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THESIS APPROVAL
By
Master of Science
in the field of Mechanical Engineering
Approved by:
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.
PLUS SOFTWARE
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
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
gasifier cold gas efficiency (Based on LHV) can be achieved for the developed model.
feasible and can be commercialized. This leads to more utilization of the bottom of oil
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
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
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
iv
TABLE OF CONTENTS
ABSTRACT ...................................................................................................................... I
DEDICATION .................................................................................................................. II
ACKNOWLEDGMENTS................................................................................................. III
PREFACE ......................................................................................................................IV
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 3. The Proximate analysis of the Tuscaloosa petcoke [5, 27] ............................. 25
Table 4. The ultimate analysis of the Tuscaloosa petcoke [5, 27] ................................ 25
Table 10. Gasifier temp. range with the syngas component flow rates ......................... 35
Table 12. Sensitivity analysis of the pressure variation on the syngas flow rates ......... 41
vii
LIST OF FIGURES
Figure 1. Pyrolysis and gasification processes [6]........................................................... 6
Figure 4. (a) Updraft, (b) Downdraft, (c) Crossflow type fixed bed gasifiers [18] ........... 17
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
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
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
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
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
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
1
Petcoke has generally been considered as an unusable byproduct due to high sulfur
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
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
synthesis gas (Syngas) which is mainly hydrogen (H2) and carbon monoxide (CO).
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
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
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
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
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
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
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
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
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
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.
6
As mentioned previously, the amount of oxidant agent is well determined in the
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.,
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:
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
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
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
Table 1. Gasification plants around the world with petcoke feedstock [2]
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
technology becomes inevitable to satisfy the world energy demand from the remaining
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
reaction provides most of the energy required for driving the endothermic gasification
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
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
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)
relatively a modern topic with limited previous published literature. In his scientific
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.
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].
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
12
2.4 Gasification Reactions
There are several thermochemical reactions taking place in the gasifier as following:
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
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.
2. Boudouard Reaction
Boudouard reaction is the reaction of carbon dioxide that produced from the volatile
and heterogeneous reaction and the carbon monoxide (CO) formation favors a high
13
3. Water- Gas Reaction
The water gas reaction is given as:
5. CO Shift Conversion
The CO shift conversion or called (Water gas shift reaction) adjust the hydrogen to
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,
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
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
Gasification Technologies
Updraft Circulating
Opposed Jet
Crossdraft Twin bed
15
A brief description of each type is given in the followings:
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
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.
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
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
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.
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
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.
The primary use of plasma gasifiers is to destroy hazardous materials and municipal
refuse are gasified to generate energy for utilities usage. Japan, Canada, India have
syngas is provided for electrical power plants [22]. Figure 6 illustrates a plasma gasifier.
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.
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,
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
which uses mass and energy balance equations, thermodynamic properties, and
reaction kinetics with a huge database and information of components and chemical
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
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
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
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
which gives it an incentive to increase the carbon conversion of the petcoke with
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
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).
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
the composition of each components (i.e., H2, CO, CO2, H2O, CH4, and H2S).
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
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
The proximate analysis of Tuscaloosa petcoke is shown in the below table [5, 27].
The ultimate analysis of the Tuscaloosa petcoke is shown in the below table [5, 27].
25
The ash composition of the Tuscaloosa petcoke is given in the below table.
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.
petcoke and supplying the refiners back with electricity, steam, and other important
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
Plots of the oxygen flow rates versus the syngas components were generated to
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
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.
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:
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
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
reactor to represent the extra heat that generates and transfers to the vicinity of the
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
heat recovery from the hot syngas can be deployed to generate steam which is
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
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
and particulate matter. After cooling it down to around 500 F, the syngas passes
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
32
CHAPTER 4
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
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
conditions of the gasifier to optimize the petcoke gasification products for the
33
4.1 Sensitivity Analysis
It is a very useful tool to calculate and find how a process reacts to different
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
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.
specific requirements regarding the syngas composition. For instance, if the desired
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
(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
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
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
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
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).
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
Figure 11. Flow rate of CO2and H2O with variation in gasifier temperature
CH4 LBMOL/HR
CH4 LBMOL/HR
38
Figure 13 shows the H2S molar flow rate with the temperature variation of the gasifier.
H2S LBMOL/HR
3.4934
H2S LBMOL/HR
3.4931 3.49325
3.49295
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. 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
40
Table 12 shows the sensitivity analysis of the gasifier pressure variation on the
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
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
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
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
requirements of downstream equipment or plant, the gasifier size, and the desired
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
oxygen). Oxygen flow rate of 60 Ibmole/hr gives the maximum H 2 and CO yields
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
40.0
35.0 40.0
35.0
30.0
15.0 20.0 25.0 30.0
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
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.
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
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
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
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
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 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
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
..(10) [29]
LHV of H2 = 51,628 Btu Ib-1 ; CO = 4,368 Btu Ib-1 ; and CH4 = 21,433 Btu Ib-1 [30]
2135 X 15,000
The gasifier cold gas efficiency reflects the optimum operation conditions according to
51
Chapter 5
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
synthesis (FTS), ammonia, methanol, fertilizer, and generating heat and steam for
industrial uses.
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
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
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.
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
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:
components.
FTS, ammonia plant, and methanol route to study the overall efficiency and the
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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and V. N. Raibhole. 2013, " Testing and parametric analysis of an updraft biomass
[19] Jayaraman, K., and Gokalp, I., 2015, "Gasification characteristics of petcoke and
[20] Azargohar, R., Gerspacher, R., Dalai, A. K., and Peng, D.-Y., 2015, "Co-
gasification of petroleum coke with lignite coal using fluidized bed gasifier," Fuel
[21] Bi, D., Guan, Q., Xuan, W., and Zhang, J., 2015, "Combined slag flow model for
[22] Blake, T., 2014, "Sky turns green with plasma gasification technology,"
[23] Khadse, A. N., 2015, "Resources and economic analyses of underground coal
[24] Sudiro, M., Zanella, C., Bressan, L., Fontana, M., and Bertucco, A., 2009,
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[25] Jang, D.-H., Yoon, S.-P., Kim, H.-T., Choi, Y.-C., and Lee, C., 2015, "Simulation
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Processes", John and Wiley & Son Ltd, West Sussex, UK, PP. 286, Chap. 10.
[27] Gilliam, K., Reilly, D., and White, P., 2013, "Las Brisas Energy Center Feasibility
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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
IN-UNITS ENG
DESCRIPTION "
General Simulation with English Units :
F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.
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
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.
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"
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
Saifsalih1@gmail.com
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
69