THE MODELING OF PETROLEUM COKE GASIFICATION USING ASPEN

PLUS SOFTWARE

by

Saif Yoseif Salih

B.Sc. of Mechanical Engineering, University of Anbar, Iraq, 2005

A Thesis

Submitted in Partial Fulfillment of the Requirements for the

Master of Science Degree

Department of Mechanical Engineering and Energy Processes

in the Graduate School
Southern Illinois University Carbondale
August 2015
 ProQuest Number: 1603256

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 THESIS APPROVAL

THE MODELING OF PETROLEUM COKE GASIFICATION USING ASPEN

PLUS SOFTWARE

By

Saif Yoseif Salih

A Thesis Submitted in Partial

Fulfillment of the Requirements

for the Degree of

Master of Science
in the field of Mechanical Engineering

Approved by:

Dr. Tomasz Wiltowski, Chair

Dr. James Mathias
Dr. Rasit Koc

Graduate School
Southern Illinois University Carbondale
June 25th, 2015
 AN ABSTRACT OF THE THESIS OF
Saif Yoseif Salih, for the Master of Science degree in Mechanical Engineering,
presented on June 25th, 2015 at Southern Illinois University Carbondale.

TITLE: THE MODELING OF PETROLEUM COKE GASIFICATION USING ASPEN

PLUS SOFTWARE

MAJOR PROFESSOR: Dr. Tomasz S. Wiltowski

Gasification of petroleum coke (Petcoke) has emerged in the last decades as one of

the attractive options and is gaining more attention to convert petcoke and oil residue to

synthesis gas (Syngas). Syngas consists mainly of hydrogen (H2), carbon monoxide

(CO), some other gases, and impurities. In this study, a simulation of Tuscaloosa

petcoke, typical gulf coast refineries petcoke, gasification was developed using ASPEN

PLUS software. Sensitivity analysis of the simulated model was performed to study the

variation in operation conditions of the gasifier such as temperature, pressure, oxygen

flow rate, and steam flow rate. The approach correlates the behavior of these

parameters with the syngas yield (i.e., H2, CO, CO2, H2O, CH4, and H2S).

Consequently, the desired syngas yield can be obtained by manipulating the gasifier

parameters. Implementing optimization calculation shows that up to (81 %) of the

gasifier cold gas efficiency (Based on LHV) can be achieved for the developed model.

Therefore, Tuscaloosa petcoke gasification under the aforementioned parameters is

feasible and can be commercialized. This leads to more utilization of the bottom of oil

barrel by upgrading it to more valuable gases with less environmental impacts.

i
 DEDICATION
I dedicated this work to my parents, my wife, and my three children. I am very

grateful to all of you for your support and encouragement through my master study to

achieve my goals.

ii
 ACKNOWLEDGMENTS
I would like to express my sincere gratitude and appreciation to my advisor Dr.
Tomasz Wiltowski for his support of my master thesis and research to make it much
productive and stimulating. I am so thankful for his guidance, motivation, enthusiasm
which helped me in all the time of research and writing of this thesis.
I would like to extend my great thankful to the rest of my thesis committee:
Dr. James Mathias and Dr. Rasit Koc for their willingness, encouragement, insightful
comments, and their dedicated time and ultimate support to complete my thesis.
Finally, I would like to show my profound gratitude to the staff of the Engineering
Computer Support Center (ECSC) at the College of Engineering for their support in
insulating ASPEN PLUS software and their invaluable scientific contributions through
my thesis simulation and analysis.

iii
 PREFACE

When the London Gas, Light, and Coke Company was founded in 1812, the

gasification technology was commercialized and widespread. Since then, gasification

plays a major role in the industrial sectors. It started with a simple use to produce the

town gas (industrial gas) from coal to illuminate roads and streets and for cooking use.

After 1900, when the electrical bulbs appeared, town gas used for heating purposes. I

have decided to write my thesis in gasification of petcoke because I believe that it is

one of the important sources of clean energy in the world. Gasification technology has a

promising future as an alternative energy source because the feedstock materials and

the products are versatile and have lots of applications. This research investigates the

keys that impact the gasification processes to optimize the products (syngas) to meet

the industry demands (i.e., ratios of H2/CO). I tried to provide in details and plots these

effects so the readers can clearly understand how the gasification processes products

be utilized in the best way.

iv
 TABLE OF CONTENTS

ABSTRACT ...................................................................................................................... I

DEDICATION .................................................................................................................. II

ACKNOWLEDGMENTS................................................................................................. III

PREFACE ......................................................................................................................IV

LIST OF TABLES .......................................................................................................... VII

LIST OF FIGURES ....................................................................................................... VIII

LIST OF EQUATIONS .................................................................................................... X

NOMENCLATURE ......................................................................................................... XI

INTRODUCTION ............................................................................................................. 1
1.1 PETROLEUM COKE DEFINITION .................................................................................. 1
1.2 MOTIVATION............................................................................................................. 3
1.3 SCOPE OF THE W ORK ............................................................................................... 4
LITERATURE REVIEW .................................................................................................. 6
2.1 THE PYROLYSIS PROCESSES .................................................................................... 7
2.1.1 Primary Pyrolysis ............................................................................................ 7
2.1.2 Secondary pyrolysis ........................................................................................ 8
2.2 GASIFICATION PLANTS IN THE W ORLD ...................................................................... 10
2.3 GASIFICATION MECHANISM...................................................................................... 11
2.4 GASIFICATION REACTIONS ...................................................................................... 13
1. Volatile Combustion Reactions ........................................................................... 13
2. Boudouard Reaction ........................................................................................... 13
3. Water- Gas Reaction .......................................................................................... 14
4. The Methanation Reaction ................................................................................. 14
5. CO Shift Conversion ........................................................................................... 14
6. Steam Methane Reforming ................................................................................. 14
2.5 GENERIC TYPES OF GASIFIERS................................................................................ 15
2.5.1 Entrained Flow Gasifiers ............................................................................... 16
2.5.2 Fixed (Moving) Bed Gasifiers ........................................................................ 17
2.5.3 Fluidized Bed Gasifiers ................................................................................. 18
2.6 PLASMA GASIFICATION ........................................................................................... 19
2.7 UNDERGROUND COAL GASIFICATION ....................................................................... 20

v
SIMULATION PROCEDURE ........................................................................................ 21
3.1 GE (TEXACO) GASIFIER SELECTION CRITERIA .......................................................... 22
3.2 DESCRIPTION OF THE DEVELOPED FLOWSHEET ........................................................ 23
3.3 GIBBS FREE ENERGY MINIMIZATION MODEL ............................................................. 24
3.4 FEEDSTOCKS ......................................................................................................... 25
3.4.1 Petcoke ......................................................................................................... 25
3.4.2 Oxidant Agent ............................................................................................... 27
3.4.3 Steam............................................................................................................ 27
3.5 REACTORS............................................................................................................. 28
3.6 SYNGAS COOLING .................................................................................................. 31
3.7 SOLIDS REMOVAL ................................................................................................... 31
RESULTS AND DISCUSSION ...................................................................................... 33
4.1 SENSITIVITY ANALYSIS ............................................................................................ 34
4.1.1 Effect of Temperature Variation .................................................................... 35
4.1.2 Effect of Pressure Variation .......................................................................... 39
4.1.3 Effect of Oxygen Variation ............................................................................ 44
4.1.4 Effect of Steam Variation .............................................................................. 47
4.2 COLD GAS EFFICIENCY OF THE TUSCALOOSA PETCOKE GASIFICATION ....................... 51
CONCLUSION AND FUTURE WORK .......................................................................... 52
5.1 CONCLUSION ........................................................................................................ 52
5.2 FUTURE W ORK ..................................................................................................... 54
REFERENCES .............................................................................................................. 55

APPENDICES ............................................................................................................... 59
APPENDIX A................................................................................................................. 59
INPUT SUMMAY of TUSCALOOSA PETCOKE GASIFICATION SIMULATION
USING ASPEN PLUS ............................................................................................ 60
APPENDIX B................................................................................................................. 65
Final Syngas Stream Yield of Tuscaloosa Petcoke Gasification ............................ 66
VITA .............................................................................................................................. 69

vi
 LIST OF TABLES
Table 1. Gasification plants around the world with petcoke feedstock [2] ..................... 10

Table 2. Gasification classification ................................................................................ 15

Table 3. The Proximate analysis of the Tuscaloosa petcoke [5, 27] ............................. 25

Table 4. The ultimate analysis of the Tuscaloosa petcoke [5, 27] ................................ 25

Table 5. Petcoke ash composition (Oxides) [28] ........................................................... 26

Table 6. ASPEN PLUS component attribute ................................................................. 28

Table 7. Component yield of Tuscaloosa petcoke in the YIELD reactor ..................... 29

Table 8. RGIBBS reactor (Gasifier) products setting .................................................... 30

Table 9. Splitter (Filter) specification of the ASPEN PLUS ........................................... 32

Table 10. Gasifier temp. range with the syngas component flow rates ......................... 35

Table 11. Sensitivity analysis of optimum syngas components .................................... 37

Table 12. Sensitivity analysis of the pressure variation on the syngas flow rates ......... 41

Table 13. Optimum gasifier parameters ........................................................................ 51

vii
 LIST OF FIGURES
Figure 1. Pyrolysis and gasification processes [6]........................................................... 6

Figure 2. Influence of heating up on pyrolysis and gasification processes [4]................. 9

Figure 3 Simplified Schematic of an entrained flow gasifier ......................................... 16

Figure 4. (a) Updraft, (b) Downdraft, (c) Crossflow type fixed bed gasifiers [18] ........... 17

Figure 5. Simplified schematic of fluidized bed gasifier [5] ........................................... 18

Figure 6. Plasma gasifier [22] ....................................................................................... 19

Figure 7. Underground coal gasification processes [23] ............................................... 20

Figure 8. Flowsheet of petcoke gasification using ASPEN PLUS ................................. 23

Figure 9. Gibbs free energy minimization approach [26] ............................................... 24

Figure 10. Flow rate of H2 and CO with variation in gasifier temperature...................... 36

Figure 11. Flow rate of CO2and H2O with variation in gasifier temperature .................. 38

Figure 12. Flow rate of CH4 with variation in gasifier temperature ................................ 38

Figure 13. Flow rate of H2S with variation in gasifier temperature ................................ 39

Figure 14. Flow rate of H2 and CO with variation in gasifier pressure ........................... 40

Figure 15. Flow rate of CO2 and H2O with variation in gasifier temperature .................. 42

Figure 16. Flow rate of CH4 with variation in gasifier pressure ...................................... 42

Figure 17. Flow rate of H2S with variation in gasifier pressure ...................................... 43

Figure 18. Flow rate of H2 and CO with variation in oxygen flow rate ........................... 44

Figure 19. Flow rate of CO2 and H2O with variation in oxygen flow rate ....................... 45

Figure 20. Flow rate of CH4 with variation in oxygen flow rate ...................................... 46

Figure 21. Flow rate of H2S with variation in oxygen flow rate ...................................... 47

Figure 22. Flow rate of H2 and CO with variation in steam flow rate ............................ 48

viii
Figure 23. Flow rate of CO2 and H2O with variation in steam flow rate ......................... 49

Figure 24. Flow rate of CH4 with variation in steam flow rate ........................................ 50

ix
 LIST OF EQUATIONS
EQUATION PAGE

Equation 1 ..................................................................................................................... 13

Equation 2 ..................................................................................................................... 13

Equation 3 ..................................................................................................................... 13

Equation 4 ..................................................................................................................... 13

Equation 5 ..................................................................................................................... 14

Equation 6 ..................................................................................................................... 14

Equation 7 ..................................................................................................................... 14

Equation 8 ..................................................................................................................... 14

Equation 9 ..................................................................................................................... 29

Equation 10 ................................................................................................................... 51

x
 NOMENCLATURE
ASPEN Advanced system for process engineering
DC Delayed coke
FC Fluid coke
MMTPA Million metric tons per annum
CPC Calcined petcoke
IGCC Integrated gasification combined cycle
SNG Synthetic natural gas
DRG Direct reduction gas
PM Particulate matter
F Fahrenheit
Psia Pound per square inch absolute
C Celsius
atm Atmospheric pressure
Bar pressure measurement unit (1 atm=1.01325 bar)
CFD Computational fluid dynamic
BGL British gas Lurgi
FB Fluidized bed
FBR Fluidized bed recirculating
UCG Underground coal gasification
HHV Higher heating value
HRSG Heat recovery steam generator
EO Equation oriented
SM Sequential modular
LHV Lower heating value
BTU British thermal unit

xi
 CHAPTER 1

INTRODUCTION

1.1 Petroleum Coke Definition

Petroleum coke or petcoke, a refinery byproduct, is a carbonaceous solid material

delivered from oil refinery coker units or other cracking processes after upgrading

remains (residue) of the distillation tower to produce gasoline and middle grade fuels.

Coking units use heat to crack or break down large hydrocarbon molecules of heavy

crude converting it to lighter fuels (Mostly gasoline) and petcoke which cant be further

processed anymore. Petcoke is a black-colored solid composed mostly of carbon, and

may consist of limited amounts of elemental forms of sulfur, metals, and non-volatile

organic and inorganic compounds[1]. It is highly stable solid fuel and has a complex

mixture of hydrocarbons. Depending on the physical and chemical structures of the

hydrocarbon molecules of the petcoke, it can be categorized as honeycomb coke,

sponge coke, needle coke, and shot coke. Another classification for the petcoke is

based on the manufacturing or production processes such as delayed coke (DC) and

fluid coke (FC).

The world production of petcoke has reached 150 million metric tons per annum

(MMTPA) in 2014. The United States alone has produced 70 MMTPA which stands for

approximately 47% of the global production of petcoke. By 2015, a 70 MMTPA is

anticipated to be added to the petcoke production of 2014 to become over than 200

MMTPA in the world because of the increasing production of heavy crude and dwindling

supply of the light crude oil [2].

1
 Petcoke has generally been considered as an unusable byproduct due to high sulfur

content and some environmental issues if it is burned directly. About 80 percent of

petcoke is used as a fuel for electric utilities and cement kilns. Steel and iron factories

use petcoke as a main feedstock because the high heating value of petcoke

(Approximately 15,000 BTU/lb) to melt raw materials and the high content of carbon [3].

Calcined petcoke (CPC) has the highest carbon purity and is used in aluminum,

graphite electrode, steel, titanium dioxide and other carbon consuming industries [4].

Nowadays, energy industries view petcoke feedstock as a good resource for energy

generation because it is relatively cheap and available in refineries as a byproduct

which makes it much economical to be used as an energy source either for the same

refineries or nearby power generation plants. Petcoke has more carbon content than

other hydrocarbons like coal, biomass, and sewage residue. Consequently, this gives

petcoke more attention as an alternative feedstock to produce energy (Heat or

electricity). Petcoke can be used in a gasification process as a feedstock fuel to create

synthesis gas (Syngas) which is mainly hydrogen (H2) and carbon monoxide (CO).

Combustible syngas is versatile and very useful mixture to generate electricity by

burning it in the gas turbines (Brayton cycle). In addition, it can be used to generate

steam to produce electricity in Rankine cycle or used in both cycles which is called the

integrated gasification combined cycles (IGCC) [5].

The gasification products of petcoke or syngas can be used in the Fischer- Tropsch

process to convert it to different types of hydrocarbons and liquid fuels with various C/H

structures such as transportation fuel and diesel. Current research efforts are underway

to fully develop and optimize petcoke as a fuel resource to produce syngas through

2
gasification technology. Any improvements in petcoke gasification process and

understanding the effects of the pressure and temperature give it a great edge over

other feedstocks to produce hydrogen, SNG, ammonia, methanol, liquid fuels,

electricity, or direct reduction gas (DRG) [3-5].

1.2 Motivation
Gasification is a well-known technology of converting high carbonaceous material

like petcoke, coal, and biomass into syngas. Although it is a very complex process,

gasification has a promising future because the high efficiency with less environmental

impacts. In addition, the world is consuming more energy as the population increasing

in the world. Energy companies are looking for alternatives of using oil and natural gas

to meet the required demand of consumers. Oil and natural gas are not renewable

sources and the world is depleting these resources. Heavy oil and residue are expected

to increase as the light crude supply is dwindling. In the light of the current

circumstances, petcoke can be considered as a good potential source of energy

because of low cost, high calorific value, and availability.

Petcoke gasification has a potential cost- effective alternative to oil and natural gas

for power generation [6]. Petcoke gasifications product which is called syngas is

versatile because of the flexibility nature of this mixture. Syngas can be used for

electricity generation, liquid fuels, chemical industries, and fertilizer. The gasification

reactions are highly exothermic which can be deployed to produce steam and increase

the efficiency of the cycle. Gasification technology decreases the dependence on oil

3
and natural gas because of the conversion diversity of carbon- based feedstocks and

support of the national energy security.

Another aspect is the environmental pollution. One of the feasible features of

petcoke gasification is that it is environmentally friendly. Using the pre-combustion

capture and CO2 sequestration technique reduce carbon dioxide (CO2), sulfur oxides

(SOx), nitrogen oxides (NOx), and particulate matter (PM) in the flue or exhaust gas

after burning it [7].

1.3 Scope of the Work

The objective of this research is to model the gasification process of petcoke and

converting it into a syngas mixture by using Aspen Plus simulation software. A

simulation model of GE (Texaco) gasifier is employed in this study because it is widely

used in the world. Firstly, the Tuscaloosa petcoke is selected as a feedstock to the

gasifier to react with the oxidant agent and steam. I use ASPEN PLUS software

(version 7.3 ASPEN PLUS) to build up the flowsheet of the gasification process. A

nonstoichiometric reactor based on known yield distribution (RYIELD reactor) was

selected to break down the non-conventional solid petcoke feedstock into its elemental

constituents. Then, Gibbs free energy minimization reactor (RGIBBS) was connected to

the RYIELD reactor. The elemental constituents of petcoke enter the RGIBBS reactor

to react with steam and a limited amount of oxygen where gasification is occurred.

These two reactors are not existed in the actual gasification process. The RYIELD

reactor is virtual to break down the petcoke to its elements.

4
 The produced syngas in the RGIBBS reactor is directed to pass through a heat

exchanger to cold it down to about 500 F. Finally, the syngas undergoes a filtration

process to remove ash and particulate matter by passing it through a cyclone (Filter).

The clean syngas consists mainly of hydrogen, carbon monoxide, and other gases.

The syngas constituents were analyzed and studied under different scenarios of the

gasification conditions to investigate the impacts of these keys on the hydrogen and

carbon monoxide and other gases. A sensitivity analysis was performed to include a

wide range of the gasification conditions. Plots of syngas composition were generated

as a dependent variables (Y-axis) versus the different gasification conditions which

were the independent variables (X-axis).

5
 CHAPTER 2

LITERATURE REVIEW
Gasification is commonly used to thermally convert petroleum coke, coal, and

biomass into useful products. The process is a partial oxidation which converts carbon

based feedstock (Petcoke, coal, and biomass) into a synthesis gas (syngas). A simple

description of the gasification process that it starts when the feedstock is fed into a

pressurized vessel (Reactor) which contains a limited amount of oxygen (O2) or air.

Also steam or water is fed to the gasifier to react with the feedstock and oxygen under a

high temperature (Up to 3000 F) and pressure (Up to 800 psia) [5, 7]. In general, the

gasification process involves a series of complex chemical reactions of carbon with

steam and oxidant agent (Mostly oxygen) to produce the syngas. There are different

configurations of mixing the feedstock with steam and oxygen but the principle concept

of carbon conversion is almost the same. At higher temperature and pressure, pyrolysis

occurs, where the reacting particles (Mixture of feedstock, steam, and oxygen)

thermally decompose into lighter gas, condensable vapor (Tar), and solid residue

(Char) [8]. This process is called either pyrolysis or devolatilization which breaks the

weaker chemical bonds of reacting material into lighter components, tar, and char.

Figure 1. Pyrolysis and gasification processes [6]

6
 As mentioned previously, the amount of oxidant agent is well determined in the

gasification process which can be described as a partial oxidation. In other words,

gasification process is a combustion process but with a limited amount of oxidant agent

and it occurs at high pressure and temperature. Figure 1 gives a visual summary of

important steps in the devotalization and gasification processes of a solid fuel (i.e.,

petcoke, coal, biomass, or a mixture of petcoke and coal).

2.1 The Pyrolysis Processes

The pyrolysis or devolatilization processes takes place with the heating up of the

feedstock in the temperature range of 650 to 1000 F [8]. The particle size, the heating

rate, temperature, and partial pressure of steam and oxidant agent play an important

role in the devolatilization pace. Generally, the pyrolysis processes can be divided into

stages as following:

2.1.1 Primary Pyrolysis

This is the initial thermal decomposition of a particle into gas, tar, and char by

heating up the feedstock mixture inside the gasifier. This initial conversion occurs

without secondary reactions. During this stage, tars and volatile gases escape from the

heated solid particles as their bonds thermally collapse and rupture. Temperature,

pressure, size of particles, time of residence, and feedstock mixture (Slurry) all affect

the primary pyrolysis [4]. Actually, this is the most important step of the gasification

process because it acts as the feed or source of reactants for the next thermochemical

decomposition. More sophisticated research is needed to understand the primary

pyrolysis and its relations with the key factors such as temperature, pressure, and

feedstock mixture.

7
2.1.2 Secondary pyrolysis
It refers to the cracking, polymerization, condensation, and carbon deposition

processes that follow the primary devolatilization. The temperature in this stage is

higher than the initial one. The gas phase reaction is homogenous. However, the

reaction is heterogeneous on the surfaces of the solid fuel and char particle. These

reactions and conversions produce the syngas which is mainly hydrogen (H2) and

carbon monoxide (CO) with a small amounts of carbon dioxide (CO 2) and methane

(CH4).

Overall, about 70 percent of the feedstock higher heating value (HHV) is associated

with the syngas components of hydrogen (H2) and carbon monoxide (CO) [9].

According to Higman and Burgt in their book (Gasification, 2 nd Edition) [4], there is a

concrete relation between the pyrolysis rate and the gasification which impacts the

product mixture (syngas composition). Accordingly, when the heat up is slow (happens

when the temperature is around 650 F), the amount to volatile materials around the

reacting particles increases quickly. Then, gasification starts when the temperature hits

1000 F. In other words, pyrolysis and gasification has a gap time and they take place

separately. If, however, the heat up is fast and quick, both pyrolysis and gasification

occur simultaneously which means no time enough to form volatiles. This is the

explanation why the entrained flow gasifier produce clean syngas in short time. The

following diagram shows both cases.

8
 Figure 2. Influence of heating up on pyrolysis and gasification processes [4]

The pyrolysis products such as tars, gases which include (H2, CO, CO2, H2O), and

hydrocarbon liquids react with a well-determined amount of oxidant agent (O2) and

steam to trigger the gasification reactions. These reactions are referred as a partial

oxidation which deplete the provided oxygen and steam to convert most of reactants

into H2 and CO with small percentage of other gases (CO2, H2O, CH4, H2S, COS, etc.).

9
 2.2 Gasification Plants in the World
The gasification technology is gaining more attention in the world because of the

higher efficiency and the flexibility of the feedstock and the products. Consequently, the

gasification industry has grown and the number of gasification power plants increased

during the last decade. China, India, Germany, Denmark, Spain, Japan, and Italy are

countries that utilize the gasification technology with different feedstocks (Petcoke, coal,

biomass, and residue waste) [4]. Table 1 shows some of the petcoke gasification plants

around the world.

Table 1. Gasification plants around the world with petcoke feedstock [2]

Country Plant name Gasification Technology Feedstock Output

USA Wabash River Energy E-Gas ConocoPhillips Petcoke Electricity
USA Polk County IGCC GE Coal and petcoke Electricity
USA El Dorado IGCC Plant Texaco Petcoke and waste oil Electricity
USA Coffeyville Syngas Plant GE Petcoke Chemicals
USA Delaware Clean Energy Texaco Fluid petcoke Electricity
USA Lima Energy IGCC ConocoPhilips Coal and petcoke Electricity
Japan Ube City Co. Plant GE Petcoke Chemicals
Japan Ube Ammonia Ind. Co. GE Coal and petcoke Chemicals
China GE China 4 GE Coal and petcoke Chemicals
India Orissa Shell Gasification Coal and petcoke Chemicals

The electricity world production from the petcoke gasification exceeds 20,000 MW

[5]. China and India have witnessed a brisk pace of increasing the gasification plants.

The amount of heavy oil (vacuum residue) in the developed countries is expected to

increase next decades. Therefore, Utilization of petcoke using the gasification

technology becomes inevitable to satisfy the world energy demand from the remaining

energy of the distillation residue.

10
2.3 Gasification Mechanism
When the feedstock (Petcoke) enters the gasifier and reacts with the steam and the

oxidant agent, a series of chemical reactions are carried out at high temperature and

pressure. Because of the high temperature (1800 to 3000F) inside the gasifier, the

endothermic reactions such as the Boudouard reaction and the water gas reaction

happen simultaneously (Equations 4 and 5). These two reactions are triggered by the

initial main exothermic reactions in the gasifier (Equations 1, 2, and 3) [10]. The

exothermic reactions that happen in limited oxidant agent which prevents the

stoichiometric combustion of the feedstock. The heat produced by the exothermic

reaction provides most of the energy required for driving the endothermic gasification

reactions with high temperature in the gasifier [11].

Synthesis gas (Syngas) is produced after the endothermic reactions which is mainly

hydrogen (H2) and carbon monoxide (CO) with other gases and impurities (CO2, H2O,

and CH4) depending on the gasifier configuration, the feedstock type, and the

operational conditions of the gasification (i.e., Pressure, temperature, feedstock to

oxidant agent ratio). The pressure of the gasifier is also high (500 800 psia) which is

necessary to help decomposing the feedstock into its components and push the syngas

out of the gasifier to be processed in the downstream stages.

The raw syngas exits from the gasifier has a high caloric value. It is at high

temperature and pressure which are due to the exothermic reactions (thermal cracking

and partial oxidation). The hot syngas cools down to around 500F and then undergoes

a filtration process to remove some containments and impurities (Solid particles and

ash). The syngas cooling is achieved either by a heat exchanger or by the direct water

11
quench. Steam can be generated from the extracted heat and used to run a turbine to

produce electricity. In addition to the syngas, ash and slag (unburned solid particles)

are accumulated in the bottom of the gasifier and removed periodically.

The state-of-art of petcoke gasification was extensively investigated and found to be

relatively a modern topic with limited previous published literature. In his scientific

article, Zhonghau has studied the petcoke gasification characterizations

comprehensively. The study was conducted in a pilot project of one ton per day of

petcoke using an entrained flow gasifier. The research was performed experimentally

and numerically to study the cold efficiency of the gasification and the carbon

conversion. The overall gasification performance was conducted also by the research.

The results of Zhonghau research showed a good agreement between the

experimental work and numerical analysis. Based on his research, the operation

temperature of the gasifier was set at 1600 C (Equals 2912F) and 1 atm pressure [12].

Shen has studied the petcoke gasification conditions and reported that the

operational pressure of 4.2 bar (60.9 psia) which corresponds to a carbon conversion of

86%. [13].

Most of the literature art publications of petcoke gasification processes were

conducted using computational fluid dynamics (CFD) software. On the other hand,

ASPEN PLUS software was recently used to simulate the coal gasification processes in

the integrated gasification combined cycle (IGCC) power plants to find the overall

efficiency of the power plant rather than the optimal gasification conditions of the

gasifier part of the plant.

12
2.4 Gasification Reactions
There are several thermochemical reactions taking place in the gasifier as following:

1. Volatile Combustion Reactions

The partial oxidation of the volatile components takes place with a limited amount of

oxygen. This is one of the most important differences between gasification and

combustion. The later happens with an excess amount of oxygen (stoichiometric or rich

combustion). The char oxidation (Eq. 1) is heterogeneous and other reactions (Eq. 2

and 3) are homogenous. These reactions release heat that is necessary to drive the

following endothermic reactions. Carbon is reacted with oxygen to produce carbon

monoxide which reacts with the remaining oxygen to form carbon dioxide. Additionally,

steam is produced from the reaction of hydrogen and the left oxygen from the first and

the second reactions. All these reactions are exothermic (partial combustion) and the

products of these reactions will be reactants for the upcoming endothermic reactions.

The volatile combustion reactions are shown below:

C + O2 CO (-111 MJ/kmol) (1)

CO + O2 CO2 (-283 MJ/kmol). (2)

H2 + O2 H2O (-242 MJ/kmol) ... (3)

2. Boudouard Reaction
Boudouard reaction is the reaction of carbon dioxide that produced from the volatile

combustion (Eq. 2) and carbon (char) to produce carbon monoxide. It is an endothermic

and heterogeneous reaction and the carbon monoxide (CO) formation favors a high

temperature to take place (Temp. > 1300 F) [4].

C (S) + CO2 (g) 2 CO (g) (+172 MJ/kmol) . (4)

13
 3. Water- Gas Reaction
The water gas reaction is given as:

C + H2O CO + H2 (+ 131 MJ/kmol).... (5)

4. The Methanation Reaction

The methanation reaction is given as,

C + 2H2 CH4 (-75 MJ/kmol) ... (6)

5. CO Shift Conversion
The CO shift conversion or called (Water gas shift reaction) adjust the hydrogen to

carbon monoxide ration of the final syngas composition. It is given as:

CO + H2O CO2 + H2 (-41 MJ/kmol) .. (7)

6. Steam Methane Reforming

The steam methane reaction is given as:

CH4 + H2O CO + 3 H2 (+206 MJ/kmol) .. (8)

The aforementioned heat of reactions (Enthalpy of reactions) are measured in

standard conditions (i.e. temperature = 298 K and pressure = 1 atm) [5, 14].

Under the condition of high carbon conversion, the Boudouard reaction, the water

gas reaction, and the methanation reaction which are heterogeneous reactions (Eq. 4,

5, and 6) can be reduced to two homogeneous gas phase reactions of CO shift

conversion (Eq. 7) and steam methane reforming reaction (Eq. 8) [14]. They last two

reactions play a key role in determining the final equilibrium synthesis gas (syngas)

composition. Sulfur in the feedstock is converted to hydrogen sulfite (H2S) and a limited

amount of carbonyl sulfide (COS) [15].

14
 2.5 Generic Types of Gasifiers
Gasifiers are usually divided to entrained flow, fluidized bed, fixed (Moving) bed

gasifiers, and plasma gasifiers. The classification is based on the configuration of the

gasifier and how the gas and fuel contact with each other. The below table shows some

more different types of gasifiers.

Table 2. Gasification classification

Gasification Technologies

1-Entrained Flow 2-Moving Bed 3-Fluidized Bed

Koppers- Totzek Gasifier Lurgi Dry Bottom Gasifier Winkler Process
KBR Transport Gasifier
Seimens SFG Gasifier BGL Slagging Gasifier
Twin Reactor Gasifier

E- Gas Gasifier (Texaco) EBARA Gasifier

GTI Membrane Gasifier
MHI Gasifier Rotating Fluidized Bed
Gasifier
Eagle Gasifier Internal Circulating Gasifier
Foster Wheeler CFB Gasifier
Coaxial Downflow Downdraft Bubbling

Updraft Circulating
Opposed Jet
Crossdraft Twin bed

15
A brief description of each type is given in the followings:

2.5.1 Entrained Flow Gasifiers

The Texaco or the E-Gas (ConocoPhillips) gasifier is a good example of the

entrained flow gasifiers. The feedstock is elutriated by the oxidant and the steam

streams. Furthermore, the gasifier introduces oxygen and steam along with feedstock in

the form of small particles from the bottom (Opposed jet type). High velocity of oxygen

and steam is required to ensure a proper contact with the feedstock stream. In addition,

the range of the particle size of the feedstock is 0.1 to 0.2 mm to ensure a high carbon

conversion. Temperature is very high, 2000 F, and the pressure is around 800 psia

[16]. The entrained flow gasifiers can handle a wide range of feedstock (coal, petcoke,

and residue waste). Because of the high temperature and pressure, tar-free syngas is

produced and the ash melts on the gasifier walls to be discharged as molten slag from

the bottom of the gasifier[17].

Entrained flow gasifiers have low residence time (0.5 to 2 seconds) due to high

temperature and pressure inside the gasifier. Figure 3 shows a typical entrained flow

gasifier.

Figure 3. The entrained flow gasifier

16
2.5.2 Fixed (Moving) Bed Gasifiers
Fixed or called sometimes moving bed gasifiers can be classified into updraft,

downdraft, and crossdraft types according to the gasification medium flow directions.

British Gas Lurgi (BGL) is an example of this type of gasifiers. The most common used

types are updraft and downdraft. In the updraft fixed bed gasifier, feedstock is fed

through the top into a lock hopper. The function of the hopper is to collect the feedstock

and then pressurize it into the reactor. However, the oxidant agent and the steam are

fed from the bottom of the gasifier. As a result, a counter- current flow occurs which

improves the carbon conversion because of the opposite movement of the feedstock

and the mixture of oxygen and steam. Some of resulting char falls and burns to provide

heat. The syngas leaves the gasifier from the top with a relative high content of

methane and tar [18]. Ash is collected in the bottom of the gasifier. Figure 4 shows the

three types of fixed (moving) bed gasifiers.

Figure 4. (a) Updraft, (b) Downdraft, (c) Crossflow type fixed bed gasifiers [18]

17
2.5.3 Fluidized Bed Gasifiers
Figure 5 shows a simple schematic of the fluidized bed (FB) gasifier. A fluidized bed

gasifier is a well-stirred or back-mixed reactor. Fluidized bed gasifiers can be classified

into two types; bubbling or recirculating. In the fluidized bed recirculating (FBR), a

consistent mixture of new feedstock particles mixed with older particles (partially

gasified particles) to form a bed with uniform temperatures. In addition, the oxidant

agent and steam must have a sufficient velocity (5 to 10 m/sec) to float the fuel

feedstock particles [19, 20]. Consequently, the feedstock particles will undergo

fluidization by mixing with high flow rate of oxidant agent and steam. Then, the gasified

particles will be lighter and smaller which make it entraining out of the reactor.

Figure 5. Simplified schematic of fluidized bed gasifier [5]

One of the important thing to mention here is that the bed maintains a constant

temperature under the initial ash fusion point to avoid de-fluidization of the bed and

clinker formation. The temperature range is (1600- 1850 F) and the residence time is

(0.5 to 2 sec) [21].

18
2.6 Plasma Gasification
Plasma technology is relatively new in the gasification industry. Plasma can be as a

charge fluid or ionized gas. It can be generated from the passing of electrical discharge

into a gas. Intense thermal energy (Heat) at very high temperature accompanies the

process of plasma torch is initiated through the reactant gases in the gasifier.

Consequently, the gasification reactions will establish to convert the carbonaceous

based-feedstock into a syngas under plasma arcs discharges.

The primary use of plasma gasifiers is to destroy hazardous materials and municipal

waste. It is known as a recycled technology in which these dangerous and municipal

refuse are gasified to generate energy for utilities usage. Japan, Canada, India have

commercialized the plasma gasification technology to recycle wastes in which the

syngas is provided for electrical power plants [22]. Figure 6 illustrates a plasma gasifier.

Figure 6. Plasma gasifier [22]

19
2.7 Underground Coal Gasification
When the coal reserve is deep in the earth, the mining of coal will be difficult and not

economical. Therefore, underground coal gasification (UCG) has been used to utilize

this un-minable underground coal. The underground coal gasification process uses the

earth crust or the reserve seam as a reactor in which the gasification reactions take

place. In addition, two vertical wells are drilled to provide oxygen and collect syngas.

The amount of provided oxidant agent (oxygen or air) must be controlled to ensure the

partial oxidation underneath the earth. The produced syngas can be used to generate

electricity, chemicals, transportation fuels, and fertilizer. The ash and other slagging

material will stay in inside the earth reservoirs and cavities which eliminates any

environmental issues with this technology [23]. Figure 7 shows the underground coal

gasification processes.

Figure 7. Underground coal gasification processes [23]

The underground coal gasification technology was used in the former Soviet Union

in the 1950s. Nowadays, however, it is used in other countries such as China, Australia,

Canada, India, and the United States.

20
 CHAPTER 3

SIMULATION PROCEDURE
A new model of the petcoke gasification process through an entrained flow gasifier

is developed using ASPEN PLUS software (ASPEN stands for advanced system for

process engineering). ASPEN PLUS software is a steady state simulation software

which uses mass and energy balance equations, thermodynamic properties, and

reaction kinetics with a huge database and information of components and chemical

reactions. ASPEN PLUS software was introduced at Massachusetts Institute of

Technology (MIT) in 1970s to optimize the use of energy resources when the oil crisis

existed in that time. By developing ASPEN PLUS software, researchers tried to look for

alternative energy resources rather than depending on oil and natural gas which had

shortages in the 1970s due to political issues between oil produced countries and the

western world.

One of the most feasible feature of the ASPEN PLUS software is it answers the

question (What if we use this?) in short time and much less cost. In other words, if an

engineer simulates a process, he/she can study more intensively the operational

conditions and see the impacts by using the ASPEN PLUS simulation flowsheet. Then,

the optimal conditions can be selected based on the sensitivity and optimization

features of ASPEN PLUS software. A wide range of scenarios can be studied in an

effective way and short time which means that more understanding and validation for

the real process reactions. During the last decade, ASPEN PLUS software has been

developed and commercialized to be used in a wide range of applications. It is the

market leading software in the processing and chemical engineering applications.

21
3.1 GE (Texaco) Gasifier Selection Criteria
The ASPEN PLUS software was used to model the petcoke gasification in which the

reactants or the feedstocks (Petcoke, oxidant agent, and steam) were converted to

syngas (H2, CO, CO2, H2O, CH4, H2S, and other gases and impurities). A GE (Texaco)

gasifier which is an entrained flow gasifier was employed in this study for the following

reasons:

1- The petcoke is a stable substance with a low reactivity which makes it unsuitable

to be used in a fixed (Moving) bed gasifier. The Fixed bed gasifier requires a

reactive feedstock to maintain the permeability of the bed. On the other hand,

the entrained flow gasifier does not imply stringent requirements regarding the

reactivity of the feedstock so it is compatible with a wide range of feedstock

types including petcoke.

2- The fluidized bed gasifiers operate at a relatively low temperature (1000 to

1800F). The reasons behind that are to prevent the ash agglomeration and

maintain the suspension or fluidization of the particles in the bed. The entrained

flow gasifiers, however, work in higher temperature ranges (2000 to 3000 F)

which gives it an incentive to increase the carbon conversion of the petcoke with

a much higher efficiency.

The entrained flow gasifiers that work in the slagging Temp. range 2000 to 300F

are appropriate for the petcoke feedstock. Beside the high temperature ranges, the

residence time is very short ( 0.5 to 5 seconds) gives a good conversion for the petcoke

to syngas with a high efficiency [24]. Other factors to be considered when select gasifier

are energy and moisture content, volatile matter, bulk density, and particles size.

22
3.2 Description of the Developed Flowsheet
The petcoke gasification flowsheet is shown in Figure 8. Petcoke is prepared and

fed into the gasifier with the oxidant agent and steam. Petcoke is solid particles which

need to be crushed to increase the gasification efficiency. We assume that the petcoke

has uniform size particles in the simulation for simplicity. Firstly, the petcoke undergoes

a decomposition process in RYIELD reactor to break it down virtually to the main

constitute elements. (C, N, H, O, S, and moisture) based on ultimate analysis of the

feedstock. Then, these decomposed elements are fed into the gasifier (RGIBBS)

reactor to mix with the oxidant agent (Oxygen or air) and steam which form a slurry

mixture. Beside the aforementioned reasons for choosing the GE (Texaco) gasifier, it is

widely used in the world especially in the integrated gasification combined cycle (IGCC).

Figure 8. Flowsheet of petcoke gasification using ASPEN PLUS

The gasification process is as fast as the combustion process with a mean

residence time from 0.5 to 5 Seconds [5, 25]. For this reason, we modeled it with a

23
single gasifier (RGIBBS reactor). The gasification reactions in the (RGIBBS) reactor are

modeled by identifying the possible products of the syngas to investigate extensively

the composition of each components (i.e., H2, CO, CO2, H2O, CH4, and H2S).

3.3 Gibbs Free Energy Minimization Model

The gasification reactions are complex because they include many different types

(endothermic, exothermic, partial oxidation, methanation, homogenous, heterogeneous,

etc.). To simplify the gasification reactions in our simulation model, it was modeled

using the approach of minimization the Gibbs free energy. Thus, we reduce the

required data of the model because the gasification reactions follow the equilibrium

constants. Consequently, the overall model is simplified which means less inaccuracies

and uncertainties of the gasification reactions [26]. Nevertheless, the required data in

the Gibbs free energy approach deals with the reactants and the products component

information. Therefore, the gasification reaction pathways are not needed as much as

the specifications of the reactants and the products of the process. The below figure

gives an overview for the Gibbs free energy minimization.

Figure 9. Gibbs free energy minimization approach [26]

24
3.4 Feedstocks
3.4.1 Petcoke
Tuscaloosa petcoke is selected as the feedstock. Most of the gulf coast refineries of

Texas in the United States by-product is Tuscaloosa petcoke. Another reason for

choosing Tuscaloosa petcoke is that it has a relatively high concentration of sulfur

which generalizes other types of petcoke with lower sulfur contents.

The proximate analysis of Tuscaloosa petcoke is shown in the below table [5, 27].

Table 3. The Proximate analysis of the Tuscaloosa petcoke [5, 27]

The ultimate analysis of the Tuscaloosa petcoke is shown in the below table [5, 27].

Table 4. The ultimate analysis of the Tuscaloosa petcoke [5, 27]

25
 The ash composition of the Tuscaloosa petcoke is given in the below table.

Table 5. Petcoke ash composition (Oxides) [28]

Components (Oxide) Weight % (As received)
Calcium, CaO 11.9
Magnesium, MgO 5.1
Sodium, Na2O 1.0
Silica, SiO2 18.9
Aluminum, Al2O3 4.8
Ferric, Fe2O3 7.6
Phosphorus, P2O5 0.1
Potassium, K2O 0.7
Sulfur, SO3 13.8
Vanadium, V2O5 30.2
Nickel, NiO 6.0

The flow rate of the petcoke is 2135 lb/hr which gives approximately 3 Megawatt of

net power. This flowrate represents a middle refinery distillation tower production which

is the current state-of-the-art [5, 28]. This power capacity is suitable to meet the

electrical power demand of the refinery facilities. Refineries need hydrogen to process

the crude oil to lighter fuel grades and the gasification products can be an economical

source for hydrogen and other gases. In addition, cooling of the syngas generates high

pressure steam which can be directed to the distillation towers of the refineries.

Gasification of petcoke offers an integrated solution for refineries by consuming the

petcoke and supplying the refiners back with electricity, steam, and other important

gases such as hydrogen.

26
3.4.2 Oxidant Agent
Oxygen was used as an oxidant agent in the simulation. The pressure of oxygen

was set at 600 psia. The oxidant agent stream (Material stream in ASPEN PLUS) was

connected directly to the RGIBBS reactor to react with the petcoke and steam. Because

of the required high temperature that ensures a good conversion of the reactants, the

GE (Texaco) gasifiers (Entrained flow gasifier) need a high oxygen rate feed to

generate high temperature. Many oxygen flow rate scenarios were investigated and

varied from (20 to 100 Ibmole/hr) by performing the sensitivity analysis of the ASPEN

PLUS software. An optimal flow rate of oxygen that meets our requirements of the

syngas components can be reached. Gasification which was defined as a partial

oxidation is so sensitive for the amount of oxygen to prevent stoichiometric combustion.

Plots of the oxygen flow rates versus the syngas components were generated to

designate the optimum oxidant agent flow rate.

3.4.3 Steam
Steam stream was linked directly to the RGIBBS gasifier with the same oxidant

agent pressure (600 psia). In the simulation input specification of the reactants, 100 %

of H2O was selected to represent the steam. In addition to the hydrogen of the petcoke,

steam is an important source of hydrogen for the gasification reactions. In the water-

gas reaction (Eq. 5), steam reacts with char to produce hydrogen and carbon

monoxide. By using sensitivity analysis of the ASPEN PLUS simulation, the molar flow

rate of steam was varied from (20 to 100) Ibmole/hr and the syngas composition

percentages were monitored accordingly to optimize the flow rate of the steam stream.

27
3.5 Reactors
The simulation has two reactors as mentioned in the description of the overall

flowsheet. Although the petcoke gasification process occurs in one gasifier (reactor),

the simulation of this process was built up using two reactors. The first reactor which

receives the material stream of petcoke (Non-conventional solid material) is the

RYIELD reactor (Decompos). The petcoke is defined in the material stream by using its

component attribution (i.e. Proxanal, ultanal, and sulfanal). This definition allows to

ASPEN PLUS software to keep track of properties that do not affect material and

energy balance calculations. The below table shows the component attribute with some

pertaining information.

Table 6. ASPEN PLUS component attribute

The heat of combustion (HHV) of the Tuscaloosa petcoke, 15,000 BTU/Ib, was

entered manually to the parameters under properties sets. The enthalpy model name

(HCOALGEN) was set to (6, 1, 1, 1) so ASPEN PLUS accepts the HHV manually. In

the real gasification process, the RYIELD reactor does not exist. It is virtually modeled

28
to decompose Tuscaloosa petcoke into its constitute elements based on the ultimate

analysis (C, H2, N2, S, O2, ash, and moisture). From the ultimate analysis of Tuscaloosa

petcoke elements, the yield distribution is entered as mass yield of components per

total mass of feed. For instance, mass of hydrogen was calculated from the following

equation:

Mass H2=(1-Xmoisture)*XH*mfeed (1-0.01)*3.8/100*2135=80.3187 ..(9)

Yield of H2= 80.3187/2135=0.03762 (Hydrogen yield per the total feed petcoke). This

was applied for other Tuscaloosa petcoke constituents. The yield of each component

was input manually as it is shown in the below table.

Table 7. Component yield of Tuscaloosa petcoke in the YIELD reactor

After breaking down the petcoke into elements, they enter the RGIBS reactor

(Gasifier) to react with the oxidant agent and steam. The sensitivity analysis of the

pressure and the temperature were performed in the RGIBBS reactor. The range of the

pressure varies from (100 to 800) psia while the temperature varies from (1400 to 3000

F). Under the products option of the RGIBBS reactor, we have chosen (Identify

29
possible products) as it is shown in table 7 to study all the component percentages of

the syngas and what are the key roles of the operational conditions. The RYIELD and

RGIBBS reactors are connected with a heat stream (DECOMHEAT dotted line)

because the gasification exothermic reactions provide the required heat for the

endothermic reactions. Another heat stream (HEATOUT) is connected to the RGIBBS

reactor to represent the extra heat that generates and transfers to the vicinity of the

gasifier (Can be utilized to generate steam).

Table 8. RGIBBS reactor (Gasifier) products setting

30
3.6 Syngas Cooling
Syngas leaves the gasifier (RGIBBS reactor) at a high temperature (2000-3000 F).

The cooling processes of the hot syngas can be achieved by either direct water quench

or by passing it through a heat exchanger (Convection and radiation). In both cases,

heat recovery from the hot syngas can be deployed to generate steam which is

essential to enhance the gasification efficiency. In our simulation in figure 8, we have

used a heat exchanger (HXSYNGAS) to cool the syngas to 500 F. Another reason to

bring the syngas temperature down to this level is that the downstream cleaning

processes have stringent temperature requirements in the range of 500 F. The

generated steam can be used for the steam feedstock of the gasifier itself or providing

the refinery facilities (Distillation towers). In the integrated combined cycle (IGCC), the

high pressure stream is directed to the heat recovery steam generation (HTSG) to run

steam turbines to generate electricity.

3.7 Solids Removal

The syngas that comes out of the gasifier has some impurities such as soot, ash,

and particulate matter. After cooling it down to around 500 F, the syngas passes

through a filtration process. A SSPLIT mixer/splitter (ASHREM in the flowsheet in figure

8) was used to purify the syngas from these contaminants. Its necessary to mention

that the syngas needs to be cooled down to around 500 F which ensure a long

operation hours for the filter. The outcomes of the splitter are the cleaned syngas and

the contaminants exit from a separated stream. Table 9 shows the input specifications

of the splitter.

31
Table 9. Splitter (Filter) specification of the ASPEN PLUS

The MIXED stream split fraction is given the value of 1 to allow to pure gases of the

syngas to pass through the syngas stream (SYNGAS). However, the CISOLID and NC

split fractions are set to zero because we need the syngas stream without any solid or

non-conventional particles (Ash, soot, and particulate matter). Instead, these impurities

(CISOLID and NC) are directed to the ASH stream (Figure 8) with a split fraction of 1 in

the ASH stream. No chemical reactions occur in the splitter as it is a physical filtration to

get rid of solid particles and contaminants. These impurities will be collected and sent to

other processing units. Vanadium and building materials are the most final products

from the ash and other solid particles.

32
 CHAPTER 4

RESULTS AND DISCUSSION

In this simulation, the Tuscaloosa petcoke gasification model was built up using the

aforementioned units. The required data was input to the model and the process

flowsheet was ready to simulate the gasification process. Then, the model was tested

to validate the results and check the compatibility with the literature and cited materials

that found in [4, 5]. The gasifier parameters and the syngas composition were the focus

of this study by performing the sensitivity analysis of ASPEN PLUS software to the

simulated model. We have studied four different scenarios of the gasifier parameters

which were temperature, pressure, oxygen flow rate, and steam flow rate. By varying

these four parameters of the gasifier (Independent variables) within the range cited in

the state-of-the-art. The simulation model of petcoke gasification (Using APSEN PLUS

software) calculated the syngas composition and flow rate of each components

(dependent variables). Again, the focus was given to specific gases such as (H 2, CO,

CO2, H2O, CH4, and H2S). This approach relates the various gasifier parameters with the

syngas composition to assign the optimal operational gasification conditions

(Parameters) which meet our demand of the different syngas components.

The sensitivity analysis of the ASPEN PLUS software is a very useful tool because it

allows us to examine the behavior of each parameter and gives us what are the impacts

of this parameter on the syngas elements. Furthermore, we investigated the operation

conditions of the gasifier to optimize the petcoke gasification products for the

appropriate use in the downstream applications (Electrical power plant, Fischer-Tropsch

synthesis, transportation fuels, ammonia, methanol, and fertilizer).

33
4.1 Sensitivity Analysis
It is a very useful tool to calculate and find how a process reacts to different

operational keys or variables. In our simulation, we have used it to vary temperature,

pressure, oxygen flow rate, and steam flow rate to study the effects of these different

parameters on the syngas compositions which were represented by the molar flow rate

of the studied gases. It is very advantageous to use the sensitivity analysis as we can

design the models specifications within the range of manipulated operational

conditions. This leads to optimize the petcoke gasification process by identifying the

economical use of input energy and much more utilization of the syngas products. Both

equation oriented (EO) and sequential modular (SM) techniques support the sensitivity

analysis which was applied in this approach of the gasifier operational conditions.

Different downstream applications of the petcoke gasification processes need some

specific requirements regarding the syngas composition. For instance, if the desired

application of the syngas is to generate electricity, we need syngas with a higher

heating value (HHV) (i.e., Rich with hydrogen and carbon monoxide). By applying the

sensitivity analysis of the petcoke gasification, we can design the gasifier working

conditions to obtain as high as possible of the HHV of the syngas.

Another example of the downstream application is the Fischer-Tropsch synthesis

(FTS) in which the syngas is converted into liquid fuels. The desired hydrogen to carbon

monoxide (H2/CO) for the FTS process is 2:1 to convert it to transportation fuel. Again,

the sensitivity analysis predicts the best operational conditions of the petcoke gasifier

that produce the appropriate ratio of (H2/CO) in the syngas products to feed it to the

(FTS) plant.

34
4.1.1 Effect of Temperature Variation
Temperature is a very crucial parameter for the gasification process. In this

simulation, we have tested the range of temperature of the gasifier from 1400 to 3000

F. Then, the syngas components were monitored within that temperature range. Plots

of the temperature range versus the molar flow rates of syngas elements were created

to study the behavior of temperature change on each component. Figure 10 shows the

variation of hydrogen and carbon monoxide flow rates with the gasifier temperatures.

From figure 10, it was found that as the gasifier temperature increases, the H 2 and

CO molar flow rate increase too. This trend of increasing in H2 and CO applies from

1400 F until the temperature reaches 2400 F. Increasing the gasifier temperature

more and more does not cause the same increasing trend in H 2 and CO after the

temperature of 2400 F. The below table gives the sensitivity analysis for the

temperature range of (1400 to 3000 F).

Table 10. Gasifier temp. range with the syngas component flow rates

35
 Sensitivity Results Curve
20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0

140.0150.0
110.0120.0130.0
30.040.050.060.070.080.090.0100.0
CO LBMOL/HR
H2 LBMOL/HR

H2 LBMOL/HR
CO LBMOL/HR

1400.0 1600.0 1800.0 2000.0 2200.0 2400.0 2600.0 2800.0 3000.0

GASIFIER TEMP F

Figure 10. Flow rate of H2 and CO with variation in gasifier temperature

We have defined the temperature of 2400 F in the design parameters of the

gasifier. This temperature corresponds with the optimum production syngas

components (Higher heating value HHV). Obviously, any increase in the gasifier

temperature beyond 2400 F will not be economical because the flow rate line of H2 and

CO in figure 10 will become horizontal (Very little increase). Table 11 illustrates the

optimum flow rate of the syngas components as the sensitivity analysis definition

(Define Variable). Note that these base-case values of each gas match the temperature

of 2400 F in the previous table in accordance to the selected temperature.

36
Table 11. Sensitivity analysis of optimum syngas components

At higher temperatures (Around 2500 F), hydrogen and carbon monoxide become

unstable gases and they start converting into fully combusted products such as H2O

and CO2 if these is enough oxygen supply. The temperature has a significant influence

on the chemical reactions of the gasification process. The methane decomposition

reaction (eq. 8 in chapter 2) decreases at higher temperatures. Therefore, the tendency

of H2 and CO gases production is less after the temperature of 2400 F.

Figure 11 shows the molar flow rate of CO2 and H2O with the gasifier temperature

variations. Clearly, both flow rates of CO2 and H2O decrease as the temperature

increases till it reaches 2400 F. This is because that the gasification reactions flavor

this range of the temperatures to produce more H2 and CO. However, at higher

temperatures (around 2500 F and higher), the steam methane reforming reaction

(Eq.8, chapter 2) (CH4 + H2O CO + 3 H2) goes in the reverse direction which leads

to more H2O (Increased from 2.10443175 to 2.12062248 Ibmole/hr after temp 2800 F).

CO2 decreases very slightly after the temperature 2400 F.

37
 Sensitivity Results Curve
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0

35.0
CO2 LBMOL/HR
30.025.0 H2O LBMOL/HR
CO2 LBMOL/HR

H2O LBMOL/HR
15.0 20.0
10.0
5.0
0.0

1400.0 1600.0 1800.0 2000.0 2200.0 2400.0 2600.0 2800.0 3000.0

VA RY 1 GAS IFIER P ARA M TEMP F

Figure 11. Flow rate of CO2and H2O with variation in gasifier temperature

Sensitivity Results Curve

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5

CH4 LBMOL/HR
CH4 LBMOL/HR

1400.0 1600.0 1800.0 2000.0 2200.0 2400.0 2600.0 2800.0 3000.0

GASIFIE R TE MP F

Figure 12. Flow rate of CH4 with variation in gasifier temperature

38
Figure 13 shows the H2S molar flow rate with the temperature variation of the gasifier.

Sensitivity Results Curve

3.49355

H2S LBMOL/HR
3.4934
H2S LBMOL/HR
3.4931 3.49325
3.49295

1400.0 1600.0 1800.0 2000.0 2200.0 2400.0 2600.0 2800.0 3000.0

GASIFIE R TE MP F

Figure 13. Flow rate of H2S with variation in gasifier temperature

4.1.2 Effect of Pressure Variation

Gasifying Tuscaloosa petcoke under a high pressure is advantageous. Pressure

plays a very important role in the downstream application. The gasifier pressure range

that we have studied varies from 100 to 800 psia with an increment of 50 psia. One

feature of the high pressurized gasification is that the reduction in the gasifier size. In

addition, it is much easier and feasible to pressure the feedstock materials rather than

the syngas components. The downstream applications require the syngas with a

relatively high pressure such as gas turbines in the IGCC. Other cleaning units (H2S

removal and CO2 sequestration) work efficiently under a relatively high pressure. In this

study, we focus more in the gasifier pressure and its impact on the syngas components.

39
 146.0 147.0 148.0 149.0 150.0 151.0 152.0 153.0 154.0 155.0
Sensitiv ity Results Curv e
65.0 66.0 67.0 68.0 69.0 70.0 71.0 72.0 73.0 74.0 75.0
H2 LBMOL/HR
CO LBMOL/HR
H2 LBMOL/H R

CO LBMOL/HR

100.0 150.0 200.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0
GASIFIER PRESS PSIA

Figure 14. Flow rate of H2 and CO with variation in gasifier pressure

The relationship between the gasifier pressure and the H2 and CO flow is shown in

figure 14. Both H2 and CO flow rates decrease with the pressure increases. Pressure

here has an opposite impact from the temperature (Previous case). This is because

that the Boudouard reaction (CO2 + C 2CO) (Eq. 4) does not favor the high pressure

which means less amount of CO is produced with a higher pressure of the gasifier. This

explanation is also applied for the water-gas shift reaction (C + H2O CO + H2). Less

hydrogen is produced with higher pressure because the reaction goes in the opposite

direction in higher pressures. In our simulation, the sensitivity analysis has chosen the

pressure of 600 psia as the optimal gasifier pressure which gives the same molar flow

rate of the gasifier temperature of 2400 F(Table 10). These observations of the gasifier

temperature and pressure give us the opportunity of understanding the influence of

these parameters on the gasification chemical reactions and syngas composition.

40
 Table 12 shows the sensitivity analysis of the gasifier pressure variation on the

syngas component flow rates.

Table 12. Sensitivity analysis of the pressure variation on the syngas flow rates

CO2 and H2O flow rates with the gasifier pressure variations are shown in figure 15.

As the pressure increases, both CO2 and H2O flow rates increase as well as shown in

the figure. There is a slight increase in the CO2 and H2O flow rates in the pressure

range of (100 to 600 psia). After 600 psia, the trend of increasing of CO 2 and H2O flow

rates goes more vertically. This is because the reverse direction of the Boudouard and

water-gas shift reactions at higher pressures. This is valid also for the reaction of the

methane formation (C + 2H2 CH4) which favors a high pressure (Figure 16).

41
 Sensitivity Results Curve

3.25
1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4

3.0 2.75
CO2 LBMOL/HR

H2O LBMOL/HR
2.25 2.5
2.0

CO2 LBMOL/HR
H2O LBMOL/HR

100.0 150.0 200.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0
GASIFIER PRES PSIA
Figure 15. Flow rate of CO2 and H2O with variation in gasifier temperature

Sensitivity Results Curve

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3
CH4 LBMOL/HR

CH4 LBMOL/HR

100.0 150.0 200.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0
GASIFIE R PRES P SIA

Figure 16. Flow rate of CH4 with variation in gasifier pressure

42
 Sensitivity Results Curve
3.493523.4935
H2S LBMOL/HR
3.49347 3.49349
3.49346

H2S LBMOL/HR

100.0 150.0 200.0 250.0 300.0 350.0 400.0 450.0 500.0 550.0 600.0 650.0 700.0 750.0 800.0
GASIFIE R PRES P SIA

Figure 17. Flow rate of H2S with variation in gasifier pressure

The above figure shows the hydrogen sulfide flow rates variation with the gasifier

pressures. There is a very slight increase in the H2S flow rate in the syngas

accompanying the gasifier pressure increase. This behavior is contradictory for the

temperature behavior in figure 13 in which the H2S yield decreases with the

temperature rise.

In general, the impacts of the gasifier temperature on the syngas yield is much more

dominant than pressure. The change of the syngas compositions with the gasifier

pressure variation is less than 1 Ibmole/hr (Decrease) for each 50 psia of pressure

increments. Therefore, the petcoke gasifier pressure is selected according to the

requirements of downstream equipment or plant, the gasifier size, and the desired

volumetric flow rate of the syngas coming out of the gasifier.

43
4.1.3 Effect of Oxygen Variation
In this simulation, pure oxygen (Assumed to be 100% of pure O2) was used as the

oxidant agent. The oxygen flow rate variation ranges from 20 to 100 Ibmole/hr to see

what the impact of O2 on the syngas yield is. Figure 18 shows the correlation between

the H2 and CO flow rates with different supplied oxygen flow rates. It is obvious from the

figure that H2 stays almost constant with the oxygen variation from 20 to 60 Ibmole/hr

while the CO increases (Doubled) from 74.04 to 150.71 Ibmole/hr for the same oxygen

domain. Then, both H2 and CO yields decline as the oxygen increases. This trend is

expected because gasification is a partial oxidation process (determined amount of

oxygen). Oxygen flow rate of 60 Ibmole/hr gives the maximum H 2 and CO yields

(Maximum HHV of the syngas).

70.0 80.0 90.0 100.0 110.0 120.0 130.0 140.0 150.0 160.0

Sensitiv ity Results Curv e

70.0

H2 LBMOL/HR
CO LBMOL/HR
65.0
60.0 55.0

CO LBMOL/HR
H2 LBMOL/H R
45.0 50.0
40.0
35.0
30.0

20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0
OXYGEN FLOW RATE LBMOL/HR

Figure 18. Flow rate of H2 and CO with variation in oxygen flow rate

44
 As the oxygen increases further than 60 Ibmole/hr, a complete oxidation

(combustion) occurs instead of gasification. As a result, the flow rates of both CO2 and

H2O (Flue gases) raise with excess supplied oxygen beyond 60 Ibmole/hr as shown in

Figure 19. In another words, H2 and CO start converting to complete combustion gases

such as H2O and CO2 with much oxygen. Consequently, this leads to increase the

amount of heat released in the gasifier (Which associated with much higher

temperature) and reduces the heating content of the syngas. Therefore, the supplied

amount of oxygen to the gasifier should be well calculated to ensure that gasification

reactions carry out instead of burning the feedstock materials. Production of oxygen is

the most expensive process in the gasification plant. Optimizing of the provided oxygen

has a significant contribution to the overall gasification efficiency.

Sensitivity Results Curve

45.0

40.0
35.0 40.0

35.0
30.0
15.0 20.0 25.0 30.0

15.0 20.0 25.0

CO2 LB MOL/HR

H2O LB MOL/HR
10.0
10.0

5.0
5.0

CO2 L BM OL /HR

H2O L BM OL /HR
0.0

20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0
OXYGEN FLOW RATE LBMOL/HR

Figure 19. Flow rate of CO2 and H2O with variation in oxygen flow rate

45
 Figure 20 shows the correlation between the methane content of the syngas and the

variation in the supplied oxygen flow rates. Generally, the CH4 flow rate goes down with

the increase of the oxygen feed. In the range of oxygen variation increasing from 20 to

60 Ibmole/hr, there is a slight decline in the methane yield. However, a major plunge in

the CH4 is observed when the oxygen feed between 60 to 67.5 Ibmole/hr. As mentioned

previously, the oxygen flow of 60 Ibmole/hr has been chosen for the best gasification

yields which boosts better syngas components. Any further amount of oxygen over this

point causes a dramatic conversion from a partial oxidation (Gasification) to a complete

oxidation (combustion) which accompanies with higher temperatures. Hence, this

hinders the methane reaction (C + 2H2 CH4) because this reaction favors low

temperature. Less amount of CH4 in the syngas is observed with more oxygen feed.

Sensitivity Results Curve

1.6

CH4 LBMOL/HR
1.4
1.2 1.0
CH4 LBMOL/HR
0.6 0.8
0.4
0.2

20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0
OXYGEN FLOW RATE LBMOLE/HR

Figure 20. Flow rate of CH4 with variation in oxygen flow rate

46
 Sensitivity Results Curve
3.49352
H2S L BMOL/HR
3.49351 3.49351 3.49352
H2S LBMOL/HR
3.4935

20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0
OXYGEN FLOW RATE LBMOL/HR

Figure 21. Flow rate of H2S with variation in oxygen flow rate
Figure 21 shows the reduction in the H2S with the oxygen variation. As the oxygen

increases from 20 to 100 Ibmole/hr, the H 2S reduces at a very slight rate from

3.4935194 to 3.49350259 Ibmole/hr.

4.1.4 Effect of Steam Variation

Tuscaloosa petcoke moisture content is 0.9 % (Weight based) as it appears in the

proximate analysis table 3 in chapter 3. Steam was provided along with oxygen directly

to the gasifier. Similar to the previous parameters, provided steam flow rate ranges from

20 to 100 Ibmole/hr with a purity of 100 % H2O. Steam provides an additional amount of

hydrogen to the existed hydrogen of the petcoke feedstock. Investigation of the

sensitivity analysis of the steam variation was objected to increase the hydrogen and

47
 Sensitivity Results Curve

152.0
90.0

148.0
85.0 80.0

144.0
CO LBMOL/HR
H2 LBMOL/HR

H2 LBMOL/HR
75.0

CO LBMOL/HR
140.0
70.0

136.0
65.0
60.0

132.0
55.0

20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0
ST EAM FLOW RA TE LB MOL/HR
Figure 22. Flow rate of H2 and CO with variation in steam flow rate

carbon monoxide in the syngas out of the gasifier. Another target was to adjust the

ratio of (H2/CO) in the syngas gas to achieve and fulfill the required purpose of the

downstream application. In the water-gas reaction (C + H2O H2 + CO), the hot char

(carbon) reacts with the steam to give both H2 and CO gases. The steam could come

from the pyrolysis (evaporation) of the petcoke moisture and from the steam feed. With

a limited amount of moisture in the Tuscaloosa petcoke, most of H 2O is supplied from

the steam feed. Figure 22 shows both H2 and CO yields for the steam variation from 20

to 100 Ibmole/hr. H2 yield goes up with steam flow rate increases because the water-

gas reaction. CO flow rate, however, peaks up at steam flow rate of 36 mole/hr and

then goes down as the steam flow rate increases. Both CO 2 and H2O yields with the

same steam range variation are shown in figure 23.

48
 Sensitivity Results Curve
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0

2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0
H2O LBMOL/HR

CO2 LBMOL/HR

H2O LBMOL/HR

CO2 LBMOL/HR
0.0

20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0
ST EAM FLOW RA TE LB MOL/HR

Figure 23. Flow rate of CO2 and H2O with variation in steam flow rate

As the steam feed increases from 20 to 36 Ibmole/hr, Both CO2 and H2O flow rates

increase slightly. Then, they both raise with the above shown tendency with more

steam feed. The declination of CO after the steam flow rate of 36 Ibmole/hr is

associated with CO2 escalation because CO starts converting to CO2 according to the

CO shift conversion (CO + H2O CO2 + H2) with much supplied steam. Methane yield

shows the same behavior as shown in figure 24 with the steam alternation. The

methane declines after the steam flow of 36 Ibmole/hr because it begins converting to

H2 and a limited amount of CO with excessive steam feed. This is in accordance to the

steam-methane reforming (CH4 + H2O CO + 3H2). As a result, 36 Ibmole/hr of

steam is selected as the optimum steam flow rate which gives as high as possible of H2,

CO, and CH4 (heating value) with less CO2 and H2O.

49
 Sensitivity Results Curve
1.0 1.1
CH4 LBMOL/HR
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
CH4 LBMOLE/HR
0.1

18.0 24.0 30.0 36.0 42.0 48.0 54.0 60.0 66.0 72.0 78.0 84.0 90.0 96.0 102.0
ST EAM FLOW RATE LBMOLE/HR
Figure 24. Flow rate of CH4 with variation in steam flow rate

50
4.2 Cold Gas Efficiency of the Tuscaloosa Petcoke Gasification
After setting the operational conditions of the gasifier to the optimum values that

were selected by the sensitivity analysis of the developed ASPEN PLUS model as the

following table. The mass flow rates of the combustible gases (H2, CO, and CH4) were

Table 13. Optimum gasifier parameters

No. Parameters of the gasifier Value
1 Temperature 2400 F
2 Pressure 600 psia
3 Oxygen flow rate 60 Ibmole /hr
4 Steam flow rate 36 Ibmole/hr
5 Petcoke flow rate 2135 Ib/hr

computed from the simulation model. Then, the cold gas efficiency of the gasifier was

calculated in accordance to the mass flow rates of the petcoke, H2, CO, and CH4. It is

based on the lower heating value (LHV) of these gases. The equation of the cold gas

efficiency is the following:

..(10) [29]

LHV of H2 = 51,628 Btu Ib-1 ; CO = 4,368 Btu Ib-1 ; and CH4 = 21,433 Btu Ib-1 [30]

The Tuscaloosa petcoke lower heat value = 15000 Btu Ib -1

(139.0939 X 51,628) + (4220.198 X 4,368) + (16.69507 X 21,433)

2135 X 15,000

81.1016 % Cold Gas efficiency of the Tuscaloosa petcoke gasifier (LHV).

The gasifier cold gas efficiency reflects the optimum operation conditions according to

the ASPEN PLUS sensitivity analysis.

51
 Chapter 5

CONCLUSION AND FUTURE WORK

5.1 Conclusion
The world is facing a rapid pace of growth in energy demand which imposes

shortages and high energy prices. No single technology or resource can solve this

problem. Relaying on more energy resources is one of the proposed solutions to meet

the required energy increases. Gasification can be a part of the solution along with

other technologies and energy efficiency programs. Because the flexibility nature of

feedstocks and products of the gasification, it has a wide range of upstream feedstocks

such as petcoke, coal, biomass, and municipal waste. The product of the gasification

process is called synthesis gas (Syngas) which is versatile for a variety of downstream

applications like integrated gasification combined cycle (IGCC), Fischer-Tropsch

synthesis (FTS), ammonia, methanol, fertilizer, and generating heat and steam for

industrial uses.

In this study, a model of Tuscaloosa petcoke gasification process was simulated

using ASPEN PLUS software. The sensitivity analysis of the entrained flow gasifier was

deployed to investigate and optimize the operation conditions of the gasifier (i.e. Temp.,

press., oxygen and steam flow rates). The purpose of studying the variation of these

parameters was to fully understand their behaviors and what the impacts on the syngas

yield are.

Tuscaloosa petcoke flow of 2135 Ib/hr was fed to the gasifier along with oxygen and

steam. The simulation and sensitivity analysis indicated that a gasifier temperature of

2400 F with a pressure of 600 psia give the optimum syngas yield (Enriched with H 2,

52
CO and less CO2, H2O). It is concluded that the gasifier temperature plays a significant

role in the syngas yields while pressure has a limited impact on the syngas

components. Therefore, the selection of pressure depends on the downstream

application of the gasification products.

Moreover, the oxygen flow rate was supplied at different values to see what the

impacts of O2 on the syngas elements are. A flow rate of 60 Ibmole/hr of pure oxygen

gives the best syngas yield. More supplied oxygen leads to turn both H 2 and CO into

fully combustible products (CO2 and H2O) which is not favorable. Optimization of Steam

flow rate assigns a 36 Ibmole/hr of pure H 2O as the optimal steam feed. H2 goes up

continuously with increasing steam. On the contrary, CO plunges and starts converting

to CO2 after the steam flow rate hits 36 Ibmole/hr because the excessive amount of

steam activates the CO shift conversion (CO + H2O CO2 + H2).

Based on the aforementioned optimal gasifier parameters, the cold gas efficiency of

Tuscaloosa petcoke gasification was calculated in accordance with the lower heating

values. Optimizing the developed model parameters enhance the efficiency to reach

81.1016 %. This reflects a high heat content in the syngas components which

represented by the flow rate of H2, CO, and CH4. This simulation can be commercialized

and marketed to extract more energy from the bottom of the oil barrel.

In conclusion, the gasification technology upgrades Tuscaloosa petcoke to high

heating value gases such as H2, CO, and CH4. These products are very crucial for the

refinery industry. Refineries demands of these essential gases can be provided by the

petcoke gasification. Therefore, Optimizing of petcoke gasification parameters is

feasible and economical as it can maximize the syngas yields with less input energy.

53
5.2 Future Work
The following considerations can be studied in the future:

1- Studying the kinetic parameters of the reacting materials in the gasifier to

achieve higher efficiency and understand the formation of different syngas

components.

2- Connecting the simulated model to a downstream application such as IGCC,

FTS, ammonia plant, and methanol route to study the overall efficiency and the

emissions of the plant.

3- The economic analysis and profitability of the gasification plant.

4- Studying the effects of blending petcoke with other feedstocks such as coal or

biomass and use different gasifier types like moving or fluidized bed gasifiers.

54
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58
APPENDICES
Appendix A

59
 INPUT SUMMAY of TUSCALOOSA PETCOKE GASIFICATION SIMULATION USING
ASPEN PLUS
;
;Input Summary created by Aspen Plus Rel. 25.0 at 23:24:07 Mon Jun 8, 2015
;Directory C:\Users\siu853378615\Desktop\petcoke gasification Filename
C:\Users\SIU853~1\AppData\Local\Temp\~ap2324.txt
;

DYNAMICS
DYNAMICS RESULTS=ON

TITLE 'Petcoke Gasification'

IN-UNITS ENG

DEF-STREAMS MIXCINC ALL

SIM-OPTIONS MASS-BAL-CHE=YES OLD-DATABANK=YES

DESCRIPTION "
General Simulation with English Units :
F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.

Property Method: None

Flow basis for input: Mole

Stream report composition: Mole flow

"

DATABANKS PURE25 / AQUEOUS / SOLIDS / INORGANIC / &

NOASPENPCD

PROP-SOURCES PURE25 / AQUEOUS / SOLIDS / INORGANIC

COMPONENTS
H2O H2O /
N2 N2 /
O2 O2 /
PETCOKE /
SS/
H2 H2 /
CL2 CL2 /
HCL HCL /
CC/
CO CO /
CO2 CO2 /
ASH /

60
 H3N H3N /
COS COS /
H2S H2S /
CH4 CH4 /
NO NO /
NO2 NO2 /
N2O N2O /
N2O4 N2O4 /
N2O3 N2O3 /
C6H6 C6H6

CISOLID-COMPS C

FLOWSHEET
BLOCK GASIFIER IN=GASIFEED STEAM OXYGEN DECOHEAT OUT= &
HOTYNGAS HEATOUT
BLOCK DECOMPOS IN=PETCOKE OUT=GASIFEED DECOHEAT
BLOCK ASHREM IN=COLDSNGA OUT=SYNGAS ASH
BLOCK HXSYNGAS IN=HOTYNGAS OUT=COLDSNGA

PROPERTIES PENG-ROB
PROPERTIES PR-BM

NC-COMPS PETCOKE PROXANAL ULTANAL SULFANAL

NC-PROPS PETCOKE ENTHALPY HCOALGEN 6 / DENSITY DCOALIGT

NC-COMPS ASH PROXANAL ULTANAL SULFANAL

NC-PROPS ASH ENTHALPY HCOALGEN / DENSITY DCOALIGT

PROP-DATA HCOMBUST
IN-UNITS ENG
PROP-LIST HCOMB
PVAL PETCOKE 15000.

STREAM OXYGEN
SUBSTREAM MIXED TEMP=77. PRES=600. MOLE-FLOW=59.78
MOLE-FRAC O2 1.

STREAM PETCOKE
SUBSTREAM NC TEMP=77. PRES=14.7 MASS-FLOW=2135.
MASS-FRAC PETCOKE 1.
COMP-ATTR PETCOKE PROXANAL ( 1. 88.5 9.6 1.9 )
COMP-ATTR PETCOKE ULTANAL ( 1.9 87.3 3.8 1.7 * 5.3 )
COMP-ATTR PETCOKE SULFANAL ( 2.385 0.53 2.385 )

STREAM STEAM
SUBSTREAM MIXED TEMP=487. PRES=600. MOLE-FLOW=36.

61
 MASS-FRAC H2O 1.

DEF-STREAMS HEAT DECOHEAT

DEF-STREAMS HEAT HEATOUT

BLOCK HXSYNGAS HEATER

PARAM TEMP=500. PRES=0.

BLOCK DECOMPOS RYIELD

PARAM TEMP=77. PRES=1. <atm>
MASS-YIELD MIXED H2 0.03762 / N2 0.01683 / H2O 0.01 / &
S 0.05247 / CISOLID C 0.86427 / NC ASH 0.01881
COMP-ATTR NC ASH PROXANAL ( 0. 0. 0. 100. )
COMP-ATTR NC ASH ULTANAL ( 100. 0. 0. 0. 0. 0. 0. )
COMP-ATTR NC ASH SULFANAL ( 0. 0. 0. )

BLOCK GASIFIER RGIBBS

PARAM TEMP=2400. PRES=600.
PROD H2 / O2 / N2 / H2O / S / CO / CO2 / H2S / &
CH4 / C SS / H3N
PROPERTIES PENG-ROB FREE-WATER=STEAM-TA SOLU-WATER=3 &
TRUE-COMPS=YES

BLOCK ASHREM SSPLIT

FRAC MIXED SYNGAS 1.
FRAC CISOLID SYNGAS 0.
FRAC NC SYNGAS 0.

EO-CONV-OPTI

SENSITIVITY OXGENVAR
DEFINE H2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2
DEFINE CO MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO
DEFINE CH4 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CH4
DEFINE H2O MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE CO2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO2
DEFINE H2S MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2S
TABULATE 1 "H2"
TABULATE 2 "CO"
TABULATE 3 "CH4"
TABULATE 4 "H2O"
TABULATE 5 "CO2"

62
 TABULATE 6 "H2S"
VARY MOLE-FLOW STREAM=OXYGEN SUBSTREAM=MIXED COMPONENT=O2
RANGE LOWER="20" UPPER="100" INCR="6"

SENSITIVITY PRESSVAR
DEFINE H2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2
DEFINE CO MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO
DEFINE CH4 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CH4
DEFINE CO2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO2
DEFINE H2O MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE H2S MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2S
TABULATE 1 "H2"
TABULATE 2 "CO"
TABULATE 3 "CH4"
TABULATE 4 "CO2"
TABULATE 5 "H2O"
TABULATE 6 "H2S"
VARY BLOCK-VAR BLOCK=GASIFIER VARIABLE=PRES SENTENCE=PARAM
RANGE LOWER="100" UPPER="800" INCR="50"

SENSITIVITY STEAMVAR
DEFINE H2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2
DEFINE CO MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO
DEFINE H2O MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE CO2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO2
DEFINE CH4 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CH4
DEFINE H2S MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2S
TABULATE 1 "H2"
TABULATE 2 "CO"
TABULATE 3 "H2O"
TABULATE 4 "CO2"
TABULATE 5 "CH4"
TABULATE 6 "H2S"
VARY MOLE-FLOW STREAM=STEAM SUBSTREAM=MIXED COMPONENT=H2O
RANGE LOWER="20" UPPER="100" INCR="4"

SENSITIVITY TEMPVARY

63
 DEFINE H2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2
DEFINE CO MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO
DEFINE CO2 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CO2
DEFINE H2O MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE CH4 MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=CH4
DEFINE H2S MOLE-FLOW STREAM=SYNGAS SUBSTREAM=MIXED &
COMPONENT=H2S
TABULATE 1 "H2 "
TABULATE 2 "CO"
TABULATE 3 "CH4"
TABULATE 4 "CO2"
TABULATE 5 "H2O"
TABULATE 6 "H2S"
VARY BLOCK-VAR BLOCK=GASIFIER VARIABLE=TEMP SENTENCE=PARAM
RANGE LOWER="1400" UPPER="3000" INCR="200"

STREAM-REPOR MOLEFLOW MASSFLOW MOLEFRAC

;
;
;
;
;

64
Appendix B

65
 Final Syngas Stream Yield of Tuscaloosa Petcoke Gasification
SYNGAS
------

STREAM ID SYNGAS
FROM : ASHREM
TO : ----
CLASS: MIXCINC
TOTAL STREAM:
LB/HR 4655.0286
BTU/HR -7.0972+06
SUBSTREAM: MIXED
PHASE: VAPOR
COMPONENTS: LBMOL/HR
H2O 2.4456
N2 1.2798
O2 2.3404-13
S 1.1964-05
H2 68.9991
CL2 0.0
HCL 0.0
C 0.0
CO 150.6654
CO2 1.8170
H3N 5.7193-03
COS 0.0
H2S 3.4935
CH4 1.0407
NO 0.0
NO2 0.0
N2O 0.0
N2O4 0.0
N2O3 0.0
C6H6 0.0

66
COMPONENTS: MOLE FRAC
H2O 1.0645-02
N2 5.5705-03
O2 1.0187-15
S 5.2073-08
H2 0.3003
CL2 0.0
HCL 0.0
C 0.0
CO 0.6558
CO2 7.9089-03
H3N 2.4894-05
COS 0.0
H2S 1.5206-02
CH4 4.5296-03
NO 0.0
NO2 0.0
N2O 0.0
N2O4 0.0
N2O3 0.0
C6H6 0.0
COMPONENTS: LB/HR
H2O 44.0583
N2 35.8519
O2 7.4890-12
S 3.8362-04
H2 139.0939
CL2 0.0
HCL 0.0
C 0.0
CO 4220.1982
CO2 79.9679
H3N 9.7403-02
COS 0.0
H2S 119.0656
CH4 16.6951
NO 0.0
NO2 0.0

67
N2O 0.0
N2O4 0.0
N2O3 0.0
C6H6 0.0
TOTAL FLOW:
LBMOL/HR 229.7469
LB/HR 4655.0286
CUFT/HR 4003.6191
STATE VARIABLES:
TEMP F 500.0000
PRES PSIA 600.0000
VFRAC 1.0000
LFRAC 0.0
SFRAC 0.0
ENTHALPY:
BTU/LBMOL -3.0891+04
BTU/LB -1524.6252
BTU/HR -7.0972+06
ENTROPY:
BTU/LBMOL-R 12.3329
BTU/LB-R 0.6087
DENSITY:
LBMOL/CUFT 5.7385-02
LB/CUFT 1.1627
AVG MW 20.2616

68
 VITA
Graduate School
Southern Illinois University

Saif Yoseif Salih

Saifsalih1@gmail.com

University of Anbar, Iraq

Bachelor of Science, Mechanical Engineering, Sep. 2005

Special Honors and Awards

1- I graduated with the second rank (out of 44 students) from Mechanical Engineering
Dept. at University of Anbar which reflects my outstanding undergraduate work.
2- I got a special order to be appointed in the Ministry of Oil (Because of my second
rank) and worked for North Oil Company (Kirkuk and Anbar provinces) for eight years.
3- A recipient of HCED (Higher Committee for Education Development in Iraq) to
pursue Master of Science Degree in the United States. (Fully funded scholarship).

Thesis Title:
The Modeling of Petroleum Coke Gasification Using ASPEN PLUS Software

Major Professor: Dr. Tomasz S. Wiltowski

69