage from the liquid. The recommended value is at least 3 second. In our case the
resistance time comes to be greater than 3 as given below

Ad hbc L
tr =
Lwd

0.48 0.479 861.5

= = 3.22 sec
61.56

So this check is also satisfactory

6.8.1.8: Calculation of Perforated Area
LW 1.50 Lh
From the graph, at 0.86 the value of 0.245
Dc 1.74 DC

So Lh = 0.245 1.74 = 0.4236

By using above value the angle subtended by chord c is calculated becomes out to be 118.
So so angle subtended by the edge of plate

a = 180- c

= 62

Since edge of un-perforated strip wr taken 50 mm and width of calming zones is taken as

wc=100mm (Because diameter is greater than 1.5 m )

Mean length of un-perforated edge strip

ls = (Dc-wr) a/180

62
ls =(1.7- 0.05)
180

= 1.82 m

Area of un-perforated edge strip

as = wr ls

= 0.05 1.82

= 0.0914 m2

mean length of calming zone,approx. lc = weir length + wr

= 1.5 + .05

= 1.55 m

Area of calming zones

ac = 2 wc lc
 = 2 .1 1.55

ac = 0.31 m2

Total area available for perforations

Ap =Aa as+ ac

=1.01 m2

Ah 0.084
As 0.083
Ap 1.01

From fig 11.33 (28)

lp
3.1
dh

Satisfactory, within 2.5 to 4

6.8.1.9: Number of Holes

Diameter of a hole = 3.5 mm

Area of one hole = 9.62 10-6 m2

Number of holes = Ah / area of one hole

= 8730

6.8.2: Specification Sheet

Table 30: Design Specification sheet for Stripper

Equipment Steam Stripper

Function Removal of Light Ends from ULSD

Height / Length (m) 24

Inside Diameter (m) 1.74

Tray Type Sieve

No. of Trays 26

Operating Pressure (kPa) 201.3

Operating Temperature(C) 237

Weir Height (mm) 70

Weir Length (m) 1.5

Hole Diameter (mm) 3.5

Tray Spacing (m) 0.9

Downcomer Area (m2) 0.48

No. of Holes 8730

Material of Construction SS-316, CS-86XX

6.9: Absorber design

Flow rate of H2S in gaseous feed = 1152.678 kg/hr

= 34kmole/hr

Flow rate of H2 in gaseous feed = 2939.478kg/hr

= 1469.7kmole/hr

Molar flow of gaseous feed =34 + 1469.7

= 1503.7kmol/hr

Mole fraction of H2S in feed = 34/1503.7

y1 = 0.02261

Suppose 1%mol of H2S goes with outlet gaseous stream.

So,

Mol. Fraction H2S in outlet =0.34/(0.34 + 1469.7)

 y2 = 0.000231

Mol. Fraction of H2S in lean DEA

x2 =0

As 99% mole of H2S goes with rich DEA = 0.99 x 34

So,

Moles of H2S in rich DEA = 33.66 kmol/hr

Moles of DEA = 182.27 kmol/hr

So,

Mole fraction of H2S in DEA = 33.66/(33.66 + 182.27)

x1 = 0.15588

Now,

Molar ratio of H2S to H2 at bottom = y1/(1-y1)

Y1 = 0.02313

Molar ratio of H2S to H2 at top = y2/(1-y2)

Y2 = 0.000231

Molar ratio of H2S to DEA solution at top

X2 =0

Molar ratio of H2S to DEA solution at bottomx1

= x1/(1-x1)

X1 = 0.18467

Now, equilibrium relation for the solution

So,

Ye = 0.15(x)(X)
 Ye1 = 0.15(0.15588)(.18467)

Ye1 = 0.00432

And,

Ye2 =0.15(0)(0)

Ye2 =0

Driving force at top of column = Y2-Ye2

= 0.000231

Driving force at bottom of column = Y1-Ye1

= 0.01881

Logarithmic mean driving force = (Y-Ye)lm

(Y-Ye)lm = ((Y1 - Ye1) (Y2 Ye2))/ ln((Y1-Ye1)/(Y2-

Ye2))

(Y-Ye)lm = 0.000.00422

Now, as we know (30)

Gm * (Y1 Y2) = KGa ( Y-Ye)lm Z

Where,

Gm = Mass flow per unit area

KGa = Overall coefficient for absorption

So,

KGa = 3.3 kmol/s-m3

= 11880 kmol/hr-m3

Gm =Gm/A
 Gm = Molar flow rate of gas

Thus,

Gm/A(Y1-Y2) = KGa(Y-Ye)lmZ

(1503.7/A) x (0.02313 -0.000231) = 11880 x 0.00422 x Z

AxZ = 30 m3

V = 30 m3

Taking cylindrical column

Then,

Volume of cylinder V =AxZ

V = (/4) d2 x Z

Taking,

Z =5xd

So,

V = (/4)d2 x5d

d =2m

Z = 10 m

A = (d2/4)

= 3.14 m2

Mole flow rate per unit area Gm = 1503.7/3.14

= 479 kmol/hr- m2

Number of Transfer Units:

No.of transfer units = NOG

= (Y1 Y2)/ (Y-Ye)lm

 = 5.2

Height of transfer unit = HOG

= Z/NOG

=2m

Berl Saddles of 50 mm size paking is used,

From Table 11.3 (30)

Pressure drop across pressure drop across one transfer unit = 101 Pa

Total pressure drop = 101 x 5.2

Pressure drop = 525.2 Pa

6.9.1: Specification Sheet

Table 31: Design Specification sheet for absorber

Equipment Scrubber

Function Removal of H2S from the Recycle Gas

Absorbent DEA 20% solution

Height / Length (m) 10

Inside Diameter (m) 2

No. of Transfer units 5.2

Operating Pressure 53 kg/cm2

Packing type Berl Saddles

Packing size (mm) 50

Material of Construction SS-316, CS-86XX

Instrumentation
&
Process Control
 Chapter #07

7: Instrumentation and control

7.1: Introduction to Instrumentation
. . The important feature common to all process is that a process is never in a state of static
. . . . . . . . . . . . . . . . .

. equilibrium except for a very short period of time and process is a dynamic entity subject to
. . . . . . . . . . . . . . . .

. continual upset or disturbance which tend to drive it away from the desired state of
. . . . . . . . . . . . .

. equilibrium the process must then be manipulated upon or corrected to derive some
. . . . . . . . . . .

. disturbance bring about only transient effect in the process behavior. These passes away and
. . . . . . . . . . . . .

. the never occur again. Others may apply periodic or cycle forces which may make the
. . . . . . . . . . . . . . .

. process respond in a cyclic or periodic fashion. Most disturbances are completely random
. . . . . . . . . . . . .

. with respect to time a show no repetitive pattern. Thus their occurrence may be expected hut
. .. .. . . . . . . . . . . . . .

cannot be predicated at any particular time. If a process is to operate efficiently, disturbances

. . . . . . . . . . . . . . .

. in the process must be controlled.

. . . . .

. Measurement is a fundamental requisite to process control. Either the control can be affected
.. . . . . . . . . . . . . .

. automatically, semi- automatically or manually. The quality of control obtainable also bears a
. . . . . . . . . . . . . . .

. relationship to the accuracy, re- product ability and reliability of the measurement methods,
. . . . . . . . . . . . . . .

. which are employed . Therefore, selection of the most effective means of measurements is an
. . . . . . . . . . . . . . .

. important first step in the design and formulation of any process control system.
. . . . . . . . . . .. .. .
. The main objectives of specifying and using of instruments and controls systems are
. . . . . . . . . . .

a) To safe the plant operation by keeping the process variables within the operating
. . . . . . . . . . . . .

. limits and detects the dangerous situations since developed. . . . . . . . .

b) To control the product rate and quality within the specified quality.
. . . . . . . . . . .

c) To operate the process at the lowest production cost

. . . . . . . .

. Since process profit is usually the most important benefit to obtained by applying automatic
. . . . . . . . . . . . .

. control. The quality of control and its cost should be compared with the economic return
. . . . . . . . . . . . . . .

. expected and the process technical objective. The economic return

. . . . . . . . . . . includes reduced .

. operating costs, maintenance and of the specification product along with improved process
. . . . . . . . . . . . .

. operability and increased throughout. . . . .

7.2: Analysis of Measurement

7.2.1: Variables to be measured
1. Pressure Measurement
2. Temperature Measurement
3. Level Measurement
4. Flow Rate Measurement

7.2.1.1: Pressure Sensing Instruments (1)

7.2.1.1.1: Application Considerations
When installing pressure sensors, care should be taken to select the correct pressure sensor
for the application.

7.2.1.1.2: Selection
Pressure- sensing devices are chosen for pressure range, overload requirements, accuracy,
. . . . . . . . . . . . . . .

. temperature operating range, line- of- sight reading, or electrical signal, and response time. In
. . . . . . . . . . . . . . . . . .

. some applications there are other special requirements. Parameters, such as hystersis and
. . . . . . . . . . . . . . .

stability, should be obtained from the manufacturers specifications. For most industrial
. . . . . . . . . . . .

. applications reading positive pressures, the Bourdon tube is a good choice for direct visual
. . . . . . . . . . . . . .

. readings and the silicon pressure sensor for the generation of electrical signals. Both types of
. .. .. . . . . . . . . . . . .

. devices have commercially available sensors to measure from a few pounds per square inch
. . . . . . . . . . . . .
. pressure FSD up to 10, 000 psi (700 MPa) FSD. Table 1 lists the operating range for several
. . . . . . . . . . . . . . . . . . . .

. types of pressure sensors .

. . . .

7.2.1.1.3: Installation
The following should be taken into consideration when installing pressure sensing devices.
. . . . . . . . . . . .. .

1. Distance between sensor and source should be kept to a minimum.

. . . . . . . . . .. .

2. Sensors should be connected via valves for ease of replacement.

. . . . . . . . . ..

3. Over- range protection devices should be included at the sensor.

. . . . . . . . . .. .

4. To eliminate errors due to trapped gas in sensing liquid pressures, the sensor should
. . . . . . . . . . . . . . .

. be located below the source.. . . ..

5. To eliminate errors due to trapped liquid in sensing gas pressures , the sensor should
. . . . . . . . . . . . . . . .

. be located above the source.. . . .

6. When measuring pressures in corrosive fluids and gases, an inert medium is

. . . . . . . . . . . . .

. necessary between the sensor and the source or the sensor must be corrosion . . . . . . . . . . . .

. resistant. . .

7. The weight of the liquid in the connection line of a liquid pressure sensing device
. . . . . . . . . . . . . . .

. located above or below the source will cause errors in the zero, and a correction must
. . . . . . . . . . . . . . . .

. be made by the zero adjustment, or otherwise compensated for in measurement

. . . . . . . . . . . .

. systems. . .

8. Resistance and capacitance can be added to electron circuits to reduce pressure

. . . . . . . . . . . .

. fluctuations and unstable readings. . . . .

7.2.1.1.4: Calibration
Pressure- sensing devices are calibrated at the factory. In cases where a sensor is suspect and
. . . . . . . . . . . . . . . . . .

. needs to be recalibrated, the sensor can be returned to the factory for recalibration, or it can
. . . . . . . . . . . . . . . . . .

. be compared to a known reference. Low- pressure devices can be calibrated against a liquid
. . . . . . . . . . . . . . . .

. manometer. High - pressure devices can be calibrated with a dead- weight tester. In a dead -
. . . . . . . . . . . . . . . . . . .

. weight tester the pressure to the device under test is created by weights on a piston. High
. . . . . . . . . . . . . . . . .

. pressures can be accurately reproduced. . . . . . .

Table 32: Approximate Pressure Ranges for Pressure-Sensing Devices

Device Maximum Range, Maximum Range,
2
Device
lb/in lb/in2
U-tube manometer
15 Diaphragm 400
Bellows
800 Capsule 50

Bourdon tube
100,000 Spiral bourdon 40,000

Helical bourdon
80,000 Piezoelectric 100,000

Strain gauge Solid state diaphragm

100,000 200

Stainless steel
----
diaphragm 100,000 ----

7.2.1.2: Temperature Measuring Instruments (2)

7.2.1.2.1: Application Considerations

7.2.1.2.2: Selection
In process control a wide selection of temperature sensors are available. However, the
. . . . . . . . . . . . . . .

. required range, linearity, and accuracy can limit the selection. In the final selection of a
. . . . . . . . . . . . . . . . .

. sensor, other factors may have to be taken into consideration, such as remote indication,
. . . . . . . . . . . . . . . .

. error correction, calibration, vibration sensitivity, size, response time, longevity,

. . . . . . . . . . . . . .

. maintenance requirements, and cost. The choice of sensor devices in instrumentation should
. . . . . . . . . . . . .

. not be degraded from a cost standpoint. Process control is only as good as the monitoring
. . . . . . . . . . . . . . . .

. elements. .

7.2.1.2.3: Range and Accuracy

Table 8.2 gives the temperature ranges and accuracies of temperature sensors. The accuracies
. . . . . . . . . . .

. shown are with minimal calibration or error correction. The ranges in some cases can be
. . . . . . . . . . . . . . .

. extended with the use of new materials.. . . . . . .

Table 33: Temperature ranges and accuracy of temperature sensors

Sensor Type
Range ( C ) Accuracy (FSD)

Expansion Mercury in glass -35 to 430 1%

Liquid in glass -180 to 500 1%
 Bimetallic -180 to 600 20%
0.5%
Liquid filled -180 to 550
Pressurespring 2.0%
Vapor pressure -180 to 550
0.5%
Gas filled -180 to 550

Metal resistors -200 to 800 5%

Resistance Platinum 180 to 650 0.5%
Nickel 180 to 320 1%
Copper -180 to 320 0.2%
Thermistor
--- 0 to 500 25%

Thermocouple -60 to 540 1%

---
-180 to 2500 10%
Semiconductor IC
--- -40 to 150 1%

7.2.1.2.4: Installation
Care must be taken in locating the sensing portion of the temperature sensor, it should be
. . . . . . . . . . . . . . . . .

. fully encompassed by the medium whose temperature is being measured, and not be in
. . . . . . . . . . . . . .

. contact with the walls of the container. The sensor should be screened from reflected heat
. . . . . . . . . . . . . . .

. and radiant heat if necessary. The sensor should also be placed downstream from the fluids
. . . . . . . . . . . . . . .

. being mixed, to ensure that the temperature has stabilized, but as close as possible to the
. . . . . . . . . . . . . . . . .

. point of mixing, to give as fast as possible temperature measurement for good control. A low
. . . . . . . . . . . . . . . . .

. thermal time constant in the sensor is necessary for a quick response. Compensation and
. . . . . . . . . . . . . .

. calibration may be necessary when using pressure- spring devices with long tubes especially
. . . . . . . . . . . . .

. when accurate readings are required.

. . . . .

7.2.1.2.5: Calibration
Temperature calibration can be performed on most temperature sensing devices by
. . . . . . . . . . .

. immersing them in known temperature standards which are the equilibrium points of solid/
. . . . . . . . . . . . .

. liquid or liquid/ gas mixtures, which is also known as the triple point. Most temperature
. . . . . . . . . . . . . . . .

. sensing devices are rugged and reliable, but can go out of calibration due to leakage during . . . . . . . . . . . . . . .

. use or contamination during manufacture and should therefore be checked on a regular basis.
. . . . . . . . . . . . .
7.2.1.2.6: Protection
In some applications, temperature sensing devices are placed in wells or enclosures to
. . . . . . . . . . . . . .

. prevent mechanical damage or for ease of replacement. This kind of protection can greatly
. . . . . . . . . . . . . .

. increase the system response time, which in some circumstances may be unacceptable.
. . . . . . . . . . . . .

. Sensors may need also to be protected from over temperature, so that a second more rugged
. . . . . . . . . . . . . . . .

. device may be needed to protect the main sensing device. Semiconductor devices may have
. . . . . . . . . . . . . .

. built in over temperature protection. A fail- safe mechanism may also be incorporated for
. . . . . . . . . . . . . . .

. system shutdown, when processing volatile or corrosive materials.

. . . . . . . . .

7.2.1.3: Level Measuring Devices (3)

7.2.1.3.1: Application Considerations
A number of factors affect the choice of sensor for level measurement, such as pressure on
. . . . . . . . . . . . . . . . .

. the liquid, liquid temperature, turbulence, volatility, corrosiveness, accuracy needed, single-
. . . . . . . . . . . . . . . .

. point or continuous measurement, direct or indirect, particulates in a liquid, free flowing

. . . . . . . . . . . . . . .

. solids, and so forth. . . . ..

. Floats are often used to sense fluid levels because they are unaffected by particulates, can be
. . . . . . . . . . . . . . . .

. used for slurries, can be used with a wide range of liquid specific weights, and flat floats due
. . . . . . . . . . . . . . . . . . .

. to their area are less susceptible to turbulence on the surface of the liquid. Figure 8. 1 shows
. . . . . . . . . . . . . . . . . . .

. a commonly used design for a float which can be attached to a level indicator. The float
. . . . . . . . . . . . . . . .

. displaces its own weight of liquid as follows: . . . . . . .

Float weight = buoyant force = L d2 h / 4

Where

L = specific weight of the liquid

d = diameter

h = immersion depth of the float

. When the float is used to measure one or more feet of liquid depth, any change in h due to
. . . . . . . . . . . . . . . . . . .

. large changes in g L will have minimal effect on the measured liquid depth.
. . . . . . . . . . . . .
. Displacers must never be completely submerged when measuring liquid depth and must have . . . . . . . . . . . .

. a specific weight greater than that of the liquid. Care must also be taken to ensure that the
. . . . . . . . . . . . . . . . . .

. displacer is not corroded by the liquid and the specific weight of the liquid is constant over
. . . . . . . . . . . . . . . .

. time. The temperature of the liquid may also have to be monitored to make corrections for
. . . . . . . . . . . . . . . .

. density changes. Displacers can be used to measure depths up to about 3 m with an accuracy
. . . . . . . . . . . . . . . .

. of 0. 5 cm. Capacitive device accuracy can be affected by the placement of the device, so
. . . . . . . . . . . . . . . . . . . .

. the manufacturers installation instructions must be followed. The dielectric constant of the
. . . . . . . . . . . .

. liquid should also be regularly monitored .

. . . . . . Capacitive devices can be used in pressurized
. . . . . . .

. containers up to 30 MPa and temperatures up to 1000 C, and measure depths up to 6 m with . . . . . . . . . . . . . . . . . . . .

. an accuracy of 1 percent.
. . . . . .

. Pressure gauge choice for measuring liquid levels can depend on a number of considerations,
. . . . . . . . . . . . . .

.. which are as follows: . . .

1. The presence of particulates that can block the line to the gauge
. . . . . . . . . . . .

2. Damage caused by excessive temperatures in the liquid

. . . . . . .

3. Damage due to peak pressure surges . . . . . .

4. Corrosion of the gauge by the liquid . . . . . . .

5. Differential pressure gauges are needed if the liquid is under pressure

. . . . . . . . . . .

6. Distance between the tank and the gauge

. . . . . . .

7. Use of manual valves for gauge repair. . . . . . .

. Differential pressure gauges can be used in pressurized containers up to 30 MPa and . . . . . . . . . . . . .

. temperatures up to 600 C to give accuracies of 1 percent, the liquid depth depend on its . . . . . . . . . . . . . . . . . .

. density and the pressure gauge used . . . . . . .. .

Bubbler devices require certain precautions when being used. To ensure a continuous air or
. . . . . . . . . . . . .

. gas supply, the gas used must not react with the liquid. It may be necessary to install a one
. . . . . . . . . . . . . . . . . . . .

. way valve to prevent the liquid being sucked back into the gas supply lines if the gas
. . . . . . . . . . . . . . .

. pressure is lost. The bubbler tube must be chosen so that it is not corroded by the liquid.
. . . . . . . . . . . . . . . . . .
. Bubbler devices are typically used at atmospheric pressure, accuracies of about 2 percent can
. . . . . . . . . . . . .

. be obtained, depth depends on gas pressure available, and so forth.

. . . . . . . . . . . .

. Ultrasonic devices can be used with pressurized containers up to 2 MPa and 100 C . . . . . . . . . . . . . . .

. temperature range for depths of up to 30 m with accuracies of about 2 percent. . . . . . . . . . . . . . .

. Radiation devices are used for point measurement of hazardous materials. Due to the . . . . . . . . . . . . .

. hazardous nature of the material, personnel should be trained in its use, transportation, . . . . . . . . . . . . . .

. storage, identification, and disposal. . . . . . . .

. Other considerations are that liquid level measurements can be effected by turbulence,
. . . . . . . . . . . .

. readings may have to be averaged, and/ or baffles used to reduce the turbulence. Frothing in
. . . . . . . . . . . . . . . . . .

. the liquid can also be a source of error particularly with resistive or capacitive probes.
. . . . . . . . . . . . . . .

7.2.1.4: Flow Measuring Devices (4)

7.2.1.4.1: Application Considerations
Many different types of sensors can be used for flow measurements. The choice of any
. . . . . . . . . . . . . . . .

. particular device for a specific application depends on a number of factors such as- . . . . . . . . . . . . . .

. reliability, cost, accuracy, pressure range, temperature, wear and erosion, energy loss, ease
. . . . . . . . . . . . . . . . . .

. of replacement, particulates, viscosity, and so forth.

. . . . . . . . .

7.2.1.4.2: Selection .

The selection of a flow meter for a specific application to a large extent will depend on the
. . . . . . . . . . . . . . . . . . . .

. required accuracy and the presence of particulates, although the required accuracy is
. . . . . . . . . . . . .

. sometimes down graded because of cost. One of the most accurate meters is the magnetic . . . . . . . . . . . . . . . . .

. flow meter which can be accurate to 1 percent of full scale reading or deflection (FSD). The
. . . . . . . . . . . . . . . . . .

meter is good for low flow rates, with high viscosities and has low energy loss , but is
. . . . . . . . . . . . . . . . . .

. expensive and requires a conductive fluid. . . . . .

. The turbine gives high accuracies and can be used when there is vapor present, but the
. . . . . . . . . . . . . . . .

. turbine is better with clean low viscosity fluids. Table 8. 3 gives a comparison of flow meter
. . . . . . . . . . . . . . . . . .

. characteristics. .

. The general purpose and most commonly used devices are the pressure differential sensors
. . . . . . . . . . . .

. used with pipe constrictions. These devices will give accuracies in the 3 percent range when
. . . . . . . . . . . . . . .

. used with solid state pressure sensors which convert the readings directly into electrical units
. . . . . . . . . . . . .

. or the rotameter for direct visual reading.

. . . . . .
. The Venturi tube has the highest accuracy and least energy loss followed by the flow nozzle
. . . . . . . . . . . . . . .

. and the orifice plate. For cost effectiveness the devices are in the reverse order. If large
. . . . . . . . . . . . . . . . . .

. amounts of particulates are present, the Venture tube is preferred. The differential pressure . . . . . . . . . . . . . .

. devices operate best between 30 and 100 percent of the flow range. The elbow should also
. . . . . . . . . . . . . . . .

. be considered in these applications. Gas flow can be best measured with an anemometer.
. . . . . . . . . . . . . . .

. Solid- state anemometers are now available with good accuracy, are very small in size, and
. . . . . . . . . . . . . . . . .

. are cost effective. . .

. For open channel applications the flume is the most accurate and best if particulates are
. . . . . . . . . . . . . .

. present, but is the most expensive. Particular attention should also be given to
. . . . . . . . . . . . . .

. manufacturers specifications and application notes. . . . .

7.2.1.4.3: Installation
Because of the turbulence generated by any type of obstruction in an otherwise smooth pipe,
. . . . . . . . . . . . . . . .

. attention has to be given to the placement of flow sensors. The position of the pressure taps . . . . . . . . . . . . . . . . .

. can be critical for accurate measurements. The manufacturers recommendations should be

. . . . . . . . . . .

. followed during installation. In differential pressure sensing devices the upstream tap should . . . . . . . . . . . .

. be one to three pipe diameters from the plate or constriction and the down stream tap up to
. . . . . . . . . . . . . . . . .

. eight pipe diameters from the constriction. . . . . .

. To minimize the pressure fluctuations at the sensor, it is desirable to have a straight run of . . . . . . . . . . . . . . . .

. 10 to15 pipe diameters on either side of the sensing device. It may also be necessary to
. . . . . . . . . . . . . . .

. incorporate laminar flow planes into the pipe to minimize flow disturbances and dampening . . . . . . . . . . . .

. devices to reduce flow fluctuations to an absolute minimum. . . . . . . . .

. Flow nozzles may require a vertical installation if gases or particulates are present. To allow
. . . . . . . . . . . . . . .

. gases to pass through the nozzle, it should be facing upwards and for particulates,
. . . . . . . . . . . . . . .

. downwards. .

7.2.1.4.4: Calibration
Flow meters need periodic calibration. This can be done by using another calibrated meter as
. . . . . . . . . . . . . . . .

. a reference or by using a known flow rate. Accuracy can vary over the range of the
. . . . . . . . . . . . . . . . .

. instrument and with temperature and specific weight changes in the fluid, which may all . . . . . . . . . . . . . .

. have to be taken into account. Thus, the meter should be calibrated over temperature as well
. . . . . . . . . . . . . . . . .

. as range, so that the appropriate corrections can be made to the readings. A spot check of the
. . . . . . . . . . . . . . . . . . .

. readings should be made periodically to check for instrument drift that may be caused by the . . . . . . . . . . . . . . .

. instrument going out of calibration, particulate build up, or erosion. . . . . . . . . . . . .

Table 34: Summary of Flow Meter Characteristics
Meter Type
Range Accuracy Percent Comments

Orifice plate Low cost and

3 to 1 3 FSD
accuracy
Venturi tube High cost, good
3 to 1 1 FSD
accuracy, low losses
Flow nozzle Medium cost,
3 to 1 2 FSD
accuracy
Dall tube Medium cost,
3 to 1 2 FSD
accuracy, low losses
Elbow Low cost, losses,
3 to 1 6 10 FSD
sensitivity
Pilot static tube
3 to 1 4 FSD Low sensitivity

Rotameter Low losses, line of

10 to 1 2 of rate
sight
Turbine meter High accuracy, low
10 to 1 2 FSD
losses
Moving vane Low cost, low
5 to 1 10 FSD
accuracy
Electromagnetic Conductive fluid,
30 to 1 0.5 of rate
low losses, high cost
Vortex meter Poor at low flow
20 to 1 0.5 of rate
rates
Strain gauge
3 to 1 2 FSD Low cost, accuracy

Nutating disc
5 to 1 3 FSD High accuracy, cost

Anemometer Low losses, fast

100 to 1 2 of rate
response
7.3: Final Control Elements
. It is the mechanism which alters the value of the manipulated variable in response to the
. . . . . . . . . . . . . . .

. output signal from and automatic controller. In a majority of systems the final control
. . . . . . . . . . . . . .

. element is and automatic control valve which throttles the flow of a manipulative variable.
. . . . . . . . . . . . . .

7.4: Controller (5)

. The job of the controller is to compare the process signal from the transmitter with the set
. . . . . . . . . . . . . . . .

. point signal and to send out an appropriate signal to the control valve. There are three basic
. . . . . . . . . . . . . . . .

. types of controllers which are

. . . .

1) Proportional action which moves the control valve indirect proportional to the
. . . . . . . . . . .

. magnitude of the error. . . .

2) Integral action (reset) which moves the control valve based on the time integral of
. . . . . . . . . . . . . . . .

. the error and the purpose of integral action is to drive the process back to its set point
. . . . . . . . . . . . . . . .

. when it has been disturbed. . . . .

3) Ideal derivative action and its purpose is to anticipate where the process is heading
. . . . . . . . . . . . . .

. by looking at the time a rate of change of the error. This is also known as
. . . . . . . . . . . . . . .

. proportional integral derivative control. . . . .

7.4.1: Modes of Control (5)

. The various types of control are called modes, and they determine type of response obtained.
. . . . . . . . . . . . . . . .

. In other words these describe the action of controller that is the relationship of output of
. . . . . . . . . . . . . .

. output signal to the input or error signal. It must be noted that is error that achieve the
. . . . . . . . . . . . . . . . .

. controller. The four basic mode of control are: . . . . . . . . . .

1. On-off control
2. Integral control
3. Proportional control
4. Rate or derivative control

. In industry purely integral, proportional or derivative modes seldom occur alone in the
. . . . . . . . . . . . .

. control system. .
7.5: Transmitter
. The transmitter is the interface between the process and its control system. The Job of the
. . . . . . . . . . . . . . . .

. transmitter is to convert the sensor signal . . . . . . . (millivolts, mechanical movement, pressure

. . . . . .

. difference etc.) into a control signal 3 to 15 psig air pressure signal, 1 to 5 10 to 50 milli
. . . . . . . . . . . . . . . . . . . . .

. ampere electrical signal etc. . . . .

7.6: Sensors
. The instruments in the process which measures the properties and important variables such
. . . . . . . . . . . .

. as temperature, pressure, flow rate and level is called sensor.

. . . . . . . . . . . .

7.7: Typical Control Systems (6)

7.7.1: Temperature measurement and control
. Temperature measurement is used to control the temperature of outlet and inlet streams in . . . . . . . . . . . . .

. heat exchangers, reactors, etc.

. . .

. Most temperature measurements in the industry are made by means of thermo- couples to
. . . . . . . . . . . . . .

. facilitate bringing the measurements to centralized location. For local measurements at the
. . . . . . . . . . .

. equipment bi- metallic or filled system thermometers are used to a lesser extent. Usually, for
. . . . . . . . . . . . . . . . .

. high measurement accuracy, resistance thermometers are used.

. . . . . .. .

. All these meters are installed with thermo- wells when used locally. This provides protection
. . . . . . . . . . . . . .

. against atmosphere and other physical elements.

. . . . . .

7.7.2: Pressure measurement & control

. Like temperature pressure is a valuable indication of material state and composition. In fact,
. . . . .. . . . . . . . . . .

. these two measurements considered together are the primary evaluating devices of industrial
. . . . . . . . . . .

. materials.

. Pumps, compressor and other process equipment associated with pressure changes in the
. . . . . . . . . . . . .

. process material are furnished with pressure measuring devices. Thus pressure measurement
.. . . . . . . . . . .

. becomes an indication of energy increase or decrease. . . . . . . . . .

. Most pressure measurement in industry is elastic element devices, either directly connected
. . . . . . . . . . . .

. for local use or transmission type to centralized location. Most extensively used industrial
. . . . . . . . . . . . .

. pressure element is the Bourdon Tube or a Diaphragm or Bellows gauges.

. . . . . . . . . . ..

7.7.3: Level measurement & Control

. In an equipment, where an interface exists between the two phases (e. g. liquid- vapor), some
. . . . . . . . . . . . . . . . . . . . .

. means of maintaining the interface at the required level must be provided. This may be
. . . . . . . . . . . . . . . .

. incorporated in the design of the equipment as is usually done for decanters or by automatic
. . . . . . . . . . . . .

. control of the flow from the equipment

. . . . . .

7.7.4: Flow measurement and control

. Flow- indicator- controllers are used to control the amount of liquid. Also all manually set
. . . . . . . . . . . . . . . . .

. streams require some flow indication or some easy means for occasional sample
. . . . . . . . . . .

. measurement. For accounting purposes, feed and product stream are metered. In addition
. . . . . . . . . . . . .

. utilities to individual and grouped equipment are also metered.

. . . . . . . .

. Most flow measures in the industry are/ by Variable Head devices. To a lesser extent
. . . . . . . . . . . . . . . .

. Variable Area is used, as are the many available types as special metering situations arise.
. . . . . . . . . . . . . . . . .

7.8: Control Loops

. For instrumentation and control of different sections and equipments of plants, following
. . . . . . . . . . . .

. control loops are most often used.. . .. . .

1. Feed backward control loop

2. Feed forward control loop

3. Ratio control loop

4. Auctioneering control loop

5. Split range control loop

6. Cascade control loop

7.8.1: Cascade Control Loop of Furnace
. This is a control in which two or more control loops are arranged so that the output of, one
. . . . . . . . . . . . . . . . . . .

. controlling element adjusts the set point of another controlling element. This control loop is
. . . . . . . . . . . . . .

. used where proper and quick control is difficult by simple feed forward or feed backward
. . . . . . . . . . . . . .

. control. Normally first loop is a feedback control loop. We have selected a cascade control
. . . . . . . . . . . . . . . .

. loop for our furnace in order to get quick and proper control.
. . . . . . . . . . . .

7.8.1.1: Primary loop

. Temperature control loop in the furnace instrumentation is the primary control loop because
. . . . . . . . . . . .

it is more sensitive and prone to fluctuation more than gas flow rate.

7.8.1.2: Secondary control loop

Beside outlet temperature of the hydrogen diesel mixture the gas flow rate to the burner is
also a key variable to control.

7.8.1.3: Manipulated variable

Natural gas flow rate is the manipulate variable

7.8.1.4: Control Variable

Outlet temperature of the diesel hydrogen mixture

7.8.1.5: Disturbance
Flow rate fluctuation in the fuel flow rate and fluctuations in the reactor outlet temperature.

T
Diesel + Hydrogen (325oC)

T.T

T.C Set point

F.C F.T

Diesel + Hydrogen (125oC)

Natural Gas

Figure 9: Cascade loop for furnace

7.8.2: Feed Forward Control Loop of Heat Exchanger
. In feed forward control inlet temperature and flow is measured and then a decision be made
. . . . . . . . . . . . . . .

. about how to manipulate the valve to compensate for them. The feed forward controller
. . . . . . . . . . . . . .

. makes the decision about how to manipulate the valve to maintain the controlled variable at
. . . . . . . . . . . . . .

. set point, depending on the inlet temperature and flow.

. . . . . . . . .

7.8.2.1: Manipulated Variable

Flow rate of the desulfurized diesel

7.8.2.2: Control Variable

Outlet temperature of the raw diesel temperature

7.8.2.3: Disturbances
Flow rate of raw diesel, inlet temperature of raw diesel, outlet temperature of desulfurized
diesel.

Raw Diesel

Desulfurized
Diesel

Desulfurized
Diesel

F.T
F

Feed Forward
Control

T.T
T

Raw
Diesel

Figure 10: Feed Forward Control for Heat Exchanger

7.8.3: Selective Control for Reactor

. Selective control is another interesting control strategy used for safety considerations and
. . . . . . . . . . .

. process optimization. In our reactor reaction is exothermic and coolant is used to maintain
. . . . . . . . . . . . . .

. the temperature to avoid catalyst damage. High selector selects the highest temperature
. . . . . . . . . . . .

. among all and action is taken according to it that is adjustment of cooling flow rate to
. . . . . . . . . . . . . . . .

. maintain the temperature.

. . .

7.8.3.1: Manipulated Variable

Flow rate of the quench hydrogen and flow rate of raw diesel.

7.8.3.2: Control Variable

Reactor bed temperature so that run away does not take place.

7.8.3.3: Disturbances
Raw diesel flow rate, and temperature.

Raw
Diesel

F.C Set Point

T
F F.T

T
T.T

T T.T

H.S.S

T
T.T

T.C
T
T.T

Quench H2

Desulfurized Diesel

Figure 11: Control Configuration for Reactor

7.8.4: Ratio Control for Absorber

. A control loop in which, the controlling element maintains a predetermined ratio of one
. . . . . . . . . . . . . .

. variable to another. Usually this control loop is attached to such as system where two
. . . . . . . . . . . . . . .

. different streams enter a vessel for reaction that may be of any kind. To maintain the
. . . . . . . . . . . . . . . .

. stoichiometric quantities of different streams this loop is used so that to ensure proper
. . . . . . . . . . . . .

. process going on in the process vessel.

. . . . . .

7.8.4.1: Variables of the ratio

Flow rates of the gas and lean DEA are the two variables whose ratios control the dynamics
of this loop. The gas stream is called wild stream while the lean DEA stream is called the
controlled stream.

H2

Lean
DEA F

F.T

Ratio
Divider Controller

F.T

H2+ H2S Wild Stream

F

Rich DEA

Figure 12: Ratio control for absorber

7.8.5: Separator

H2 + H2S

Set Point
Set Point
P.C

F.T F.C
P
P.T

Diesel + H2 +H2S

L
L.T

L.C Set Point

Diesel

Figure 13: Control configuration of separator

Cost Estimation & Project
 Chapter #08

8: Cost Estimation & Project Evaluation

.

8.1: PLANT COST ESTIMATION .

. As the final process - design stage is Complete, it becomes possible to make accurate cost
. . . . . . . . . . . . . . . . .

. estimation because detailed equipment specification and definite plant facility information
. . . . . . . . .

. are available. Direct price quotation based on detailed specification can then be obtained
. . . . . . . . . . . . .

. from various manufacturers. However o design project should proceed to the final stages
. . . . . . . . . . . . . .

. before costs are considered and cost estimate should be made through out all the early stages
. . . . . . . . . . . . . . .

. of the design when complete specifications are not available. Evaluation of costs in the
. . . . . . . . . . . . . .

. preliminary design is said predesign cost estimation. Such estimation should be capable of
. . . . . . . . . . . . . .

. providing a basis for company management to decide if further capital should be invested in
. . . . . . . . . . . . . .

. the project.
.
Evaluation of costs in the preliminary design phase is some time called guess estimations. A
. . . . . . . . . . . . . . .

. plant design obviously must present a process that is capable of operating under condition
. . . . . . . . . . . . .

. which will yield a profit. . . . .

. A capital investment is required to any industrial process, and determination of the necessary
. . . . . . . . . . . . . .

. investment is an important part of a plant design project. The total investment for any
. . . . . . . . . . . . . . .

. process consists of the physical. Equipment and facilities in the plant plus the working
. . . . . . . . . . . . . .

. capital for money which must be available to pay salaries keep raw materials and products
. . . . . . . . . . . . . .

. on hand and handle other special items requiring a direct cast out lay.
. . . . . . . . . . .

8.2: CAPITAL INVESTMENTS

. Before an industrial plant can be put into operation, large amount of
. . . . . . . . . . . . .- money must be
. . .

. supplied to purchase and install the necessary machinery and equipment, land and service
. . . . . . . . . . . . .

. facilities must be obtained and the plant- must be erected. Complete with all pipe controls inn
. . . . . . . . . . . . . . . . .

. services. In addition it is necessary to have money available for payment of expenses

. . . . . . . . . . . . . .

. involved in the plant operation. . . . .

. The capital needed to supply the necessary manufacturing and plant facilities is called the
. . . . . . . . . . . . .

. fixed capital investment while the necessary for the operation of the plant is termed as the
. . . . . . . . . . . .

working capital investment.

8.2.1: Working Capital Investment

. The capital which is necessary for the operation of the plant is called working capital
. . . . . . . . . . .

investment.

8.2.2: Fixed Capital Investment

. The capital needed to supply flu- necessary maMiif'acttirini1 and plant facilities is called
. . . . . . . . . . . . .

. fixed capital investment.

. . .

The fixed capital investment classified in to two sub divisions,

a) Direct Cost
b) Indirect Cost
8.2.2.1: Direct Cost

. The direct cost items arc incurred in the construction of the plant in addition to the cost of
. . . . . . . . . . . . . . .

equipment.

a) Purchased Equipment
b) Purchased Equipment Installation
c) Instrumentation and Control
d) Piping
e) Electrical Equipment and Materials
f) Building (Including Services)
g) Yard Improvement
h) Services Facilities
i) Land

8.2.2.2: Indirect Cost

a) Design and Engineering

b) Contractor's Expenses
c) Contractor's Fee
d) Contingency

8.3: Methods Of Estimating Capital Investment

. Various methods are employed for estimating capital investment. The choice of any method
. . . . . . . . . . . . .

. depends on the foil owing-factors,

... . . .

a) Amount of detailed information available

b) Accuracy desired

Five methods of estimating capital investments are outlined,

a) Detailed item estimate

b) Unit estimate
c) Percentage of delivered equipment cost
d) Lang factorial Method
e) Investment cost per capacity
. The accuracy of an estimate depends on the amount of design detail available; and the
. . . . . . . . . . . . . . . . . . .

. accuracy of the cost data available; and the time spent on preparing the estimate. In the early
.. .. . . .. . . . . . . .. . . . . .

. stages of a project only an approximate estimate will be required and justified by the amount
. .. . . . . .. . . . . . . . ..

. of information by then developed. We will go with Lang

. . . . . . . . . .

8.3.1: SUMMARY OF THE FACTORIAL METHOD

. Many variations on the factorial method are used. The method outlined below can be used
. . . . . . . . . . . . . . . . . .

. with the data given in this chapter to make a quick, approximate, estimate of the investment
. . . . . . . . . . . . . . . . .

. need for a project.

. .. .

8.3.1.1: Procedure
a) Prepare material and energy balances, draw up preliminary ow- sheets, size major
. . . . . . . . . . . . . . . .

equipment items and select materials of construction.

. . . . . . . .

b) Estimate the purchase cost of the major equipment items.

. . . . . . . . .

c) Calculate the total physical plant cost (PPC), using the factor available in the
. . . . . . . . . . . . . . . .

literature. .

d) Calculate the indirect costs from the direct costs using the factors available in the
. . . . . . . . . . . . . .

literature. .

e) The direct plus indirect costs give the total xed capital.
. . . . . . . .. . .

f) Estimate the working capital as a percentage of the xed capital; 10 to 20 per cent.
. . . . . . . . . . . . . . . .

g) Add the xed and working capital to get the total investment required.
. . . . . . . . . . . .

8.3.2: Capital Cost Calculation

8.3.2.1: Heat Exchanger Cost

Year = 2004

S = 13.99 m3

a = 24000

b = 46

n = 1.2

PCE = a + b*(S)n

PCE = $ 25090.78
8.3.2.2: Furnace:

Year = 2004

S = 19.422 MW

a = 68500

b = 93000

n = 0.8

PCE = $ 1066479.651

As we have three furnaces

So,

PCE = 3199438.954

8.3.2.3: Reactor:

Year = 2004

From Fig 6.56, we have

Equipment cost = 300*1000

= 300000

Pressure factor = 2.2

Material factor = 2 (S.S)

Total cost = 1320000

Cost of miscellaneous (needing Alumina) = $42/ft3

= $148/m3

So at 720 m3,

Cost of Alumina = $1067095.5

Total reactor cost = 1320000+1067095.5

= $2387095.572

8.3.2.4: Pump:

Year = 2004

S = 74 lit/sec

a = 6900

b = 206

n = 0.9

PCE = $16812.33

8.3.2.5: Stripper:

Year = 2004

From Fig 6.5a

Equipment cost = 85*1000

Material Factor = 1

Pressure Factor = 1

Shell cost = 85000

Plate cost from Fig 6.7a = 1300

Material Factor = 1

Plate cost = 1300

Total cost = 1300+85000

= $86300
8.3.2.6: Absorption Column:

Year = 2004

Equipment cost = 28*1000

Material Factor = 1

Pressure Factor = 1.8

Now, Equipment cost = 50400

Packing cost from Table 6.3

= $960/m3

Volume of Packing = 30 m3

Packing cost = 960*30

= $28800

Total Cost = 28800+50400

= $79200

8.3.2.7: Compressor:

Year = 2004

S = 7858.47 kW

a = 490000

b = 16800

n = 0.6

PCE = 4141842.86

8.3.2.8: Recycle Gas Booster:

Year = 2004

S = 1086 kW

a = 490000

b = 16800

n = 0.6

PCE = $1603799.906

Marshell & Swift cost index 2004 = 1123.6

Marshell & Swift cost index 2011 = 1622.5

% Inflation = ( )

Using average inflation rate as 3.84% we get

Marshell & Swift cost index 2014 = 1622.5*(1.03843)

= 1814.58

Marshell & Swift cost index 2014 = 1814.58

Cost index factor = 1.53

Sr.# Equipment Price in 2004($) Price in 2014($)

1 Heat Exchanger 25090.78 38388.89

2 Furnaces 3199438.954 4895142
3 Reactor 2387095.572 3652256
4 Stripper 86300 132039
5 Absorption Column 79200 121176
6 Compressor 4141842.86 6337020
7 Recycle Gas Booster 1603799.906 2453814
8 Pump 16812.33 25722.86
Total 11539580.4 17655558
Purchased cost of Equipment (PCE) = 17655558

Table 6.1 [1]

Now using Factorial Method, to estimate Direct and indirect cost

Total Physical Plant cost (PPC) = PCE (1+f1+f2+f3+. +f9)

PPC = 17655558(3.40)

= $ 60028897.2

Fixed Capital cost (F) = PPC (1+f10+f11+f12)

= $60028897.2 (1.45)

= 87041900.94

Working Capital cost(W) = 10% of F

= 0.1(87041900.94)

= $ 8704190.094

Total Capital investment(TCI) = W+F

= $8704190.094+ 87041900.94

Total Capital Investment (TCI) = 95746091.03

Operating Cost of the Plant

8.4: OPERATING COSTS

. An estimate of the operating costs, the cost of producing the product, is needed to judge the
. . . . . . . . . . . . . . . . . .

. viability of a project, and to make choices between possible alternative processing schemes.
. . . . . . . . . . . . . . . .

. These costs can be estimated from the ow- sheet , which gives the raw material and service
. . . . . . . . . . . . . . . . .

. requirements , and the capital cost estimate... . . . . . . .

. The cost of producing a chemical product will include the items listed below. They are
. . . . . . . . . . . . . . . .

. divided into two groups.

. . .
8.4.1: Fixed operating costs:
. All those cost that do not vary with production rate. These are the bills that have to be paid
. . . . . . . . . . . . . . . . . . . .

. whatever the quantity produced. These costs include

. . . . . . .

a) . Maintenance (labour and materials). . . . .

b) . Operating labour. .

c) . Laboratory costs. .

d) . Supervision. .

e) . Plant overheads. .

f) . Capital charges. .

g) . Rates (and any other local taxes). . . . .

h) . Insurance. .

i) . Licence fees and royalty payments. . . .

8.4.2: Variable operating costs:

. Costs that are dependent on the amount of product produced. These costs include
. . . . . . . . . .

a) . Raw materials. . .

b) . Miscellaneous operating materials. . .

c) . Utilities (Services). .

d) . Shipping and packaging. . .

. The division into xed and variable costs is somewhat arbitrary. Certain items can be
. . . . . . . . . . . . . .

. classied without question, but the classication of other items will depend on the
. . . . . . . . . . . . .

. accounting practice of the particular organization. The items may also be classied
. . . . . . . . . . . .

. differently in cost sheets and cost standards prepared to monitor the performance of the
. . . . . . . . . . . . .

. operating plant. For this purpose the xed - cost items should be those over which the plant
. . . . . . . . . . . . . . . . .

. supervision has no control, and the variable items those for which they can be held
. . . . . . . . . . . . . .

. accountable. . .

. The costs listed above are the direct costs of producing the product at the plant site. In
. . . . . . . . . . . . . . . .

. addition to these costs the site will have to carry its share of the Companys general
. . . . . . . . . . . . . . .

. operating expenses. These will include: . . . . .

a) . General overheads. .

b) . Research and development costs. . . .

c) . Sales expense. . .

d) . Reserves. . .

. How these costs are apportioned will depend on the Companys accounting methods. They
. . . . . . . . . . . . . .

. would add about 20 to 30 per cent to direct production costs at the site.
. . . . . . . . . . . . .
8.5: Estimation of operating cost
. In this section the components of the xed and variable costs are discussed and methods
. . . . . . . . . . . . . . .

. given for their estimation. It is usually convenient to do the costing on an annual basis.
. . . . . . . . . . . . . . . .

8.5.1: Raw materials

. These are the major (essential) materials required to manufacture the product. The quantities
. . . . . . . . . . . . . . .

. can be obtained from the ow- sheet and multiplied by the operating hours per year to get the
. . . . . . . . . . . . . . . . . .

. annual requirements. The price of each material is best obtained by getting quotations from
. . . . . . . . . . . . . .

. potential suppliers, but in the preliminary stages of a project prices can be taken from the
. . . . . . . . . . . . . . . .

. literature. . .

. The American journal Chemical Marketing Reporter, CMR (2004), publishes a weekly
. . . . . . . . . . . .

. review of prices for most chemicals. The prices for a limited number of chemicals in Europe
. . . . . . . . . . . . . . . .

. can be found in European Chemical News, ECN (2004). U. S. prices, converted to the local
. . . . . . . . . . . . . . . . . . . .

. currency at the current rate of exchange, can be used as a guide to the probable price in other
. . . . . . . . . . . . . . . . . . .

. countries. .

8.5.2: Miscellaneous materials (plant supplies)

. Under this heading are included all the miscellaneous materials required to operate the plant
. . . . . . . . . . . . . .

. that are not covered under the headings raw materials or maintenance materials.
. . . . . . . . . . . .

. Miscellaneous materials will include: . ... .

a) . Safety clothing: hard hats, safety glasses etc. . . . . . . .

b) . Instrument charts and accessories . .

c) . Pipe gaskets .

d) . Cleaning materials .

An accurate estimate can be made by detailing and costing all the items needed, based on
. . . . . . . . . . . . . . . .

. experience with similar plants. As a rough guide the cost of miscellaneous materials can be . . . . . . . . . . . . . . .

. taken as 10 per cent of the total maintenance cost.

. . . . . . . . .

8.5.3: Utilities (services)

. This term includes, power, steam, compressed air, cooling and process water, and efuent
. . . . . . . . . . . . . . . .

. treatment; unless costed separately. The quantities required can be obtained from the energy
. . . . . . . . . . . . . .

. balances and the ow - sheets. The prices should be taken from Company records, if . . . . . . . . . . . . . . . . .

. available. They will depend on the primary energy sources and the plant location. The
. . . . . . . . . . . . . .

. gures given in Table 6. 5 can be used to make preliminary estimates. The current cost of
. . . . . . . . . . . . . . . . . .
. utilities supplied by the utility companies: electricity, gas and water, can be obtained from
. . . . . . . . . . . . . . .

. their local area ofces. . . . .

8.5.4: Shipping and packaging

. This cost will depend on the nature of the product. For liquids collected at the site in the
. . . . . . . . . . . . . . . . .

. customers own tankers the cost to the product would be small; whereas the cost of . . . . . . . . . . . . . . . .

. packaging and transporting synthetic bers or polymers to a central distribution warehouse . . . . . . . . . .

. would add signicantly to the product cost. . . . . . . . .

8.5.5: Maintenance
. This item will include the cost of maintenance labour, which can be as high as the operating
. . . . . . . . . . . . . . . . .

. labour cost, and the materials (including equipment spares) needed for the maintenance of
. . . . . . . . . . . . . . .

. the plant. The annual maintenance costs for chemical plants are high, typically 5 to 15 per
. . . . . . . . . . . . . . . . .

. cent of the installed capital costs. They should be estimated from a knowledge of the
. . . . . . . . . . . . . .

maintenance costs on similar plant. As a rst estimate the annual maintenance cost can be . . . . . . . . . . . . . .

taken as 10 per cent of the xed capital cost; the cost can be considered to be divided evenly
. . . . . . . . . . . . . . . . . . .

. between labour and materials. . . .

8.5.6: Operating labour

. This is the manpower needed to operate the plant: that directly involved with running the
. . . . . . . . . . . . . .

. process. The costs should be calculated from an estimate of the number of shift and day
. . . . . . . . . . . . . .

. personnel needed, based on experience with similar processes. It should be remembered that . . . . . . . . . . . .

. to operate three shifts per day, at least ve shift crews will be needed. The gures used for
. . . . . . . . . . . . . . . . . .

. the cost of each man should include an allowance for holidays , shift allowances, national . . . . . . . . . . . . .

. insurance, pension contributions and any other overheads. The current wage rates per hour in . . . . . . . . . . . . . .

. the UK chemical industry (mid- 2004) are 15- 20, to which must be added up to 50 per cent
. . . . . . . . . . . . . . . . . . . . . . .

. for the various allowances and overheads mentioned above. Chemical plants do not normally
. . . . . . . . . . . .

. employ many people and the cost of operating labour would not normally exceed 15 per cent
. . . . . . . . . . . .. . .

of the total operating cost. The direct overhead charges would add 20 to 30 per cent to this
. . . . . . . . . . . . . . . . . .

. gure. Wessel (1952) gives a method of estimating the number of man- hours required based
. . . . . . . . . . . . . . . . . .

. on the plant capacity and the number of discrete operating steps.

. . . . . . . . .

8.5.7: Supervision
. This heading covers the direct operating supervision: the management directly associated
. . . . . . . . .

. with running the plant. The number required will depend on the size of the plant and the
. . . . . . . . . . . . . . . .

. nature of the process. The site would normally be broken down into a number of manageable
. . . . . . . . . . . . . . . .
units. A typical management team for a unit would consist of four to ve shift foremen, a
. . . . . . . . . . . . . . . .

. general foreman, and an area supervisor (manager) and his assistant. The cost of supervision
. . . . . . . . . . . . . . . . .

. should be calculated from an estimate of the total number required and the current salary
. . . . . . . . . . . . .

. levels, including the direct overhead costs. On average, one supervisor would be needed
. . . . . . . . . . . . . . .

. for each four to ve operators. Typical salaries, mid- 2004, are 20, 000 to 45, 000, . . . . . . . . . . . . . . . . . . .

. depending on seniority. An idea of current salaries can be obtained from the salary reviews . . . . . . . . . . . . . .

. published periodically by the Institution of Chemical Engineers. . . . . . . . .

8.5.8: Laboratory costs

. The annual cost of the laboratory analyses required for process monitoring and quality
. . . . . . . . . . . .

. control is a signicant item in most modern chemical plants. The costs should be calculated
. . . . . . . . . . . . . . .

. from an estimate of the number of analyses required and the standard charge for each
. . . . . . . . . . . . . .

. analysis, based on experience with similar processes. As a rough estimate the cost can be
. . . . . . . . . . . . . . .

. taken as 20 to 30 per cent of the operating labour cost, or 2 to 4 per cent of the total
. . . . . . . . . . . . . . . . . .

. production cost. .

8.5.9: Plant overheads

. Included under this heading are all the general costs associated with operating the plant not
. . . . . . . . . . . . . . .

. included under the other headings; such as, general management, plant security, medical, . . . . . . . . . . . . . . .

. canteen, general clerical staff and safety. It would also normally include the plant technical
. . . . . . . . . . . . . .

. personnel not directly associated with and charged to a particular operating area. This group . . . . . . . . . . . . . .

. may be included in the cost of supervision, depending on the organizations practice. The
. . . . . . . . . . . .

. plant overhead cost is usually estimated from the total labour costs: operating, maintenance
. . . . . . . . . . . . .

. and supervision. A typical range would be 50 to 100 per cent of the labour costs; depending
. . . . . . . . . . . . . . .

. on the size of the plant and whether the plant was on a new site, or an extension of an
. . . . . . . . . . . . . . . . .

. existing site. .

8.5.10: Capital charges

The investment required for the project is recovered as a charge on the project. How this
. . . . . . . . . . . . . . . .

. charge is shown on an organizations books will depend on its accounting practices. Capital
. . . . . . . . . . . . . .

. is often recovered as a depreciation charge, which sets aside a given sum each year to repay
. . . . . . . . . . . . . . .

. the cost of the plant. If the plant is considered to depreciate at a xed rate over its
. . . . . . . . . . . . . . . . . .

. predicted operating life, the annual sum to be included in the operating cost can be easily . . . . . . . . . . . . . . .

. calculated. The operating life of a chemical plant is usually taken as 10 years , which gives a . . . . . . . . . . . . . . . . . .

. depreciation rate of 10 per cent per annum. The plant is not necessarily replaced at the end . . . . . . . . . . . . . . . . .
. of the depreciation period. The depreciation sum is really an internal transfer to the
. . . . . . . . . . . . . .

. organizations fund for future investment. If the money for the investment is borrowed, the . . . . . . . . . . . . . .

. sum set aside would be used to repay the loan. Interest would also be payable on the loan at
. . . . . . . . . . . . . . . . .

. the current market rates. Normally the capital to nance a particular project is not taken as a
. . . . . . . . . . . . . . .

. direct loan from the market but comes from the companys own reserves. Any interest . . . . . . . . . .

charged would, like depreciation, be an internal (book) transfer of cash to reect the cost of
. . . . . . . . . . . . . . . . .

. the capital used. Rather than consider the cost of capital as depreciation or interest, or any
. . . . . . . . . . . . . .

. other of the accounting terms used, which will depend on the accounting practice of the
. . . . . . . . . . . . .

. particular organization and the current tax laws, it is easier to take the cost as a straight, . . . . . . . . . . . . . . . .

. unspecied, capital charge on the operating cost. This would be typically around 10 per cent . . . . . . . . . .

. of the xed capital, annually, depending on the cost of money. As an approximate estimate
. . . . . . . . . . . . . .

the capital charge can be taken as 2 per cent above the current minimum lending rate. For
. . . . . . . . . . . . . .

. a full discussion on the nature of depreciation and the cost of capital see Happle and Jordan
. . . . . . . . . . . . . .

( 1975), Holland et al. (1983), Valle-Riestra (1983).

.. .. . . . . . . . . . . . .

8.5.11: Local taxes

. This term covers local taxes, which are calculated on the value of the site. A typical gure
. . . . . . . . . . . . . . . . . .

. would be 1 to 2 per cent of the xed capital. . . . . . . . . . .

8.5.12: Insurance
. The cost of the site and plant insurance: the annual insurance premium paid to the insurers;
. . . . . . . . . . . . . . . . . .

. usually about 1 to 2 per cent of the xed capital. . . . . . . . . .

8.5.13: Royalties and licence fees

. If the process used has not been developed exclusively by the operating company, royalties
. . . . . . . . . . . . .

. and licence fees may be payable. These may be paid as a lump sum, included in the xed
. . . . . . . . . . . . . . . . . .

. capital, or as an annual fee; or payments based on the amount of product sold. The cost
. . . . . . . . . . . . . . .

. would add about 1 per cent to 5 per cent to the sales price. . . . . . . . . . . . .

8.6: Summary of production costs

. The various components of the operating costs are summarized below. The typical values
. . . . . . . . . . . . .

. given here can be used to make an approximate estimate of production costs.

. . . . . . . . . . . .

8.6.1: Variable costs

Typical values

1. Raw materials From ow-sheets

2. Miscellaneous materials 10 per cent of item (5)

3. Utilities From ow-sheet

4. Shipping and packaging Usually negligible

Sub-total A ....................................

8.6.2: Fixed costs

5. Maintenance 5-10 per cent of xed capital

6. Operating labour From manning estimates

7. Laboratory costs 20-23 per cent of 6

8. Supervision 20 per cent of item (6)

9. Plant overheads 50 per cent of item (6)

10. Capital charges 10 per cent of the xed capital

11. Insurance 1 per cent of the xed capital

12. Local taxes 2 per cent of the xed capital

13. Royalties 1 per cent of the xed capital

Sub-total B ......................

Direct production costs A+B ......................

13. Sales expense 20-30 per cent of the direct

14. General overheads production cost Negligible

15. Research and development Negligible

Sub-total C .....................

Annual production cost = A+B+C

Production cost $/kg =

8.7: Total Production Cost Calculation
8.7.1: Variable cost
8.7.1.1: Raw material cost
Basis = Per year

Hydrogen

Hydrogen required = 5879 kg/hr

= 4.656*107 kg/year

Hydrogen production cost = $ 4.5/kg

Total hydrogen price = $2.095*108

Total Raw material = 2.095*108

8.7.1.2: Miscellaneous Costs

= (0.1)(Maintenance cost)

= 0.1( 6.53*106)= 6.53*105

8.7.1.3: Utility cost

= 0.1(TCI)

= 0.1(95746091.03)

= 9574609.103

8.7.1.4: Shipping and Packaging

= usually Negligible

Total variable cost = 2.192*108

8.7.2: Fixed Costs

8.7.2.1: Maintenance cost
= (0.075*87041900.94 = 6.53*106

8.7.2.2: Operating labor cost

= 0.1 (TCI) = 0.1(95746091.03)
 =9574609.103

8.7.2.3: Laboratory cost

= 0.22(Operating labor cost)

=0.22(9574609.103)

= 2.11*106

8.7.2.4: Supervision cost

= 0.2(Operating labor cost)

= 0.2*(9574609.103)

= 1.914*106

8.7.2.5: Plant overhead

= 0.5(Operating labor)

= 0.5(9574609.103)

= 4.79*106

8.7.2.6: Capital Charge

= 0.1( F)

= 0.1( 87041900.94)

=8704190.094

8.7.2.7: Insurance
= 0.01(F)

= 0.01(87041900.94)

=870419.0094

8.7.2.8: Local taxes

= 0.02(F)

= 0.02(87041900.94)

= 1.74*106
8.7.2.9: Royalties and License fee
= 0.01(F)

= 0.01(87041900.94)

= 870419.0094

Fixed cost = 3.71*107

Direct production cost = Variable costs + fixed costs

Direct production cost (DPC) =2.192*108 +3.71*107

= $2.56*108

8.7.2.10: Sale Expenses

Sales Expenses = 0.25*(DPC)

=0.25*(2.56*108)

= 6.4*107

8.7.2.11: General overheads

= Negligible

8.7.2.12: Research & development

= Negligible

Annual Production cost = 2.56*108 + 6.4*107= $3.2*108

8.8: Project Evaluation

8.8.1: Processing cost per liter
$ 3.2*108 Hr 1 day 1 year 1bbl
Year 1666.67bbl 24 hr 330day 159liter

Processing cost per liter = $0.1524

8.8.2: Profit Per liter

Raw diesel price (2000ppm) = Rs.83.42/liter

= $ 0.82/liter
Production cost per liter = 0.82+ 0.1524

= $0.9724/liter

Market Price in High speed diesel (50ppm) = Rs 107/liter

= $ 1.0523/liter

Profit per liter = 1.0523-0.9724

= $0.07992/liter

8.8.3: Total Profit Annually

Total profit annually = 1.6769*108

8.8.4: Cash Flow Diagram

0 1 2 3 4

4.15*108 1.677*108 1.677*108 1.677*108 1.677*108

Figure 14: Cash flow diagrm

8.8.5: Pay Back Period

Pay Back period =

8.8.6: Discounted Pay Back Period

Interest rate = 10%

0 1 2 3 4

10%

4.15*108

4.15*108 1.525*108 1.39*108 1.26*108 1.15*108

Discounted Pay Back period = 2+

Hence the payback period is less than five year so the project is feasible.

8.8.7: Net positive value

Add all the four net cash flows based on 10 % interest rate and subtract it from the initial
investment.

NPV = 5.31549*108-4.15746*108

= 1.158*108

As the value is positive so the project is feasible.

8.8.8: Profitability index

P.I =

8.8.9: Book value of the plant

Reducing Balance method

n V R Vn Dn
0 9.60*107 0.1 96000000 0
1 --- --- 86400000 9600000
2 --- --- 77760000 8640000
3 --- --- 69984000 7776000
4 --- --- 62985600 6998400
5 --- --- 56687040 6298560
6 --- --- 51018336 5668704
7 --- --- 45916502 5101834
8 --- --- 41324852 4591650
9 --- --- 37192367 4132485
10 --- --- 33473130 3719237
 Environmental

Impact Assessment
 Chapter # 09

9: Environmental Impact Assessment

9.1: Purpose of This Document

. This Environmental Impact Report (EIR) is an informational document intended to disclose
. . . . . . . . . .

. to the public and decision- makers the environmental consequences of the proposed Pak-
. . . . . . . . . . . . .

. Arab Refinerys Ultra Low Sulfur Diesel (USLD)/ Strategic Modernization Project. This
. . . . . . . . . . . . .

. document assesses the environmental impacts due to the project, as well as the cumulative
. . . . . . . . . . . . .

. environmental impacts in the vicinity of the project area. The Pakistan Environmental
. . . . . . . .

. Protection Agency requires potential environmental impacts of proposed projects be

. . . . . .

evaluated, and that feasible methods to reduce, avoid, or eliminate identified significant
. . . . . . . . . . . .

. adverse impacts of these projects be included as part of the project. This document is . . . . . . . . . . .

. intended as an information document that, in itself, does not determine whether a project will
. . . . . . . . . . . .

be approved, but aids in the local planning and decision-making process.

. . . . . . . . . ..

9.2: Project Overview

. As already described in chapter one that in December 2000, the United States Environmental
. . . . . . . . . .

. Protection Agency (U. S. EPA) promulgated regulations requiring that the sulfur content in
. . . . . . . . . . . .

. motor vehicle diesel fuel be reduced from 500 ppm to 15 ppm by June 1, 2006. This diesel
. . . . . . . . . . . . . .
. fuel, referred to as Ultra Low Sulfur Diesel or ULSD, is a motor fuel that has been processed
. . . . . . . . . . . . . . .

in a manner that removes an extremely high proportion of the sulfur bearing compounds that
. . . . . . . . . . .

. otherwise would result in air pollutant emissions when combusted. The ULSD component of .. . . . . .. . . .

. the proposed Project, in this regard, would allow Pak- Arab Refinery to meet this challenge. . . . . . . . . . . . . . . .

. Thus, a primary objective of the Project is to produce ultra low-sulfur diesel fuels as required
. . . . . . . . . . . . . . . .

by the PEPA as well. All project elements are scheduled to be ready for tie- in and startup as
. . . . . . . . . . . . . . . .

. soon as possible to compete with the modern world and also with our neighbor country
. . . . . . . . . .

. India.

The Project would implement a series of modifications and additions focused on three
objectives:
a) Produce diesel containing less than 15 parts per million (ppm) sulfur.
b) Allow the Refinery to efficiently use a broader array of crude oil as feedstock.
c) Improve Refinery efficiency and increase crude throughput capacity. As a result of
this change, gasoline production levels would be maintained at current levels and
there would be an increase in diesel production.
. The Project components would consume 194 gallons per minute of freshwater for cooling
. . . . . . . . . .

. tower service in the new hydrotreater, and would increase Refinery wastewater flows to the . . . . . . . . . .

. water treatment plant by 60 gallons per minute. As a part of the Project, we propose
. . . . . . . . . . . . .

. concurrent reductions in fresh water use at the Refinery (a reduction of 200 gallons per
. . . . . . . . . . . .

minute). The result would be no net increase in freshwater consumption or wastewater flow .
. . . . . . . . . . . ..

. Electrical power consumption at the Refinery would approximately increase by 5. 5

. . . . . . . . .

. megawatt . (MW); the additional power would be generated in the facilitys on- site
. . . . . . . . . .

. cogeneration plant or purchased from WAPDA . Normal operations would produce small . . . . . . . . .

. quantities of hazardous waste (selenium cake, copper cake and oily contaminated material). . . . . . . . . . . . .

. In addition, relatively small amounts (40 cubic yards) of hazardous waste will be created
. . . . . . . . . . . . .

during periodic maintenance turnarounds. . . . .

. The Project involves the construction and modification of facilities and equipment to
. . . . . . . . .

. produce ULSD fuel to comply with regulatory requirements. The Project also involves
. . . . . . . . .

. Strategic

. Modernization upgrades that will allow the Refinery to use a broader array of domestic crude . . . . . . . . . . . .

oils, including those with higher sulfur content, provide additional operating flexibility and
. . . . . . . . .

. efficiency.
The Project includes the following additions and modifications:

a) Construct a new ULSD hydrotreater on the site of a previously demolished Refinery

unit to provide 30,000 barrels per day of blended diesel product that meets the new
regulatory requirements.
b) Improve the efficiency of the existing sulfur recovery plants by adding oxygen
enrichment facilities.
c) Construct a new sour water stripper to accommodate the increased volumes of sour
water produced.
d) Modify the amine stripper to increase the capacity to scrub sulfur from Refinery fuel
gas.
e) Construct caustic treatment units at the fuel gas center to remove sulfur from fuel gas
used to fire new heaters.
f) Modify the crude/coker unit; primarily replace and upgrade the existing atmospheric
crude distillation tower and existing vacuum distillation tower (both of which are at
the end of their operating lives), and install a new furnace to preheat the feed to the
vacuum tower.
g) Modify the existing crude distillation unit to add pumps and piping to gather sour
water from existing processing units and to reroute unit production streams.
h) Convert the existing diesel hydrotreater, if any, to a light naphtha hydrotreater as part
of the reconfiguration of facilities made possible by the new ULSD hydrotreater and
modify auxiliary equipment to support the above process unit changes, such as new
piping and relief systems outside the new/modified units, and utility modifications to
support the new hydrotreater.
i) Install Cooling Tower controls (reduce cooling tower cycles).

. The incremental crude oil that would be processed at the Refinery as a result of the proposed
. . . . . . . . . . . .

facilities would generally be imported and transported to the Refinery by an existing

. . . . . . . . . .

pipeline. The Project would involve very small increases in vehicle, rail, and barge traffic.
. . . . . . . . . . . . .

. The Project would create one additional full- time position (4 to 5 employees ) at the
. . . . . . . . . . . . .

Refinery. .

. The Project would require a 16 - month construction period. During the six - month peak
. . . . . . . . . . . .

. period of construction, there would be an average construction workforce of approximately

. . . . . . . . .

. 570 people. With the exception of the new sour water stripper, project construction would
. . . . . . . . . .
. take place entirely on sites previously or currently used for Refinery activities. Thus, the
. . . . . . . . . . .

. Project would involve minimal grading and modifications to existing storm water drainage
. . . . . . . . . .

. systems.

9.3: Key Areas of Environmental Concern

. This study examined the potential impacts of the proposed project. All of the topics in the
. . . . . . . . . . . .

. current PEPA Checklist were studied: Aesthetics, Air Quality, Agriculture Resources ,
. . . . . . . . . . .

. Biological Resources, Cultural Resources, Energy, Geology and Soils, Hazards and . . . . . . . . . .

. Hazardous Materials, Hydrology and Water Quality, Land Use and Planning, Mineral
. . . . . . . . . .

. Resources, Noise, Population and Housing, Public. . . . . . . Services, Parks and Recreation, . . .

. Transportation/ Traffic, and Utilities and Service Systems.

. . . . .. . .

9.4: Organization of the Document

This document is organized into the following sections:

9.4.1: Summary of Environmental Impacts:

. Summarize environmental impacts that would result from implementation of the proposed
. . . . . . . .

. project. The summaries indicate the level of significance of those impacts

. . . . . . . . . . .

9.4.2: Environmental Settings, Impacts and Mitigation Measures:

. Contain an analysis of environmental issue areas. Discussion of each issue area is divided
. . . . . . . . . . . .

. into:

a) The setting, which describes environmental conditions and regulatory information;

b) The standards of significance for determining the degree or level of potential

environmental impacts for each issue;

c) Potential impacts, which indicate the environmental effects that are anticipated from the
proposed project,

d) Mitigation.

9.4.3: Alternatives
Describes the alternatives to the proposed project and lists their associated environmental
effects.
9.5: Summary of Environmental Impacts

9.5.1: Summary of Impacts of the Proposed Project

. This section provides a summary of the environmental impacts of the proposed Ultra Low
. . . . . . . . .

. Sulfur Diesel (ULSD )/Strategic Modernization Project, as developed during this analysis.
. . . . . . . . . .

. The impacts of the proposed Project and the mitigation measures that are included as a part
. . . . . . . . . . .

. of the proposed project have been extracted from the analyses and evaluations presented. To
. . . . . . . . . .

assist readers with a brief overview of the results of the analysis contained in this document,
. . . . . . . . . . . . .

Section 9.2. 2 presents summary statements of impacts from each environmental area of
. . . . . . . . . . . . .

. study. Each summary statement is a formal statement of impact and proposed mitigation as
. . . . . . . . . .

. well as level of significance before and after mitigations is applied.

. . . . . . . . . .

9.5.2: Review of Proposed Project Impacts

9.5.2.1: Aesthetics, Visual Quality, Light and Glare

. . Placement of the new facilities and modification of other existing facilities would result in
. . . . . . . . . .

. physical changes at the existing Refinery. Although noticeable changes in aesthetics and . . . . . . . . .

. visual quality would occur, the aesthetic, visual and glare impacts of the proposed . . . . . . . . . .

. ULSD/Strategic Modernization Project would be less than significant. No mitigation would

. . . . . . . . . . . .

. be required.
.

The visual and aesthetic changes are summarized as follows:

a) The new equipment and facilities of the Project could be seen from public view
corridors. Project operations could cause increases in the frequency and/or magnitude
of flaring events and water vapor plumes at the Refinery. In addition, the Proposed
Projects new facilities could introduce new lighting on-site.

9.5.2.2: Air Quality

. The construction and implementation of the proposed Project would lead to impacts on both . . . . . . . . . .

. the local and regional air quality. The Project would lead to two potentially significant
. . . . . . . . . . . .

. impacts. .

a) Construction of the project could cause local air quality impacts from fugitive dust
and emissions.
 b) Operational activities associated with the implementation of the Project would
increase air pollutant emissions by potentially significant values.
. With the implementation of proposed mitigation measures, both construction and operational
. . . . . . . .

. impacts of the proposed Project on the regional and local air quality would be reduced to a
. . . . . . . . . . .

. less than significant level.

. . .

9.5.2.3: Biological Resources

. Placement of the new facilities and modification of other existing facilities could result in the
. . . . . . . . . .

. following impacts on biological resources:

. . . .

a) Increased ship traffic associated with increased refinery capacity has a small but
present potential to result in accidental releases of toxic materials in Arabian Sea that
may affect the waters there, as well as nearby wetlands.
These impacts can be reduced to less than significant levels with the implementation of
the proposed mitigation measures.

9.5.2.4: Cultural Resources

. Construction of the Project facilities may cause substantial adverse changes to the . . . . . . . . .

significance of currently unknown cultural resources. This potentially significant impact

. . . . . . . .

. would be reduced to less than significant by standard mitigation measures and legal
. . . . . . . . .

. requirements.

9.5.2.5: Energy
. The Project, as proposed, would not encourage activities that result in the use of large
. . . . . . . . . . . .

. amounts of fuel or energy, nor would it use fuel or energy in a wasteful or inefficient
. . . . . . . . . . . .

. manner. The overall impact of the proposed Project on energy resources would be less than
. . . . . . . . . . .

. significant. The net increase in electrical energy would be approximately 5. 5 MW. This
. . . . . . . . . . . . .

. power would be supplied from the onsite cogeneration Project or purchased from WAPDA
. . . . . . . . . .

. as already described. . . .

In addition, the additional heat input for these processes would typically be provided by
. . . . . . . . . . . .

. refinery gas, but under some supply or market conditions, natural gas would be used to
. . . . . . . . . . . . . . .

. supplement the use of refinery gas at these facilities. . . . .. . . . .

9.5.2.6: Geology, Soils and Seismicity
. Several potential impacts related to geology, soils, and seismicity are identified for the
. . . . . . . . . . . .

. ULSD Project. Each of these impacts would be reduced to less than significant by prescribed
. . . . . . . . . . .

. mitigation measures. Effects that could occur as a result of the implementation of the Project
. . . . . . . . . . . . .

are: . .

a) Facilities would be exposed to expansive soils and natural settlement.

b) In the event of a major earthquake in the region, seismic ground shaking could
potentially injure persons at the project site due to structural damage of facility
structures. Ground shaking could potentially expose persons and property to seismic-
related hazards, including localized liquefaction, earthquake-induced land sliding and
seismically induced settlement.
The potentially significant impacts would be reduced to less than significant by compliance
. . . . . . . . . .

. with applicable rules and regulations, and incorporation of proposed mitigation measures.
. . . . . . . . . .

9.5.2.7: Public Health

. Public exposure to toxic air contaminant (TAC) emissions from the Project can result in an
. . . . . . . . . . . .

. increase in health risks. However, the incremental health risks from the Project are extremely
. . . . . . .. . . . . .

. small when compared to typical day- to- day health risks. Since the predicted health risk
. . . . . . . . . . . . . .

. increments from the Project are less than the significance thresholds, the impacts are less
. . . . . . . . . . .

. than significant. No additional mitigation measures would be required.

. . . . . . .. .

9.5.2.8: Public Safety

. The risks to public safety from potential accidents from the proposed Project are low , and the
. . . . . . . . . .. .

. impacts from plausible accidental releases would be less than significant. Possible accidental
. . . . . . . . . .

. releases of acutely hazardous substances that might result from the Proposed Project were
. . . . . . . . . .

evaluated, and none were found to cause an unhealthful offsite impact and occur within the
. . . . . . . . . . . .

. expected 30-year life of the plant. No additional mitigation measures would be needed.
. . . . . . . . . . . ..

9.5.2.9: Hydrology and Water Quality

. The proposed Project could result in an increase of pollutants in the process wastewater . . . . . . . . . .

stream. The refinery is required to adequately treat the increase in effluent contaminants to
. . . . . . . . . . .

avoid exceeding discharge limits. In addition, operation of some Project units would produce
. . . . . . . . . . .

. additional wastewater and construction activities could generate wastewater and storm water
. . . . . . . .

. runoff volumes that could increase wastewater inflow into the Refinery wastewater treatment
. . . . . . . . .
. plant. Conservation measures are proposed as part of the Project to yield no net increase in
. . . . . . . . . . . . .

. wastewater or discharge. This resulting wastewater volume would not exceed the maximum
. . . . . . . . .

. hydraulic capacity or available retention capacity of the wastewater treatment plant at the
. . . . . . . . . . .

. Refinery. The potentially significant impacts would be reduced to less than significant by
. . . . . . . . . . .

standard mitigation measures and legal requirements. No additional mitigation measures

. . . . . . . . . .

. would be required. . .

9.5.2.10: Land Use, Plans and Policies

All land use effects of the Project either would be less than significant or would result in no
impact. No mitigation is required.

a) Project construction may result in temporary secondary impacts to adjacent industrial

uses and nearby residences.
b) The Project would not conflict with established plans, policies and ordinances.
c) The Project would not potentially divide an established community.
d) The Project would not affect a habitat conservation plan or natural community plan.

9.5.2.11: Noise
. . The Project would impact the ambient noise environment during both the construction and
. . . . . . . . . .

. operational phases of the Project. Since the Project would be located on refinery property,
. . . . . . . . . . .

. Project-related noise impacts would primarily be to offsite residential receptors. Noise during
. . . . . . . . . .

. construction of the proposed Project would temporarily increase the ambient noise levels at
. . . . . . . . . . .

. the residential receptors to levels above those specified in the Pak EPA standards. This
. . . . . . . . . . .

. impact would be mitigated to a less than significant level with the incorporation of the
. . . . . . . . . . . . . .

. proposed mitigation measures. . . .

9.5.2.12: Public Services

. This review concludes since there was no Initial Study that all effects related to the
. . . . . . . . . . .

. implementation of the Project would be less than significant. No mitigation would be

. . . . . . . . . .

. required.

a) The Project would not adversely affect the ability of the Fire Department to provide
fire suppression and emergency response services to the refinery.
b) The Project would not adversely affect the Police Office ability to provide police
protection services to the Project site and area as a whole.
 c) The proposed Project would not substantially degrade the quality of existing park and
recreation facilities or require the provision of new or expanded facilities.
d) The proposed Project would not adversely affect other public services such as
libraries or hospitals.

9.5.2.13: Transportation
. The construction phase of the Project during the major turnaround (which includes both the . . . . . . . . . . .

turnaround and the Project construction traffic) at the Refinery would generate additional
. . . . . . . . .

. daily and peak hour trips.

. . . .

a) The proposed construction phase of the Project would result in a potentially

. . . . . . . .

. significant impact to the a.m. peak hour operations during peak Project construction.
. . . . . . . . . . . .

. Operation of the Project would add up to four to five new employees, generating up to two
. . . . . . . . . . . . .

new a. m. peak hour trips, and two p.m. peak hour trips. The project will increase operational
. . . . . . . . . . . . . . . . . .

. truck traffic for coke, sulfur and waste trucking.

. . . . . . . .

9.5.2.14: Utilities and Service Systems

. The implementation of the Project would not result in an incremental increase in refinery
. . . . . . . . . .

. raw water demand. The Project would have less than significant effects on the other utilities
. . . . . . . . . . .

. and services systems:

. . .

a) The Project would not cause wastewater effluent discharges to exceed wastewater
quality limitations of the Regional Water Quality Control Board.
b) Implementation of the proposed Project would not substantially increase the amount
of wastewater treated at the wastewater treatment plant.
c) The proposed Project would slightly increase the quantity of spent catalyst and sludge
from the refinery wastewater treatment plant.
No mitigation would be required for effects on other utilities and services systems.

9.5.2.15: Agriculture
. The Project is located entirely within the developed area of the Refinery . There are no
. . . . . . . . . . . .

. agricultural resources on or in the vicinity of the project site. All construction and operation . . . . . . . . . . . .

activities would take place in the already developed portions of refinery property. Thus, the
. . . . . . . . . . .

. Projects impact on agricultural land use would be less than significant. The project would . . . . . . . . . . .

. have no impact. No mitigation measures are required.

. . . . . . . .
9.5.2.16: Mineral Resources
There are no mineral resources mapped within the vicinity of the Refinery. Therefore,
. . . . . . . . . . .

. implementation of the Project would not result in the loss of availability of a locally . . . . . . . . . . .

. important mineral resource recovery site delineated on a local General Plan Maps.
. . . . . . . . . . .

9.5.2.17: Population and Housing

. Housing or population would not be displaced as a result of the ULSD / Strategic
. . . . . . . . . . . .

Modernization Project, nor would population growth be stimulated. For these reasons, there . . . . . . . . . . .

. would be no significant Project impacts on population or housing. It is anticipated that up to

. . . . . . . . . . . .

. 4 or 5 new permanent employees would be required in the long-term operation of the

. . . . . . . . . . . . .

Project. This increase in employment at the Refinery would be a less than significant impact.
. . . . . . . . . . . . . .

. No mitigation would be required.

. . . . .

9.5.2.18: Parks and Recreation

. The ULSD/Strategic Modernization Project would have no impact on lands designated for
. . . . . . . . .

. Park and Recreation use. There are no Parks or Recreation facilities on or in the vicinity of
. . . . . . . . . . . . . .

. the project site. No mitigation measures are required. . . . . . . .

9.6: Environmental Setting, Impacts and Mitigation

. To achieve the objectives of the proposed project, the Pak Arab Refinery would modify
. . . . . . . . . .

. existing and install new refining equipment. The nature of the project includes substantial
. . . . . . . . . . . .

. flexibility as to whether and how to implement the various project components, and
. . . . . . . . . . . .

. therefore, a range of project variables must be considered in the impact analysis.

. . . . . . . . . . . . .

9.6.1: Project Variables

9.6.1.1: Design
. Detailed designs of the Project components themselves are not available, however the
. . . . . . . . . .

. general changes in operation and the major pieces of equipment . . . . . . . (including prominent
. .

. physical features ) are known. Dimensions are provided only for Project components of
. . . . . . . . . . . .

. substantial size and those dimensions are necessarily approximate. . . . . . .

9.6.1.2: Location
. All modifications would be located within the refinery boundaries, generally placed among . . . . . . . . . .

. similar existing equipment. The locations of the Project components are noted or discussed if
. . . . . . . . . . . . .

. those locations are not close to the related existing facilities.

. . . . . . . . . .

9.6.1.3: Schedule
. Pak Arab Refinery would implement the project in a series of steps. If all of the components
. . . . . . . . . . . .

. were to be built, construction would be completed in 16 months. The schedule for each
. . . . . . . . . . .

. component typically describes essential steps in construction or the relationship to refinery

. . . . . . . .

. maintenance turnarounds, instead of fixed dates, since construction of any Project . . . . . . . . .

. component may be delayed or may be foregone. . . . . . . .

9.6.1.4: Certainty
Possible variations in the final project design, project component installation location, and
exact implementation schedule introduce a degree of uncertainty into this analysis.

9.6.2: Project Impact Analysis .

. A refinery consists of process units that cannot operate independently. Changes in the
. . . . . . . . . . . .

. operation of one process unit would result in changes to the operations of other process units
. . . . . . . . . . . . . . . .

. . The individual contributions of each affected interdependent refinery component result in

. . . . . . . . . . .

. an impact of the Project that is the sum of these individual contributions. Examples of such
. . . . . . . . . . . . . . . .

. impacts include visual, air quality, noise and traffic impacts. The analysis in this
. . . . . . . . . . . . . . .

. Environmental Impact Report . . . (EIR) presents the impacts that would result from
. . . . . . . . .

. implementing the full Project, which is construction and operation of each and every . . . . . . . . . . . . .

. component described as part of the project. In nearly all cases, the analysis of the full project
. . . . . . . . . . . . . . . . . .

. reveals the greatest or worst- case impacts that could occur under any combination of
. . . . . . . . . . . . .

. components and leads to the mitigations that would be necessary to reduce those worst- case . . . . . . . . . . . . . . .

. impacts to less than significant. . . . .

. In a few instances, however, the worst-case impact for a given environmental issue might
. . . . . . . . . . . . . . . .

. not occur under the full Project, but would occur as a result of one of the project variables.
. . . . . . . . . . . . . . . . . . .

. Thus the impact analysis in this EIR also considers the possible effects of the project
. . . . . . . . . . . . . . . .

variables Design, Location, Schedule and Certainty in the Project as proposed, on

. . . . . . . . . . . . . . . . .

. environmental impacts. If any aspect of these four variables would result in a substantive . . . . . . . . . . . . . .

. difference in the environmental impact of the ULSD/ Strategic Modernization Project or in

. . . . . . . . . . . . .
. the mitigation that might be applied, those aspects are discussed and the individual effects
. . . . . . . . . . . . .

. are traced. If these variables would not result in an increase in impact or require a material
. . . . . . . . . . . . . . . .

. change in mitigation, they may not be discussed. . . . . . . . .

. In the event that specific operational considerations, dimensions of the components,

. . . . . . . . . . .

. equipment locations, and variations in the timing of construction or the absence of any . . . . . . . . . . . .

. project component were critical to identifying or mitigating a potential environmental impact

. . . . . . . . . .

. of the project, these considerations are discussed under the related impact or mitigation
. . . . . . . . . . . . .

. presentations in this section. . .. .

9.7: Project Alternatives

. The discussion of alternatives does not need to be exhaustive. The key issue is whether the
. . . . . . . . . . . . . . .

. Reasonable range of alternatives is considered that could feasibly accomplish the basic . . . . . . . . . . .

. objectives of the project and could avoid or substantially reduce significant environmental
. . . . . . . . . .

. impacts of the project. Thus, the EIR provides decision- makers and the public with the
. . . . . . . . . . . . . . . .

. mitigation measures and the feasible alternatives available to reduce or avoid those . . . . . . . . . .

. substantial adverse effects that would result from the proposed project. However, an EIR . . . . . . . . . . . . .

. need not consider alternatives for which the effects cannot be reasonably determined and for
. . . . . . . . . . . .

. which implementation is remote and speculative.

. . . . .

9.7.1: Development and Selection of Alternatives

9.7.1.1: Alternatives and Project Objectives

The PAK-ARABs Ultra Low Sulfur Diesel / Strategic Modernization Project, also called the
Project, would implement a series of modifications and additions that are focused on three
primary objectives, as follows:

a) Produce diesel containing less than 15 ppm sulfur.

b) Allow the Refinery to efficiently use a broader array of crude oil as feedstock.
c) Improve refinery efficiency and increase crude throughput capacity.

. .As a result of this change, gasoline production levels would be maintained at current levels
. . . . . . . . . . . . . . .

. and there would be an increase in diesel production. A proposed alternative to the project
. . . . . . . . . . . . . .

. must permit feasible attainment of the proposed projects basic objectives, even if that
. . . . . . . . . . .

. alternative would be more costly than the project or would not fully attain the project goals.
. . . . . . . . . . . . . .
Expected to be among the likely candidates are the various alternatives that the project
sponsor investigated in the development of the project itself.

. In addition to alternatives that meet project objectives, the PEPA also requires the evaluation
. . . . . . . . . . . . .

. of a no project alternative. The no project alternative includes changes and on - going

. . . . . . . . . . . . . . . . . .

activities needed to keep the Refinery in operation, such as regular major and minor . . . . . . . . . . . .

. maintenance activities and other reasonably foreseeable future refinery projects that would . . . . . . . . . .

. be undertaken on an ongoing schedule if the proposed project were not considered.

. . . . . . . . . . . . .

9.7.2: Proposed Alternatives to the Project

9.7.2.1: No Project Alternative

. The No Project alternative would consist of the existing Refinerys configuration and
. . . . . . . . . . .

operation, together with on- going maintenance activities and other projects planned or
. . . . . . . . . . . .

. currently underway. Furthermore, the Refinerys regular maintenance turnarounds also must
. . . . . . . . . .

. continue to occur. Thus, the no project alternative includes those changes, as well as the
. . . . . . . . . . . . . . . . . .

. ongoing activities needed to keep the Refinery in operation into the future. Under the No
. . . . . . . . . . . . . .

. Project alternative, refinery could not satisfy any of its three objectives. The Refinery
. . . . . . . . . . . . . .

. would not be able to produce diesel fuel for on-road use, so any diesel produced would not
. . . . . . . . . . . . . . . .

. be available to the market. The economic consequences to the Refinery from the loss of
. . . . . . . . . . . . . .

diesel sales cannot be determined. The following summarizes the potential environmental
. . . . . . . . .

. impacts of the No Project alternative and compares them to the potential impacts of the . . . . . . . . . . . .

. Project:

9.7.2.1.1: Aesthetics, Visual Quality, Light and Glare:

. No new structures would be built, except for other on- going cumulative refinery projects,
. . . . . . . . . . . . . .

. which would manifest the only visible changes at the Refinery. Even so, the visual impacts
. . . . . . . . . . . . .

. of the No Project alternative would be quite similar to, although of lesser overall magnitude
. . . . . . . . . . . .

. than, and distinguishable from the visual impacts of the Project.

. . . . . . .

9.7.2.1.2: Air Quality:

. The Projects less than significant increases in air emissions would not occur. Criteria
. . . . . . . . .

pollutant emissions levels from the Refinery process stacks would remain at or below current
. . . . . . . . . .

emission limits. The No Project alternative would make no contribution to the regional air . . . . . . . . . . . . .

. quality benefit from the manufacture of ultra low sulfur diesel fuel.
. . .. . . . . . . .
9.7.2.1.3: Biological Resources:
. Limited construction would occur at the Refinery. The biological impacts of the No Project
. . . . . . . . . .

. on aquatic organisms would be essentially the same as those of the Project.

. . . . . . . . .

9.7.2.1.4: Energy:
. Under the No Project alternative, the Refinery would be less energy efficient than under the
. . . . . . . . . . . .

. proposed Project. .

9.7.2.1.5: Public Health and Safety:

. The public health and public safety impacts of the No Project alternative would be
. . . . . . . . . .

essentially the same as those of the Project, except that the No Project alternative would
. . . . . . . . . . .

. make no contribution to the regional air quality benefit from the manufacture of ULSD fuel.
. . . . . . . . .

9.7.2.1.6: Hydrology and Water Quality:

. The hydrology and water quality impacts of the No Project alternative would be essentially
. . . . . . . . . . .

the same as those of the proposed Project.

.. . . . .

9.7.2.1.7: Land Use, Plans and Policies:

. The impacts of the No Project alternative would be essentially the same as proposed Project
. . . . . . . . .

. impacts. .

9.7.2.1.8: Noise:
. The noise impacts of the No Project would be the same as the impacts of the proposed
. . . . . . . . . . . . .

. Project.

9.7.2.1.9: Transportation:
. No change. Under the No Project alternative, Refinery turnarounds would continue. Traffic
. . . . . . . . . .

. impacts of the turnarounds would dominate the traffic effects of the construction of the
. . . . . . . . . . .

. Project and the differences in traffic impacts between the Project and the No Project
. . . . . . . . .

alternative would be minor.

9.7.2.1.10: Utilities and Service System:

. Raw water use at the refinery would not change under the No Project alternative and would
. . . . . . . . . . .

. be less than under the existing conditions. Solid waste quantities would be similar to those
. . . . . . . . . . . . .

under the Project. . . .

9.7.2.1.11: Public Services / Agriculture / Mineral Resources / Employment & Housing
Recreation:
The impacts would be essentially the same as proposed Project impacts.

9.7.2.2: Different Project Schedule

. Traffic impacts could occur when Project construction coincides with refinery turnarounds.
. . . . . . . .

These are significant impacts that would result from construction traffic congestion. Such
. . . . . . . .

. construction traffic congestion could be reduced by constructing the ULSD / Strategic . . . . . . . . .

. Modernization Project at a time other than during a refinery turnaround. This alternative . . . . . . . . . .

would avoid the significant traffic impacts of the Project.

. . . . . . . . .

. Construction of the ULSD / Strategic Modernization Project would require that various . . . . . . . .

. refinery units be shut down to enable critical mechanical equipment to be installed and all
. . . . . . . . . . . . .

. piping connections to be made. These actions, taken outside of a normal refinery turnaround,
. . . . . . . . . . .

. could disrupt the normal operation of the Refinery, interfere with refinery production and
. . . . . . . . . . . .

. add to the cost of the Project. The shift in the time of Project construction would reduce the
. . . . . . . . . . . . . . .

. traffic impacts from project construction. Although reducing the construction traffic impacts
. . . . . . . . . .

. of the Project, this alternative would not necessarily eliminate the significant construction
. . . . . . . . . . .

. traffic impact that would occur during the Refinery turnaround, regardless of the Project
. . . . . .

. construction. That significant traffic impact would remain. Although construction of the
. . . . . . . .

project outside of the normal turnaround would add substantially to the cost of this
. . . . . . . . . . .

. alternative, there would be little benefit from the added expense because the significant
. . . . . . . . .

. traffic impact that would occur during the next refinery turnaround would not be eliminated.
. . . . . . . . . . . . .

. This alternative could satisfy all three Project objectives. This alternative would reduce the
. . . . . . . . . .

. significant adverse traffic impact to less than significant. With the exception of the traffic
. . . . . . . . . . . .

. congestion impacts, the effects of the Project Schedule alternative would be essentially
. . . . . . . . .

. identical to the impacts of the project. . . . . .

9.7.2.3: Modified Project Combination

. This alternative would attempt to address the potentially significant unavoidable water . . . . . . . .

quality impacts described in previous section. The proposed Project includes components to
. . . . . . . . . . .

. produce ULSD, components to improve the efficiency of Refinery processes and

. . . . . . . . .

. components that increase the throughput of the Refinery, to meet the Project objectives. The
. . . . . . . . . . . . .

. operations of these components would result in the water quality effects that have
. . . . . . . . . .
. conservatively been considered here to be potentially significant unavoidable impacts of the . . . . . . . . .

. Project. It may be possible to reduce the overall Refinery throughput or modify the Refinery
. . . . . . . . . . . .

. equipment or feed stocks (or a combination of these) in order to eliminate the potentially . . . . . . . . . . . . . .

significant unavoidable impacts of the Project. It is not known whether any of the strategies . . . . . . . . . .

. or any combination of strategies would yield the desired result, namely the elimination of the
. . . . . . . . . . . .

. significant water quality impacts. For example, continuing to use the crude now shipped to . . . . . . . . . . . . .

. the Refinery would keep the total sulfur, as well as other impurities in the crude feed stocks,
. . . . . . . . . . . . . . .

. at current levels. However, the need to remove more sulfur and impurities from the ULSD
. . . . . . . . . . . . .

. would increase the amounts of that material processed at the wastewater treatment facility,
. . . . . . . . . .

. with the possible result of increasing the toxics loading in the wastewater effluent. Thus, it is
. . . . .. . . . . . . .

. not apparent that the desired benefit would result. This alternative would attain the first
. . . . . . . . . . .

. Project objective, in the production of ULSD fuel. However, elimination of some of the . . . . . . . . . .

. strategic modernization equipment would not permit the Project to satisfy the second project
. . . . . . . . . .

objective and attain its efficiency goal. Reducing the throughput would adversely affect the
. . . . . . . . . . .

. third Project objective. . .

. The EIR conservatively lists the two water quality impacts as potentially significant because
. . . . . . . .

. of the uncertainties both in the amount of the increases and in the ability of the receiving
. . . . . . . . . . . .

. waters to assimilate those increases. This alternative would not meet the basic objectives of
. . . . . . . . . . . .

the project and it is uncertain whether and to what extent such an alternative might reduce
. . . . . . . . . . . .

. these potentially significant environmental impacts.

. . . .

9.7.2.4: Project at an Alternate Site

. Consideration of an alternate site alternative is commonly included among the reasonable . . . . . . . . .

. range of alternatives. However, due to the nature of the Project, constructing the ULSD /
. . . . . . . . . . . . . . .

Strategic Modernization Project at an alternate site could require construction of the ULSD
. . . . . . . . . .

facilities at another operating refinery, or construction of an entire new refinery, which

. . . . . . . . . . .

would be a greatly larger project than the Project and would result in new environmental
. . . . . . . . . . . .

impacts related to that site. The ULSD / Strategic Modernization Project proposed by
. . . . . . . . . . .

refinery would focus development only within the active area of the existing refinery, and
. . . . . . . . . . . . .

would not result in development in new or previously undisturbed areas within the existing
. . . . . . . . . . . .

refinery footprint. It is clearly infeasible to consider an alternative location for the ULSD /
. . . . . . . . . . . .

Strategic Modernization Project as a whole, since as a series of components and . . . . . . . . . . .

. modifications to existing components, the project cannot stand on its own. This alternative is . . . . . . . . . . . .

. considered to be infeasible and is not considered further. . . . . . . .. .

HAZOP Analysis
 Chapter # 10

10: HAZOP Analysis

. The technique of Hazard and Operability Studies, or in more common terms HAZOPS, has
. . . . . . . . . . . . . . .

. been used and developed over approximately four decades for 'identifying potential hazards
. . . . . . . . . . .

and operability problems' caused by 'deviations from the design intent' of both new and
. . . . . . . . . . . . . .

. existing process plants. . . .

10.1: Potential Hazard and Operability Problems

You will note the capitalized 'AND' in the heading above. Because of the high profile of
. . . . . . . . . . . . . . .

. production plant accidents, emphasis is too often placed upon the identification of hazards to
. . . . . . . . . . . .

. the neglect of potential operability problems. Yet it is in the latter area that benefits of a
. . . . . . . . . . . . .

. Hazop Study are usually the greatest. To quote an example, a study was commissioned for a
. . . . . . . . . . . . .

. new plant. Some two years previously, and for the first time, a similar study had been
. . . . . . . . . . . . . . .

. carried out on different plant at the same site which was then in the process of being
. . . . . . . . . . . . . .

. designed. Before the latest review commenced, the Production Manager expressed the hope
. . . . . . . . . . .

. that the same benefits would accrue as before, stating that "in his twenty years of experience,
. . . . . . . . . . . .
.. never had a new plant been commissioned with so few problems, and no other plant had ever
. . . . . . . . . . . .

. achieved its production targets and break - even position in so short a time".
. . . . . . . . . . .

10.2: Deviation from Design Intent

. To deal firstly with 'design intent', all industrial plant is designed with an overall purpose in
. . . . . . . . . . . .

. mind. It may be to produce a certain tonnage per year of a particular chemical, to

. . . . . . . . . . .

. manufacture a specified number of cars, to process and dispose of a certain volume of . . . . . . . . . . . .

. effluent per annum, etc. That could be said to be the main design intent of the plant, but in . . . . . . . . . . . . . . . . .

. the vast majority of cases it would also be understood that an important subsidiary intent
. . . . . . . . . . .

. would be to conduct the operation in the safest and most efficient manner possible.
. .. . . . . . . . . ..

10.3: The Basic Concept

. Essentially the Hazops procedure involves taking a full description of a process and . . . . . . . . .

. systematically questioning every part of it to establish how deviations from the design intent . . . . . . . . . . .

. can arise. Once identified, an assessment is made as to whether such deviations and their
. . . . . . . . . . . . . .

. consequences can have a negative effect upon the safe and efficient operation of the plant. If . . . . . . . . . . . . . .

. considered necessary, action is then taken to remedy the situation. . . . . . . . . . . .

. This critical analysis is applied in a structured way by the Hazop team , and it relies upon
. . . . . . . . . . . . . .

. them releasing their imagination in an effort to discover credible causes of deviations. In

. . . . . . . . . . . . . .

. practice, many of the causes will be fairly obvious, such as pump failure causing a loss of
. . . . . . . . . . . . . . .

. circulation in the cooling water facility mentioned above. However, the great advantage of . . . . . . . . . . . .

. the technique is that it encourages the team to consider other less obvious ways in which a
. . . . . . . . . . . .

. deviation may occur, however unlikely they may seem at first consideration. In this way the
. . . . . . . . . . . . . . .

. study becomes much more than a mechanistic check -list type of review. The result is that
. . . . . . . . . . . . . . .

. there is a good chance that potential failures and problems will be identified which had not
. . . . . . . . . . . .

. previously been experienced in the type of plant being studied. . . . . . . . . .

10.4: The HAZOP Team

. The team who will conduct the Hazop study should consist of personnel with a good
. . . . . . . . . . .

understanding of the process and plant to be reviewed. The group should ideally contain . . . . . . . . . . . . .

about six members, with perhaps an absolute upper limit being set at nine. In a study in
. . . . . . . . . . . . . . . .

which both contractor and client are participating, it is desirable to maintain a balance
. . . . . . . . . . . . .

between the two in terms of team membership so that neither side feels outnumbered.
. . . . . . . . . . . .
. The participants should consist of people from a range of disciplines, and this aspect is one . . . . . . . . . . . .

. of the strengths of the Hazop methodology:

. . . . . .

a) With a team of people, each with differing backgrounds and experience, potential
. . . . . . . . . . .

. problems are likely to be identified which would be missed by one or two people . . . . . . . . . . . .

. working on their own. . . . .

b) It is often the case that one person's solution can become a problem to another
. . . . . . . . . . . .

. department within the project. For example, a Process Engineer conducting his own . . . . . . . . . . .

review in isolation may identify a potential problem for which he considers that
. . . . . . . . . .

. another instrument and alarm would be desirable. When this requirement is passed to
. . . . . . . . . . .

. the Control & Instrumentation Engineer, it transpires that no suitable channels are
. . . . . . . . . .

available within the appropriate section of the electronic control system, which has . . . . . . . . . .

. already been ordered and is currently being manufactured by the vendor. . . . . . . . . . . . .A

protracted inter- departmental discussion and correspondence then ensues as to . . . . . . . . .

. possible alternative remedies, and the potential cost penalty of re- specifying the . . . . . . . . . . .

. control system. All of this could have been settled within a few minutes had both
. . . . . . . . . . . .

. departments participated in the study. . . . ..

c) A spirit of co- operation and common purpose is engendered which crosses

. . . . . . . . . .

. departmental boundaries , and this will persist even after the Hazop Study has been . . . . . . . . . . .

. completed. Personnel will understand better the views, concerns and constraints . . . . . . . . . .

. within which other disciplines have to work, and will take these into account when
. . . . . . . . . . . .

. making decisions affecting the project. . . . .

. The actual composition of the Hazop team will vary according to the type of plant being
. . . . . . . . . . .

. reviewed. . One person who should always be included is a representative from . . . . . . . . .

. Operations. He or she should have first hand experience of day- to- day operations on either
. . . . . . . . . . . . . . .

. the plant being reviewed , or one that is very similar in nature. The contribution of this team
. . . . . . . . . . . . . . .

. member to the discussion can be invaluable, as it introduces an operational perspective to

. . . . . . . . . . . . . . .

. other participants who may have never, for example, had to climb down into a vessel . . . . . . . . . . . . . . .

. wearing breathing apparatus to carry out repairs or an inspection.

. . . . . . . . .

. To summarize, a team should be selected so that a balanced approach to the study is . . . . . . . . . . . .

. ensured. In addition, the intention should be that questions raised during the meeting can be
. . . . . . . . . . . . .

. answered immediately, rather than having to resort to the time consuming process of
. . . . . . . . . . .

. referring to outside expertise. It is not of course necessary for the same people to participate
. . . . . . . . . . . . .

. in the study from beginning to end. If the " core" of the group consisted of five people, for
. . . . . . . . . . . . . . . . . .
. example, additional members could be called in from session to session as and when their
. . . . . . . . . . . .

. particular expertise was needed. . . . .

. As with all group activities, there needs to be a person appointed who will be in overall
. . . . . . . . . . . . . . .

charge; with Hazop Studies this person is usually called the Chairman or Study
. . . . . . . . . .

. Leader. Ideally, he should not have been too closely associated with the project under
. . . . . . . . . . . .

. review as there might be a risk of him not being sufficiently objective in his direction of the
. . . . . . . . . . . . . .

team. As the Chairman's role is of vital importance in the smooth and efficient progress of
. . . . . . . . . . . . . . .

. the study, he should be carefully chosen and be fully conversant with the Hazop
. . . . . . . . . . . .

. methodology. . .

Another important member of the team will be the Secretary. His contribution to the
. . . . . . . . . . . . .

discussion may well be minimal, as his main function during the sessions will be to record . . . . . . . . . . . . .

. the study as it proceeds. He will therefore need to have sufficient technical knowledge to be
. . . . . . . . . . . .

. able to understand what is being discussed.

. . . . . . .

10.5: Hydrogen Sulfide Poisoning

. Hydrogen sulfide is an extremely poisonous gas. Hydrogen sul-fide poisoning results from . . . . . . . . . .

. breathing hydrogen sulfide gas . . . (2$), even in very low concentration. Two forms of
. . . . . . . . . .

poisoning occur - acute and sub acute. . . . .. . .

10.5.1: Acute Hydrogen Sulfide Poisoning

. Breathing air or gas containing as little as 0. 10 % . . . . . . . . . (40- 60 grains of H2S per 100 standard
. . . . . . .

. cubic feet) for ONE MINUTE can cause acute poisoning.

. . . . . . . . .

. Much sour natural or refinery gas contains more than 0. 10% (60 grains per 100 cubic feet), . . . . . . . . . . . . . .

. so care must always be taken to avoid breathing such sour gas. The naphtha hydro treating
. . . . . . . . . . .

. recycle gas and high pressure stripper gas contain from 0.5 to 5 % H2$, while the low
. . . . . . . . . . . . . . .

pressure stripper gases contain from 10 to 50% H2S, . . . . . . . . .

. These gases must NEVER be breathed. One full breath of high concentration hydrogen
. . . . . . . . .

. sulfide gas will cause unconsciousness, and may cause death, particularly if the victim falls
. . . . . . . . . . . .

. and remains in the presence of such gas.

. .. . . . .
The operation of any unit processing gases containing H2S is perfectly safe, provided
. . . . . . . . . .

ordinary precautions are taken and the poisonous nature of the gas is . recognized. No work
. . . . . . . . . . . .

. should be undertaken on the unit where there is danger of breathing H2S, and one should
. . . . . . . . . . . . .

. never enter or remain in an area' containing it without wearing a suitable fresh air mask. . . . . . . . . . . . . .

10.5.1.1: Symptoms of Acute Hydrogen Sulfide Poisoning

. Muscular spasms, irregular breathing, lowered pulse, odor to the breath, nausea. Loss of
. . . . . . . . . . . . .

. consciousness and suspension of respiration quickly follow. . . . . . .

After apparent recovery, edema (dropsically swelling) of the air passages or lungs may cause
severe illness or death in 8 to 48 hours.

10.5.1.2: First Aid Treatment of Acute Poisoning

. Remove the victim at once to fresh air. If breathing has not stopped , keep the victim in fresh . . . . . . . . . . . . . .

. air and keep him quiet. If possible, put him to bed. Secure a physician and keep the patient
. . . . . . . . . . . . . . . .

quiet and under close observation for about 48 hours for possible edema of the air passages
. . . . . . . . . . . .

. or lungs. . .

. In cases where the victim has become unconscious and breathing has stopped, artificial
. . . . . . . . . .

. respiration must be started at once. If a Pulmotor or other mechanical equipment is available,

. . . . . . . . . . . . .

. it may be used by a trained person; if not, artificial respiration by mouth- mouth method must
. . . . . . . . . . . . . . . .

be started as soon as possible. Speed in beginning the artificial respiration is essential . Do

. . . . . . . . . . . . . . .

. not give up. Men have been revived after more than four hours of artificial respiration.
. . . . . . . . . . . . . .

. If other persons are present, send one of them for a physician. Others
. . . . . . . . . . . .should rub . the
patient's arms and legs and apply hot water bottles, blankets or other sources of warmth to
.. . . . . . . . . . .

. keep him warm. . . .

. After the patient is revived, he should be kept quiet and warm, and remain under observation
. . . . . . . . . . . .

. for 48 hours 'for the appearance of edema of the air passages or lungs.
. . . . . . . . . .

10.5.2: Sub-acute Hydrogen Sulfide Poisoning

. Breathing air or gas containing 0. 01 to 0. 6% H S (6 to 40 grains per 100 cubic feet) for an . . . . . . . . . . . . . . . . . . . .

. hour or more may cause sub acute or chronic hydrogen sulfide poisoning.
. . . . . . . . . . . .
10.5.2.1: Symptoms of Sub acute Poisoning

Headache, inflammation of the eyes and throat, dizziness, indigestion, excessive saliva, and
. . . . . . . . . . . .

. weariness are all symptoms which follow continued exposure to H2$ in low concentrations. . . . . . . . . . . .

. Edema of the air passages and lungs may also occur.

. . . . . . . .

10.5.2.2: Treatment of Sub acute Poisoning

. Keep the patient in the dark to reduce eyestrain and have a physician treat the inflamed eyes
. . . . . . . . . . . .

. and throat. Watch for possible edema . . . . . ..

. Where sub acute poisoning has been suspected, the atmosphere should be checked repeatedly
. . . . . . . . .

. for the presence of H2S by such methods as testing by odor, with moist lead acetate paper,
. . . . . . . . . . . . . . .

. and by Tutwiler determination to make sure that the condition does not continue.
. . . . . . . . . . .

10.5.3: Prevention of Hydrogen Sulfide Poisoning

... The best method for prevention of H2O poisoning 1s to stay out of areas known or suspected
. . . . . . . . . . .

. to contain it. The sense of smell is not an infallible guide as to its presence, for although the
. . . . . . . . . . . . . . . .

. compound has a distinct and unpleasant odor (rotten eggs), it will frequently paralyze the . . . . . . . . . . . .

. olfactory nerves to the extent that the victim does not realize that he is breathing it . This is
. . . . . . . . . . . . . . .

. particularly true of higher concentrations of the gas. . . . . . . . . .

. Fresh air masks or gas masks suitable for use with hydrogen sulfide must be used in all work
. . . .. . . . . . . . . . . ..

. where exposure to it is likely to occur. Such masks must be checked frequently to make sure' . . . . . . . . . . ... . .

. that they are not exhausted. Whenever work is done on or in equipment containing
. . . . . . . . . . . .

. appreciable concentrations of H2S, men must wear fresh air masks and should work in pairs
. . . . . . . . . . .

. so that one may effect a rescue or call for help should-the other be overcome.
. . . . . . . . . . . . . .

. As mentioned above, , the atmosphere in which men work may be checked from time to time
. . . . . . . . . . . . . .

. for small concentrations such as would cause sub acute poisoning.

. . . . . . . . .

. Remember - just because your nose says it's not there, doesn't mean that it's not.
. . . . . . . . . . . .. .

10.5.4: Further Information

A more detailed information booklet, The Chemical Safety Data Sheet SD36, may be
obtained by writing to:
Manufacturing Chemists Association 1825 Connecticut Avenue, NW Washington, DC 20009

10.6: Safety Precautions for Entering a Contaminated

Atmosphere

. Anyone entering a vessel which contains- an inert or contaminated atmosphere must follow . . . . . . . . . .

all prescribed standard safety precautions and regulations which apply. In particular, when
. . . . . . . . . .

. entering a reactor containing

. . . used catalyst, and which therefore can contain some
. . . . . . .

hydrocarbons and H2S along with possible pyrophoric iron sulfide deposits, there are a
. . . . . . . . .

. number of additional precautions which apply and which should not be overlooked. For this
. . . . . . . . . . . . . .

discussion, it is assumed that entry into a reactor containing used catalyst under a nitrogen
. . . . . . . . . . . . .

blanket is planned. In this case, the following precautions should be included in the standard
. . . . . . . . . . . . . .

. procedure: .

a) The reactor should be isolated by positive action, such as blinding, to exclude all
. . . . . . . . . . . . .

sources of hydrocarbon, hydrogen, air, etc. . . . .

b) Just prior to entry, all purging of nitrogen through the catalyst bed should be
. . . . . . . . . . .

. discontinued, and nitrogen purge lines should be inserted at points ABOVE the . . . . . . . . . .

. catalyst bed.
This is to assure that there will be no forced flow of vapors passing upward through
the catalyst bed and into the working area.
c) Install an air mover outside the reactor near the open man way nozzle to sweep away
. . . . . . . . . .

. the vapors leaving, the reactor.

. . .

d) The man entering the reactor must be equipped with a fresh air mask in proper
. . . . . . . . . . . .

working condition, with a proper air supply. . . .

e) "There should be available and ready for immediate use and transfer to the man in the
. . . . . . . . . . . . . .

. reactor, a separate spare air supply which is independent of electrical power.

. . . . . . . . .

f) The man entering the reactor should wear a safety harness with a properly attached
. . . . . . . . . . .

. safety line.
g) There should be a minimum of two backup men at the man way nozzle in continual
. . . . . . . . . . . . .

. surveillance of the actions of the man in the reactor. . . .

h) There should be a spare fresh air mask complete with its own separate air supply to
. . . . . . . . . . . . .

. allow a second man to enter the reactor quickly in case of an emergency. Therefore,
. . . . . . . . .
 this spare equipment must be compact enough to allow the second man to enter
through the man way while wearing the equipment.
i) It is recommended that any man working in a. reactor which is under a nitrogen
. . . . . . . . . . . . .

. blanket not be permitted to descend through any appurtenance, such as a tray or

. . . . . . . . . . . .

quench gas distributor. The reason for this precaution is that should the man develop
. . . . . . . . . . . . .

some difficulty while below a tray, for example, to the point where he could not
. . . . . . . . . . . . . . . .

. function properly or lost consciousness, it would be extremely difficult for the . . . . . . . . . .

. surveillance team outside the reactor to pull the man up through the small tray man
. . . . . .

way by use of the safety line.

j) As an added precaution, it is suggested that the man in the reactor have available to
. . . . . . . . . . . . . .

him in the reactor, an emergency self-contained air supply and appropriate associated
. . . . . . . . . . .

. equipment . Preferably, the emergency air supply could be connected to the fresh air
. . . . . . . . . . . . .

. mask he is wearing. Such "reserve air supply" systems are available commercially.
. . .
APPENDICES
 Appendix A

Material Balance Detail Calculations:-

Basis for calculation:-

Reactor:-
We will perform material balance on the basis of one hour operation.

Overall composition of feed stream

Compound Composition %
Sulfur compounds 1.42
Nitrogen 2.5
compounds
Olefins 4
Aromatics 26
Halide 2.5
Paraffin 63.58
Sulfur Compounds
As sulfur compounds composition is = 1.42 %

Total flow rate of feed = 229237.1 kg

So, total sulfur compounds present = 3255.16 kg

As there are 5 reactions involving sulfur compounds,

So the amount of each sulphur compound in each reaction will be = 651.03kg

Mercaptans
Total Mercaptans = 651.03kg

Form balance chemical equation

90kg mercaptans required hydrogen = 2kg

651.03kg mercaptans required hydrogen = (2/90) x651.03 kg

90 kg mercaptans produce C4 = 58

651.03 kg mercaptans produce C4 = (58/90)*(651.03)

Amount of C4 produce from mercaptans = 419.55 kg

90 kg mercaptans produce H2S = 34kg

651.03 kg mercaptans produce H2S = (34/90)*(651.03)

Amount of H2S produce = 245.94 kg

Mercaptans
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Mercaptans 651.03 C4 419.55

H2 14.467 H2S 245.94

Total 665.497 Total 665.49

Similarly by following above given procedure we apply the material balance for each
reaction. Keeping eye on the time requirement we bypass the above given manual calculation
for each reaction rather we include the final values

Sulfide
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Sulphide 651.03 C2 434.02

H2 28.934 H2S 245.94

Total 679.964 Total 679.96

Disulphide
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Disulphide 651.03 C2 320.17

H2 32.017 H2S 362.869

Total 683.047 Total 683.039

Cyclic Sulphide
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Cyclic Sulphide 651.03 C4 429.08

H2 29.592 H2S 251.53

Total 680.622 Total 680.61

Thiophene
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Thiophene 651.03 C4 449.52

H2 62 H2S 263.51

Total 713.03 Total 713.03

Nitrogen Compounds

Pyridine
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Pyridine 1910.309 C5+ 1741.04

H2 241.18 NH3 411.07

Total 2151.989 Total 2152.08

Quinoline
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Quinoline 1910.309 C5+ 1777

H2 118.46 NH3 251.746

Total 2028.769 Total 2028.746

Pyrrole
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Pyrrole 1910.309 C4 1653.70

H2 228.096 NH3 484.70

Total 2138.405 Total 2138.4

Olefin Saturation:-

Linear olefins
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Linear olefins 4584.742 C5+ 4693.9

H2 109.2 -- ---

Total 4693.9 Total 4693.9

Cyclic olefins
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Cyclic olefin 4584.742 C5+ 4696.56

H2 111.82 ---- ----

Total 4696.56 Total 4696.56

Aromatic saturation

Benzene
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Benzene 29800.823 C5+ 32093.194

H2 2292.37 ---- ----

Total 32093.194 Total 32093.194

Phenol
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Phenol 29800.832 C5+ 26630.52

H2 2536.24 H2O 5706

Total 32336.52 Total 32336.52

Halide Removal
Feed Stream Product Stream

Compound kg/hr Compound kg/hr

Halides 5731 C5+ 4451.26

H2 74.19 HCl 1353.93

Total 5905.19 Total 5905.19

NH4Cl & Free NH3
Sum up all the ammonia produce in above reactions. Now keeping in view the balance
chemical equation of the reaction between NH3 /HCl and the respective kmoles we came to
know that HCl is a limiting reactant.

NH3 + HCl NH4Cl

From the above given equation one mole of ammonia react with one mole of HCl to form one
mole NH4Cl. So now we will look into the kmoles of two reactants to decide which one is the
limiting reactant.

Total ammonia produce = 1147.516kg

= 67.51kmole

Total HCl produce = 1353.93kg

= 37.094kmole

As the less No. of kmole of HCl present in the reactant mixture so it will the limiting reactant
for our calculations.

Feed Stream Product Stream

Reactants kg/hr Products kg/hr

NH3 1147.51 NH4Cl 1984.16

HCl 1353.93 NH3 Free 517

Total 2501.44 Total 2501.16

Paraffin
Feed Stream Product Stream

Reactants kg/hr Products kg/hr

Paraffins 145748.9482 C5+ 145748.9482

Total 145748.9482 Total 145748.9482

 Hydrogen Required
On the basis of 50% excess hydrogen

( )

Hydrogen Entering =5878.956*(50/100 +1)

= 8818.434 kg

Free hydrogen = (8818.434-5878.956) kg

=2939.478 kg

Component kg/hr
H2 8818.434

Component kg/hr
H2 S 1369.789
H2 2939.478
Component kg/hr
NH3 517
Sulfur Compounds 3255.15 NH4Cl 1984.16
Nitrogen 5730.92 5706
H2 O
Compounds C2 754.19
Olefins 9169.47 2951.85
C4
Aromatics 59601.6 221832.414
C5+
Halides 5731.00 238055.534
Total
Paraffin
HP Hot 145748.94
separator balance
Total 229237.1
Assumptions
1. H2 is most lightest gas so it is recovered from the top
 2. C2 (ethane) is very light gas so it is recovered from the top completely
3. C4 is heavier comparatively so 90% is recovered from the top
4. NH4Cl is in vapor form so it is recovered from the top about 90%
5. H2S is relatively heavier gas 85% is recovered from the top
6. Water recovered is about 5 % from the top
7. 90% NH3 is removed from the top
8. C5+ recovered from the top is 0.1%
Feed Stream Product Stream

Component Feed Stream Top Products Bottom Products

kg/hr kg/hr kg/hr

H2 S 1369.789 1164.321 205.468

H2 2939.478 2939.478 ---

NH3 517 465.3 51.7

NH4Cl 1984.16 1785.744 198.416

H2 O 5706 285.3 5420.7

C2 754.19 754.19 ---

C4 2951.85 2656.665 295.185

C5+ 221832.414 221.833 221610.518

Total 238054.881 10273.831 227782.05

 Component kg/hr
H2 S 1164.321
H2 2939.478
NH3 465.3
NH4Cl 1785.744
H2 O 285.3
C2 754.19
Component kg/hr C4 2656.665
H2 S 1369.789 C5+ 221.833
H2 2939.478 Total 10273.831
NH3 517
NH4Cl 1984.16
H2 O 5706
C2 754.19
Component kg/hr
C4 2951.85
H2 S 205.468
C5+ 221832.414
H2 ---
Total 238055.534
NH3 51.7
NH4Cl 198.416
H2 O 5420.7
C2 ---
C4 295.185
C5+ 221610.518
Total 227782.05

HP cold separator

Assumptions
Temperature decreases from 200C to 40 C while pressure decreases from 54.9 to
53.2 Kg/cm2
C4 will b condensed completely and C2 will condensed partially
 C4 is recovered from the bottom about 99%
C2 is recovered from bottom about 97%
H2S 1% is recovered at the bottom

Hp Separator top product as per assumptions

Feed Stream Product Stream

Component Feed stream Top Products Bottom Products

kg/hr kg/hr kg/hr

H2 S 1164.321 1152.678 11.643

H2 2939.478 2939.478 ---

NH3 465.3 --- 465.3

NH4Cl 1785.744 --- 1785.744

H2 O 285.3 --- 285.3

C2 754.19 22.626 731.564

C4 2656.665 26.566 2630.099

C5+ 221.833 --- 221.833

Total 10273.831 4141.348 6131.483

 Component kg/hr
H2 S 1152.678
H2 2939.478
C2 22.626
C4 26.566
Total 4141.348

Component kg/hr
H2 S 1164.321
H2 2939.478
NH3 465.3
NH4Cl 1785.744
H2 O 285.3
C2 754.19 Component kg/hr
C4 2656.665 H2 S 11.643
C5+ 221.833 NH3 465.3
Total 10273.831 NH4Cl 1785.744
H2 O 285.3
C2 731.564
Absorber C4 2630.099
C5+ 221.833
Assumptions Total 6131.483
1. In absorber there is high pressure and low temperature, so C2 and C4 will condensed
and some quantity will be recovered from the bottom
2. 20% C4 will be recovered from the top product
3. 60% C2 will be recovered in the top product
4. 99% H2S is being recovered from the top
Feed Stream Product Stream

Component Gas Stream(Bottom) Liquid Stream(Top) Liquid Stream (Bottom) Gas Stream(Top)
 kg/hr kg/hr kg/hr kg/hr

H2S 1152.678 ---- 1152.678 ----

H2 2939.478 ---- --- 2939.478

C2 22.626 ---- 9.05 13.576

C4 26.566 ---- 21.253 5.313

DEA ---- 19211.3 19211.3 ----

(20%
Sol)
Total 4141.348 19211.3 20394.281 2958.367

Component kg/hr Component kg/hr

H2 S --- H2S ---
H2 --- H2 2939.478
C2 --- C2 13.576
C4 --- C4 5.313
DAE 19211.3 DAE ---
(20%) (20%)
Total 19211.3 Total 2958.367

Component Kg/hr
H2 S 1152.678 Component kg/hr
H2 2939.478 H2 S 1152.678
C2 22.626 H2 ---
C4 26.566 C2 9.05
DAE --- C4 21.253
(20%) DAE 19211.3
Total 4141.348 (20%)
Total 20394.281
 Stripper

Assumptions
1. As a stripping temperature is 180C, we assume 80% of water to be evaporated.
2. 100% of ammonia and H2S is to be recovered from the top
3. C4 is recovered at the top totally
4. NH4Cl evaporated at the top is 90%
5. C5+ having boiling point above 200 C as 0.5% of it is removed at the top
Feed Stream Product Stream

Component kg/hr Stream (Bottom) kg/hr Stream(Top) kg/hr

H2 O 5420.7 1084.14 4336.56

NH3 51.7 --- 51.7

NH4Cl 198.416 19.842 178.574

H2 S 205.468 --- 205.468

C4 295.185 --- 295.185

C5+ 221610.581 220502.528 1108.053

Total 227782.05 221606.51 6175.54

 Component kg/hr
H2 S 205.468
NH3 51.7
NH4Cl 178.574
H2 O 4336.56
C4 295.185
C5+ 1108.053
Total 6175.54

Component kg/hr
H2 S 205.468
Component kg/hr
NH3 51.7
NH4Cl 19.842
NH4Cl 198.416
H2 O 1084.14
H2 O 5420.7
C5+ 220502.528
C4 295.185
Total 221606.51
C5+ 221610.518
Total 227782.05

Dryer Balance

Assumptions
Component kg/hr
1. 90 % H2O removed in top product of dryer.
NH4Cl 16.864
2. 85 % NH4Cl is removed in top product of dryer.
H2 O 975.726
3. 0.1 % C5+ is removed in top product of dryer.
C5+ 220.503
Total 1213.093

Component kg/hr
NH4Cl 19.842
H2O 1084.14 Component kg/hr
C5+ 220502.528 NH4Cl 2.976
Total 221606.51 H2 O 108.414
C5+ 220282.025
Total 220393.415
 Appendix B

Energy Balance Detail Calculations

Energy balance around heater

Heat in:
As two streams are entering in heater at different temperature so heat entering in heater is
sum of heats of both streams.

Total Heat entering = Heat enter with diesel+ Heat enter with H2 stream

For feed stream (F3)

Mass flow rate of feed, mdiesel = 229237.1 kg/hr

Temperature of feed, Tdiesel = 125 oC

Reference temperature Tref = 0oC

Specific heat capacity at 125 oC Cp = 3.1 kJ/kg-oC

Heat present in feed stream F1, Qdiesel = mdieselCp Tdiesel

 Qdiesel = 229237.1 x 3.1 x 125

Qdiesel = 88829376.25 kJ/hr

For H2 stream (F):

Mass flow rate of H2, mH2 = 8818.43 kg/hr

Temperature of H2, T H2 = 25oC

Specific heat of hydrogen at 25 oC = 14.30 kJ/kg-oC

Heat present in H2 stream F, QH2 =

QH2 = 8818.43x 14.30 x 25

QH2 = 3152590.155kJ/hr

So,

Total heat entering in heater,

Qin = Qdiesel + QH2

Q in = 91981966.41 kJ/hr

After mixing, temperature of both streams changes which can be found from the following
relationship

Where,

TR = reference temperature= 0 oC

And,

Cp diesel = 3.1 kJ/kg-oC

91981966.41= ((229237.1 x 3.1) + (8818..43 x 14.30)) x (T - 0)

T = 117 oC
Heat out
As outlet stream of heater is the mixture of diesel and H2 so,

Total heat out of heater, Q out = Qdiesel + QH2

A. For diesel
Mass flow rate of diesel, mdiesel = 229237.1 kg/hr

Outlet temperature, Tdiesel = 325 oC

Cp at 325 oC = 3.5 kJ/kg-oC

Qdiesel = mdieselCpTdiesel

Q diesel = 229237.1x 3.5 x (325-0)

Q diesel = 260757201.3 kJ/hr

For H2
Mass flow rate of H2 m H2 = 8818.434 kg/hr

Outlet temperature of H2, T H2 = 325 oC

Specific heat of H2 at 325 oC Cp = 14.38 kJ/kg- oC

QH2 = m H2CpT H2

QH2 = 8818.434 x 14.38 x 325

QH2 = 17872260.64 kJ/hr

So,

Total heat out

Q out = 301740873.3kJ/hr

Heat added by heater/furnace:

Thus heat supplied by heater, Q = Qout- Qin

Q = 301740873.3- 91981966.41

Q = 209758906.9 kJ/hr
Source of heating
Natural gas is used for heating purposes,
209758906.9 kJ 1m3 gas 1 kcal
Gas required for heating hr 7979 kcal 4.184KJ
=

= 6283.191m3/hr

Air require to react with natural gas

1 +2 1 +2

So moles of air required for complete combustion of 1 mole of CH4 is

= 2/0.21

=9.52moles

= 9.52m3

Air required for 1m3 CH4 = 9.52 m3

So,

6283.191 m3/hr natural gas need air to complete combustion = 59839.914 m3/hr

Normally 35% excess air is used =1.35 x 59839.914

Actual air required = 80783.88 m3/hr

Raw Diesel
Qin(kJ/hr) 88829376.25
Temperature 125
Diesel+H2
(oC)
Qout(kJ/hr) 301740873.3
Hydrogen H2 Temperature 325
Qin(kJ/hr) 3152590.155 (oC)
Temperature 25
(oC)

CH4 + Air
QHeater(kJ/hr) 209758906.9
Temperature 25
(oC)
11:
Air (m3/hr) 80783.88
CH4 (m3/hr) 6283.191

Energy balance around Reactor:

Heat entering in reactor

Qin = Qin-diesel + Q in-H2

Mass flow rate of feed, mdiesel = 229237.1kg/hr

Temperature of feed, Tdiesel = 325 oC

Reference temperature, TR = 0 oC

Cp at 325 oC = 3.5 kJ/kg-oC

Heat present in feed stream, Qin-diesel = mdieselCp Tdiesel

Qin-diesel = 229237.1 x 3.5 x (325 0)

Qin-diesel = 260757201.3kJ/hr

Mass flow rate of H2, mH2 = 8818.43 kg/hr

Temperature of H2, T H2 = 325oC

Reference temperature, TR = 0 oC

Cp at 325 oC = 14.30 kJ/kg-oC

Heat present in H2 stream, Qin-H2 = mH2Cp T

Qin-H2 = 8818.43 x 325 x 14.38

Qin-H2 = 41287727.3 kJ/hr

Qin = Qin-diesel + Q in-H2

Qin =302044928.6kJ/hr

Heat out from reactor:

Qout = QC5++QC4+QC2+QNH4Cl+QNH3+QH2S+QH2O+Q
H2

Sample Calculations Q = m x Cp x (T-TR)

Component Flow rate-m Cp T Qout

(kg/hr) (KJ/kg-oC) (oC) (KJ/hr)

C5+ 221832.414 3.5 355 224587604

C4 2951.85 3.5 355 5467268.24

C2 754.19 0.59 355 324917.973

H2 S 1369.78 1.1 355 1373099.68

NH4Cl 1984.16 1.8 355 1073662.19

NH3 517 2.43 355 378109.478

H2 O 5706 4.39 355 6557940.55

H2 2939.37 14.38 355 5957420.21

Total heat out of reactor, Total Qout = 305599396.5 kJ/hr

Heat generation in reactor can be calculated as follows,

Qgeneration = Qout - Qin

Qgeneration = 5268336.213kJ/hr

Energy Balance around Heat exchanger:

For Cold Stream:

Mass of stream, mdiesel = 229237.1 kg/hr

tavg = (125+60)/2 = 92.5 oC

Specific Heat Capacity Cp at 92.5 oC = 2.8 kJ/kg-oC

Q = mdiesel x Cp x (t2 t1)

Q = 41721152.2 kJ/hr

For Hot Stream:

Mass of stream, mdesulfurized = 215966.5773kg/hr

Specific Heat Capacity Cp at 355 oC = 3.9 kJ/kg-oC

Q = mdiesel x Cp x (T3 T4)

= 41721152.2

= 238054.881 x 3.9 x (355 T4)

T4 = 310 oC
Hot Reactor outlet Cold outlet

Qin(kJ/hr) 329586983 Qin(kJ/hr) 80232985

Temperature 355 Temperature 125

(oC) (oC)

Hot outlet
Qin(kJ/hr) 287865831
Temperature 310
(oC)

Cold Inlet
Qin(kJ/hr) 38511833
Temperature 60
(oC)

Energy Balance around Absorber:

Using sample calculation

Sample Calculations

Q = m x Cp x (T-TR)

Heat entering in absorber:

Qin-Total = Qin-C4 +Qin-C2 + Q in-H2S + Q in- H2

Components Flow rate-m Cp T Tr Qin

o o
(kg/hr) kJ/kg- ( C) ( C) (kJ/hr)
o
C
C4 26.566 1.84 40 0 193.0
C2 22.626 1.84 40 0 1665.27
H2 2939.478 14.64 40 0 1721358.31
H2 S 1152.678 1.05 40 0 48412.47
Lean DEA 19211.3 3.5 40 0 2689582
 Qin-Total =4461211.05 kJ/hr

Heat out from absorber:

From top,
Qout-top = Qout-C4 +Qout-C2 + Q out-H2S + Q out- H2

Components Flow rate-m Cp T Tr Qout

(kg/hr) kJ/kg- (oC) (oC) (kJ/hr)
o
C
C4 5.313 1.84 40 0 391.1
C2 13.576 1.84 40 0 999.19
H2 2939.478 14.64 40 0 1721358.31

Qout-top = 1722748.6 kJ/hr

From bottom,
Qout-bottom = Qout-C4 +Qout-C2 + Q out-H2S + Q out- DEA solution

Components Flow rate-m Cp T Tr Qout

(kg/hr)
kJ/kg-oC (oC) (oC) (kJ/hr)

C4 21.253 1.84 40 0 1564.22

C2 9.05 1.84 40 0 666.08

H2 S 1152.678 1.05 40 0 48412.48

Rich DEA 19211.3 3.2 40 0 2459046.4

Qout-bottom = 2509689.18 kJ/hr

Total Heat out, Qout = Qout-top + Qout-bottom

Qout =4232437.8 kJ/hr

 Heat losses Qloss = Qin - Qout

Heat losses Qloss = 228773.27 kJ/hr

Lean DEA 20% Gas stream

Qin(kJ/hr) Qout(kJ/hr)
DEA 20% 2689582 C4 391.1
C2 999.19
H2 1721358.31

Gas stream Rich DEA

Qout(kJ/hr) Qout(kJ/hr)
C4 193.0 C2 666.08
C2 1665.27 C4 1564.22
H2 1721358.31 H2 S 48412.48
H2 S 48412.47 DEA 20% 2459046.4
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