Petroleum Coke Gasification: A Review

Bontu N. Murthy,1,2 Ashish N. Sawarkar,1,3 Niteen A. Deshmukh,1,2 Thomas Mathew2 and

Jyeshtharaj B. Joshi1,4*
1. Department of Chemical Engineering, Institute of Chemical Technology, Matunga, Mumbai, 400 019, India
2. Reliance Technology Group, Reliance Industries Ltd., Ghansoli, Navi Mumbai, 400 701, India
3. Department of Chemical Engineering, Anuradha Engineering College, Chikhli‐443201, Buldana, Maharashtra, India
4. Homi Bhabha National Institute, Anushaktinagar, Mumbai, 400 094, India

The production of petroleum coke (petcoke) in the refineries is progressively peaking up because of the trend of processing heavy crudes and in turn, a
renewed interest in delayed coking process. Therefore, an efficient, economical, and environmentally safe utilisation of petcoke has become
imperative in the current petroleum refining scenario. Gasification of petcoke has emerged as one of the attractive options and is gaining increasing
attention to convert the petcoke to value‐added products. The process offers the refiners a variety of product slates mainly via synthesis gas route. The
products include steam, hydrogen, electricity, chemicals (viz. methanol, ammonia, etc.), liquid fuels via Fischer–Tropsch (F‐T) synthesis and so on.
Petcoke has been identified as a potential feedstock for about 15% of the total planned gasification capacity worldwide. In the present
communication, the published literature pertaining to petcoke gasification has been extensively analysed and a state‐of‐the‐art review has been
written that includes: (1) the importance of petcoke gasification in the present petroleum refining scenario; (2) petcoke gasification reaction
mechanism, kinetics and typical product profile; (3) parametric sensitivity of the operating variables such as temperature and pressure; (4) various
gasifiers for petcoke gasification; (5) modelling efforts on different types of gasifiers and (6) future prospects of petcoke gasification. An attempt has
been made to get the afore‐mentioned aspects together in a thematic framework so that the information is available at a glance and is expected to be
useful as a single point source to the researchers and practicing refiners.

Keywords: petcoke, gasification, kinetics, synthesis gas, fixed bed, fluidised bed, entrained flow gasifiers, gasifier modelling

INTRODUCTION future because of the progressive increase in heavy crude oil

supply.[11–13] An additional capacity of about 70 MMTPA petcoke is

T
he global petroleum refining capacity has reached about
4600 million metric tons per annum (MMTPA) processed in
about 750 refineries. Petroleum refining industry is witness-
ing a major transition as the industry has moved into the 21st
century. The issues, viz. soaring crude oil prices, progressively
increasing demand for distillates and the ever‐dwindling supply of
light sweet crude oil have affected the refining business. The
decreasing supply of light sweet crude oils is a matter of serious
concern for the petroleum refining industry because the distillation
of heavy crude oils leaves behind a significant amount of vacuum
residue (about 40% of the total crude processed).[1] The quantity of
heavy residues is expected to increase in the future in view of the
progressively increasing heavier nature of the crudes.[2–6] In order
to satisfy the changing pattern of product demand, significant
investments in the refining conversion processes has become
inevitable to profitably utilise the heavy crude oils.[7] It has been
widely envisaged that the window of opportunity is for those
refineries which can process low grade crudes to produce high
grade products.
The trend of processing heavy crudes in the refineries and in turn
a renewed interest in the delayed coking process has led to the
progressive increase in the production of petcoke.[8] The refiners,
in fact, are facing a flood of petcoke.[9,10] The global petcoke
production capacity has reached about 150 MMTPA, out of which
United States alone produces about 70 MMTPA (about 47% of the
total capacity) of petcoke. ConocoPhillips is the world’s largest
petcoke producer and also licenses coker technology. Recently,
M/s Bechtel acquired license from ConocoPhillips. It has been
envisaged that petcoke production will grow at a brisk pace in the
anticipated to be added to the existing capacity by 2015. Petcoke
can be classified as sponge coke, honeycomb coke, shot coke and
needle coke depending upon its physical structure.[14,15] Out of the
aforementioned cokes, needle coke is a premium‐quality coke
which is obtained by processing aromatic rich feedstocks with
sulphur content less than 1 wt%. The petcoke which is obtained
from the delayed coking unit is called delayed coke (DC) and the
one obtained from the fluid coking unit is referred to as fluid coke
(FC). It may be pointed out that the coke produced by processing
heavy residues (high sulphur, metal and conradson carbon residue
(CCR)) is considered as a byproduct, where the main aim is to
maximise the distillate production. The coke produced poses
disposable problems because of the high sulphur (5–7 wt%) and
vanadium (about 500 ppm) content. The fact that delayed coking is
going to continue as a workhorse in the future in regards to the
bottom‐of‐the‐barrel conversion to lighter products,[5] inevitably
calls for an economical and environmentally safe utilisation of
petcoke. Another reason for giving extra attention to the utilisation
of petcoke is that, as of late, with the continual increase in the
crude oil prices, it has become imperative to get the maximum
possible value‐addition out of every possible refinery stream. It
*Author to whom correspondence may be addressed.
E‐mail address: jb.joshi@ictmumbai.edu.in
Can. J. Chem. Eng. 92:441–468, 2014
© 2013 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.21908
Published online 5 October 2013 in Wiley Online Library
(wileyonlinelibrary.com).

VOLUME 92, MARCH 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 441
 Table 1. Characteristics of petcoke and sub‐bituminous coal 2004, two US electric producers namely, Wabash River Energy Ltd.
(Terre Haute, IN) and Tampa Electric (Polk County, FL) with
Value
integrated gasification combined cycle (IGCC) units had switched
Characteristic Unit Petcoke Sub‐bituminous coal over to petcoke from coal as a gasification feedstock. Wabash River
Energy Ltd. employs 100% coke since August 2000 while Tampa
Moisture wt% 6.23 19.0 Electric employs 60% coke. Gasification of petcoke offers refiners a
Total sulphur wt% 6.94 0.22 variety of product slates mainly via synthesis gas (syngas) route.
Heat content (HHV) MJ/kg 35 21.5 The products include steam, electricity, chemicals (viz. methanol,
Proximate analysis received ammonia, etc.), liquid fuels via Fischer–Tropsch (F‐T) synthesis
Ash wt% 0.34 7.6 and so on.[23–32] However, the choice of the final product out of
Volatile material wt% 12.88 46.8
gasification depends on the refinery configuration and market
Fixed carbon wt% 86.78 45.6
requirements. A high pressure steam can be produced by
Ultimate analysis (dry)
recovering heat from the hot gasification products directly in the
C wt% 89.45 65.6
H wt% 2.8 4.53 gasifier and/or in the syngas cooler. An intermediate and low
N wt% 0.05 0.83 pressure steam is produced in the heat recovery systems
Cl wt% 0.01 0.1 downstream from the syngas cooler. If electricity is the final
S wt% 7.48 0.18 product, most of the steam and synthesis gas are utilised in the
Ash wt% 0.2 7.61 steam turbine and gas turbine, respectively.[16]
O2 wt% 0.01 21.15 The first gasification plant solely based on petcoke went on
stream in November 1995 at Wabash River Energy Ltd.[33] Table 2
shows major petcoke gasification plants operating all over the
may be pointed out that Furimsky[16] has written a review on the world. Table 3 shows major planned gasification projects
different aspects pertaining to the gasification of oil sand coke worldwide with petcoke as feedstock. The fact that the petcoke
(obtained by processing tar sands, whose reserves are abundantly has been identified as a potential feedstock for about 15% of the
available in Canada). However, as the name suggests, the total planned gasification capacity globally corroborates the
discussion was limited to oil sand coke in particular. In the growing interest in petcoke gasification.
present communication, an attempt has been made to bring Gasification, in general, chemically converts hydrocarbon feed-
together the information on the gasification of petcoke in general stocks to a mixture of carbon monoxide and hydrogen and small
irrespective of the origin of the parent crude oil. concentrations of other gases. The oxygen to carbon ratio is
adjusted to ensure that most of the carbon in the feed gets converted
to CO and most of the hydrogen to H2. Gasification process has
PERSPECTIVE OF PETCOKE GASIFICATION superior environmental performance vis‐à‐vis combustion pro-
Gasification of petcoke has emerged as one of the promising routes cesses in dealing with the solid feeds such as petcoke. All the
and is gaining increasing attention for the complete and economi- combustion processes that use solid fuels, apart from gas
cal utilisation of petcoke.[13,17–21] The heating value of petcoke emissions, produce solid residues viz., slag and fly ash which
(30.25–34.91 MJ/kg) is about 20% higher than that of coal (24.45– have been found to be hazardous. These products may have a
30.25 MJ/kg). Another advantage of coke is its low ash content contaminant effect on the environment.[34] Unlike that of
(0.1–0.3 wt%) vis‐à‐vis coal (8–20 wt%).[22] However, the issues, combustion processes, the by‐product ash and slag from the
viz. high sulphur, high vanadium content, and low reactivity[19] in gasification technologies have been shown to be non‐hazardous.
regards to the petcoke are critical and need to be attended Furthermore, gasification provides both upstream (feedstock
judiciously. flexibility) and downstream (product flexibility) advantages.[32]
Table 1 shows the typical properties of petcoke and sub‐ Typical synthesis gas composition with petcoke as gasification
bituminous coal. The availability of raw material (petcoke) for feedstock is shown in Table 4. The raw gas produced in the first step
gasification right in the refinery premises makes the case of petcoke is cleaned to remove sulphur compounds and particulates. The
as a gasification feedstock more compelling and economical. Till former are converted into pure sulphur in the Claus plant, while

Table 2. Major petcoke based gasification plants

Gasification Feedstock input Output

Country Plant name technology Products, year (tones/day) (MW)

Japan Ube City CO Plant GE Chemicals, 1982 Petcoke 95 27.3

Japan Ube Ammonia Industry Co. Ltd. GE Chemicals, 1984 Coal and petcoke 1650 165a
USA Wabash River Energy Limited E‐GAS ConocoPhillips Electricity, 1995 Petcoke 2000 262
USA Polk County IGCC Project GE Electricity, 1996 Coal and petcoke 2200 250
USA El Dorado IGCC Plant Texaco Electricity and high Waste oils and petcoke 164 35
pressure steam, 1996
Spain Puertollano IGCC Plant Uhde PRENFLO Electricity, 1998 Coal and petcoke 2600 335
USA Coffeyville Syngas Plant GE Chemicals, 2000 Petcoke 1100 293a
USA Delaware clean energy Texaco Electricity and high Fluid petcoke 2000 120
cogeneration project pressure steam, 2002
China GE China 4 GE Chemicals, 2005 Coal and petcoke (not available) 157a
USA Lima Energy IGCC Plant ConocoPhilips Electricity, 2013 Coal and petcoke (not available) 540
a
Based on synthesis gas output.

442 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, MARCH 2014
 Table 3. Major planned petcoke based gasification plants The overall reaction can be summarised with several basic
chemical reactions[35] such as gasification with O2:
Country Plant name Type Products

Japan Marifu IGCC plant Texaco Electricity C þ 1=2O2 ! CO DH R ¼ 123:1 MJ=kmol ð1Þ
India Reliance Industries Ltd. ConocoPhillips Electricity,
chemicals combustion with O2:
India Bhatinda IGCC Texaco Electricity
USA Lima Energy IGCC Plant ConocoPhillips Electricity C þ O2 ! CO2 DH R ¼ 405:9 MJ=kmol ð2Þ
USA Edison Mission Energy GE Electricity
USA Sweeney Gasification ConocoPhillips Electricity gasification with CO2:
Project
USA Mississippi ConocoPhillips Gaseous fuels
C þ CO2 ! 2CO DH R ¼ 159:7 MJ=kmol ð3Þ
Gasification LLC
USA Valero Energy Corp. ECUST OMB Gaseous fuels
gasification with steam:

C þ H2 O ! CO þ H 2 DH R ¼ 118:9 MJ=kmol: ð4Þ

particulates are recycled to the gasifier. Thus, almost 100% carbon
conversion can be achieved. Metals, viz. vanadium and nickel are
Here most of the O2 fed to the gasifier is consumed in reactions (1)
concentrated in the slag/ash, saleable for metal recovery. Thus, no
and (2). These reactions generate heat to increase temperatures in
solid byproduct is left for disposal. The clean synthesis gas can be
which chemical bonds are broken and gasification reactions (3)
converted to valuable products such as electricity, steam, hydrogen
and (4) become favourable. If the gas is considered for the
and chemicals.[35]
subsequent synthesis, the following water–gas shift reaction (5) is
employed:
REACTION MECHANISM, KINETICS AND TYPICAL PRODUCT
PROFILE CO þ H2 O ! H2 þ CO2 DH R ¼ 40:9 MJ=kmol: ð5Þ

The gasification process, in general, includes a devolatilisation step

(pyrolysis) and a char gasification step. During pyrolysis, the The water–gas shift reaction, alters the hydrogen to CO ratio
carbonaceous material is heated and rapidly loses hydrocarbons, (H2/CO) in the final mixture, but does not greatly impact the
tars and other volatiles. This step is much faster than the char heating value of synthesis gas.
gasification step. Consequently, char gasification is the rate
limiting step during gasification of solid fuels. However, pyrolysis C þ 2H2 ! CH4 DH R ¼ 75 MJ=kmol ð6Þ
determines the amount of char produced and structural properties.
The char gasification involves reactions with the various gaseous CO þ 3H2 ! CH4 þ H2 O DH R ¼ 206 MJ=kmol: ð7Þ
species present in the gasifier such as H2O, CO2 and the reduced
amount of O2 remaining after combustion of the volatile species. Methane formations, via the two methanation reactions, shown
The progress of char particle gasification is a function of the particle above, are favoured by high pressures and low temperatures.
size, porosity, gasifying agent chemical composition, gasifying Methane formation is a highly exothermic reaction and does not
agent partial pressure, reactor temperature, geometry of the consume oxygen and therefore increases the efficiency of
particle, pore structure, number of active sites, number of reactive gasification and the final heating value of synthesis gas. Further,
sites, ash content, inhibitors partial pressure and total pressure. sulphur in the feed is converted mainly to H2S and a small amount
Gasification can be described as the partial oxidation process in of carbonyl sulphide (COS).
which carbonaceous solids react with oxygen, or oxygen enriched In order to develop a flexible, efficient and economically
air, or air according to the following overall reaction:[35] competitive gasification process for petcoke gasification, it is
important to understand the gasification kinetics of petcoke. This
Cn Hm þ n=2 O2 ! nCO þ m=2H2 : exercise, in turn, can provide valuable information for proper
design and operation of gasifiers. Tyler and Smith[36] investigated
gasification reactivity of petcoke of different sizes, viz. 2900, 900
and 200 mm. The order of the reaction rate with respect to carbon
dioxide concentration was found to be about 0.6 and activation
Table 4. Typical synthesis gas composition with petcoke as gasification
feedstock; Heaven[124] energy in the range of 203–237 kJ/mol for petcoke. Furimsky[26]
has investigated the gasification reactivities of DC and FC in fixed
Component Composition (mol%) bed and fluidised bed at atmospheric pressure. The objective of this
CO 47.72
work was to identify a relationship between the fixed bed and
H2 30.33 fluidised bed systems in terms of the extent of reactivity. The fixed
CO2 17.88 and fluidised bed reactors were operated at 830–1010°C and 805–
H2O 0.12 1020°C, respectively. And residence times were 60 and 30 min in
CH4 0.01 the former and the later one. It was observed that the carbon
Ar 0.83 conversion increased with increasing temperature in the fixed bed
N2 1.27 reactor. The carbon conversion was found to decrease when
H2S 1.76 gasification media changed from air þ steam to H2 þ steam. The
COS 0.02 bulk reactivity of FC coke was higher than that of DC coke in both

VOLUME 92, MARCH 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 443
the reactors. The bulk density of FC was found to be higher than
that of DC, when comparing 250–840 mm particles in fluidised bed
and 840–1400 mm particles in fixed bed, respectively.
Revankar et al.[37] have investigated the effect of particle size,
porosity, and thickness of a pellet on the steam gasification of
petcoke both in the presence and absence of a catalyst. They have
used K2CO3/Ni as the catalyst and bentonite as the binder. The rate
constant was found to increase with an increase in particle size as
well as with a decrease in thickness of the flat plates. For non‐
catalytic gasification, activation energy was found to be invariant
with particle size, while for catalytic gasification the frequency
factor was found to remain constant for all the particle sizes
investigated. Watkinson et al.[28] have investigated the continuous
autothermal gasification of DC and FC in spouted and fluidised
beds. At 950°C and 85% carbon conversion, a typical product gas
contained about 34% H2, 24% CO, 39% CO2 and 3% H2S (dry
basis). FC gasified in a fluidised bed with cyclone char recycle
yielded lower carbon conversion and heating values vis‐à‐vis DC.
They reported that to attain conversions above 80 wt%, temper-
atures should be higher than 1000°C. For both the cokes, recycling
fine particle improved the overall carbon conversion. The carbon
conversion was further increased by employing potassium
carbonate as a catalyst. Sulphur in the product gases was reduced
by up to 95% by using beds of dolomite. Nguyen and Watkinson[29]
have studied the kinetics of petcoke (DC and FC) gasification with
steam in the temperature range of 800–930°C and at atmospheric
pressure in a 63.5 mm diameter stirred and fixed bed reactor.
Scanning electron microscopy, surface area analysis and mercury
porosimetry were employed to relate physical structure changes in
the solids. Using Brunauer–Emmett–Teller (BET) surface area
analyser they observed that the surface area increased when
carbon conversion reached a maximum around 30% conversion
and then declined. This is a typical behaviour reported by many
authors working on gasification of microspores carbons. In fact, the
well‐known Random Pore Model (RPM)[38] has been developed
based on the same assumptions. The rapid initial increase in the
surface area is attributed to the reopening of the closed micropores
during heat treatment; however, as the gasification reactions
proceed micropores will gradually grow in size and coalesce to
form meso and macropores which manifests itself in the reduction
of the surface area in the later stages of gasification. It was found
that DC and FC are relatively unreactive to steam gasification below
850°C. Particle size effect was found to be significant for a particle
having a size greater than 1000 mm. The diffusional effect was
described by an empirical correlation to the observed reaction rate
constant which was found to decrease with an increase in the
particle size. Further, they have used three representative gas–
solid models, viz. RPM of Gavalas,[38] random capillary model of
Bhatia and Perlmutter,[39] and modified volumetric model (VM) of
Kasaoka et al.,[40] in order to describe the gasification rate. Overall,
in this study the modified VM gave the best fit to the experimental
data. Because of the particle size they used in their experiments (in
the order of millimeter), their results suffered from diffusional
effects. Therefore, they represented the reaction rate constants as a
function of particle diameter.
Zou et al.[13] have studied the kinetics of petcoke gasification
with CO2 in the temperature range of 975–1050°C and at 0.1 MPa
pressure using a pressurised thermogravimetric analyser (TGA).
The study revealed that higher temperature leads to shorter
gasification finishing time and the higher gasification rate of
petcoke CO2 gasification. Gasification rate was found to increase
with increasing conversion and then decreases rapidly after
reaching the maximum rate. The conversion corresponding to
444 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
the maximal gasification rate was around 0.3. In the later period,
the low gasification rate was due to the low gasification reactivity
because of the graphitisation interaction. Compared with coal char,
petcoke has higher crystallinity and degree of order, and it was
essentially a part‐graphitised carbon material. Activation energy of
petcoke‐CO2 gasification was found to be 198 kJ/mol and the
estimated reaction order was found to be 0.54, 0.59, 0.63, 0.88 for
reaction temperature of 975, 1000, 1025, 1050°C, respectively.
They considered shrinking the core model, the integrated
model,[41] the RPM and the normal distribution function model
to fit the kinetic data of petroleum coke gasification with CO2,
respectively. It was reported that the normal distribution function
model was able to describe well the variation of gasification rate
with conversion. They stated that the obvious graphitisation that
makes the gasification rate decrease rapidly in the later stage of
petroleum coke CO2 gasification is the reason why random pore
cannot fit well.
Fermoso et al.[42] studied the steam gasification reactivity and
kinetics of five different types of fuels (two coals, a petroleum coke
and two samples of biomass). In this work, all the experiments
were carried out using TGA under isothermal conditions at
different temperatures depending on the nature of the sample
(725–1050°C). For this purpose, three different mathematical
models were applied [VM, grain model (GM) and RPM], and their
validity in predicting the conversion and reactivity of the samples
during gasification in steam was assessed. Kinetic parameters
were derived in order to determine the kinetic model which best
represents the behaviour of the chars during the gasification
process. The fuel chars were obtained by pyrolysis in a fixed‐bed
reactor at a temperature of 1373 K for 30 min. The gasification tests
were carried out by thermogravimetric (TG) analysis at different
temperatures and steam concentrations. The reactivity study was
conducted in the kinetically controlled regime. The RPM was found
to be the most suitable model for predicting the behaviour of the
chars during steam gasification.
Wu et al.[43] investigated the physical properties and gasification
reactivity of coal char and petroleum coke under various pyrolysis
conditions. The temperature was varied from 950 to 1400°C and
pressure was up to 3 MPa. They employed thermo‐gravimetric
analyser and the particle size of the sample was up to 73 mm. The
increasing pyrolysis temperature leads to the decrease of BET
surface areas of coal chars, while those of petroleum coke present
an opposite variation trend. Hence, the high pyrolysis temperature
favoured petroleum coke gasification. With the increase of the
pyrolysis pressure this resulted in the increase of the gasification
activity of coal chars and had almost no effect on the petroleum
coke. They found that the gasification activity of petroleum coke
was lower than that of coal char and even lower than that of natural
graphite.
Fermoso et al.[44] investigated the co‐gasification of coal,
biomass and petroleum coke at high pressure in a bench scale
fixed bed reactor. They considered binary blends of a bituminous
coal with different types of biomass and petcoke (up to 60%) as
well as ternary blends of coal–petcoke–biomass (45–45–10%). It
was observed that the addition of up to 10% biomass into the blend
of coal and pet‐coke (1:1) led to an increase in H2 and CO
production. However, beyond 10% biomass with coal and
petroleum coke blend did not yield any significant change in H2
and CO production. The maximum temperature studied in their
work was around 1000°C and the pressure was varied from 1 to
1.5 MPa. Later Fermoso et al.[45] studied the co‐gasification of
different rank coals with biomass and petroleum coke. They used
tubular reactor with fuel sample size of 75–150 mm. They
VOLUME 92, MARCH 2014
considered four coals of different rank and steam and oxygen
mixture (15 and 25 vol%, respectively) as gasifying agents. The
gasification of the coals was carried out isothermally (1000°C) at
pressures of 0.1 and 1.5 MPa. Regardless of coal rank, gasification
at atmospheric pressure led to the production of a greater amount
of H2 and syngas, and better cold gas efficiencies and carbon
conversions than those obtained at 1.5 MPa. The increase in
pressure exerted a negative effect on the gasification process, and
this effect was more pronounced in the case of low rank coals.
Zhan et al.[19] carried out studies of CO2 gasification of petcoke
using black liquor as a catalyst in the temperature range of 1050–
1400°C at atmospheric pressure. It was found that the gasification
reactivity of petcoke was improved significantly by black liquor at
appropriate loadings from 1 to 15 wt%. They have also observed
that the gasification reactivity was affected by different loading
methods in the order: wet grinding > dry grinding > physical
impregnation > dry mix. The gasification reactivity of petcoke with
20 wt% black liquor loading was found not to be higher than that of
petcoke with 15 wt% black liquor loading. Authors attributed this
to the blocking of pores in petcoke, caused by the excess catalyst
loading, restricts the access of CO2 to the surface of pores in
petcoke. Temperatures, loadings and loading methods are great
factors influencing the catalytic activity of black liquor.
Lee et al.[20] investigated the gasification of petcoke alone as well
as gasification of mixture of petcoke and lignite in the 1 tonne/day
entrained‐flow gasifier. The authors determined and compared the
characteristics of syngas flow rate, gas composition, heating value,
cold gas efficiency and carbon conversion of both the gasification of
petcoke and the mixture of petcoke and lignite. It was found that
the average concentrations of H2, CO, CO2 produced from petcoke
gasification were 22%, 39% and 34%, respectively. With regard to
the gasification of mixture of petcoke and lignite, the average
concentrations of H2, CO, CO2 were found to be 25%, 43% and
27%, respectively. The heating value and cold gas efficiency of
the mixture were found to be about 9000 kJ/kg and about 65%,
respectively and were higher than those of only petcoke
gasification due to improved syngas composition. The authors
made out that the co‐gasification in an entrained‐flow gasifier
might be an excellent method to use lignite with high moisture
content and petcoke with low reactivity.
From the above studies, it is clear that blending petcoke with
lignite can enhance reactivity and efficiency of the gasification.
Further, Zhan et al.[21] made an attempt to investigate the effect of
blending methods especially the grinding process on the co‐
gasification reactivity of petcoke and lignite. For this purpose, two
different blending methods and six kinds of grinding time were
used. It was observed that the co‐gasification reactivity was
significantly influenced by blending methods. Wet grinding was
found to be more effective than dry grinding. The long grinding
time made lignite show greater BET specific area. And the sample
in long grinding time has more association chances between
petcoke and alkali‐ and alkaline‐earth‐metallic (AAEM) species.
Similar to Zhan et al.,[19] Liu et al.[46] studied the catalytic effect
of coal liquefaction residue instead of black liquor on the
gasification reactivity of petcoke with CO2 at different temperatures
and loading of coal liquefaction. The temperature range of the
experiments was 900–1050°C and the isothermal kinetics was
compared to evaluate the effect of loading of the coal liquefaction
residue on the gasification reactivity of petcoke. The gasification
reactivity, X‐ray diffraction, scanning electron microscopy images
and BET specific surface area were investigated. At the loading of
coal liquefaction the residue (CLR) was 20%, the catalytic
gasification reactivity of the mixture was almost three times
VOLUME 92, MARCH 2014
higher than that of pure petcoke at 1050°C, while it was nearly 1.5
times higher at 900°C. With increasing coal liquefaction residue
loading, the ratio of the catalytic content of AAEM species and iron‐
sulphur species increased. Therefore, the gasification reactivity of
the petcoke was found to be substantially high with increasing CLR
loading. They reported that the alkali metals, alkaline‐earth
metals, and transition metals in CLR promote the co‐gasification
reaction, while asphaltene and oils had no effect.
It is apparent from the published literature that the high‐pressure
char gasification has been studied for a wide range of coal char
types, however, kinetic studies of gasification with petcoke at high
pressures are scarce in the literature. Therefore, Malekshahian and
Hill[47] took up the intrinsic kinetics of CO2 gasification of petcoke
up to pressure of 2.4 MPa. They also studied the effect of CO2
concentration, and the temperature on the reaction rate of CO2
gasification of petcoke chars. The temperature varied between 900
and 975°C. The reaction order with respect to CO2 was found to be
0.49  0.02 for the pressure range of 0.1–2.4 MPa at 950°C and
activation energies were 260  24 kJ/mol for 0.1 MPa and
254  12 kJ/mol for 1.4 MPa. Similar activation energies at
different pressures suggest that the fundamental mechanism of
the carbon reaction with CO2 is similar for different pressures
and the reactions happening at different pressures are the same.
The difference in the reaction order of this study with that of the
previous studies may be attributed to the different origin of the
petcoke as well as the range of the particle size and temperature
used in this study. To calculate the kinetic parameters at different
pressures, the grain, volume, and random‐pore models were
applied to the experimental results. The random‐pore model gave a
best fit to the experimental data of gasification of petcoke char at
950°C and different pressures. However, the grain and volume
models failed to predict the maximum rate in the reactivity profile.
Shen et al.[48] studied the co‐gasification performance of coal and
pet‐coke blends in a pilot‐scale pressurised entrained flow gasifier.
The gasification experiments were carried out in the temperature
range of 900–975°C and pressure was up to 2.4 MPa. The fuel
particle size was less than 75 mm. Two subbituminous and
bituminous coals were individually blended with a petcoke.
They observed that the slagging problem due to high ash content of
subbituminous coal was improved when 70% or more coke was
mixed with the coal. They found stable operation by mixing
petcoke with bituminous coal in any ratio because of its high
moisture and volatile matter and the low ash content. They also
observed that higher oxygen to carbon ratios resulted in a drop in
syngas production with O2/C ratio between 0.6 and 0.65 m3/kg
resulting in maximum syngas production. However, the study did
not consider the effect of steam in the gasification performance.
Furthermore, a long term gasification operation requires much
closer attention to ash composition of coke for elements such V and
Ni which cause refractory failure and fouling in the economiser and
shift reactor as well.
Xu and Sun[49] also studied the co‐gasification behaviour of
biomass and petroleum in a fixed‐bed reactor to determine the
effect of the blending ratio and particle size of petroleum coke on
the tar yield and gas heat value. For the case of biomass fuel
gasification alone at 700°C, the results showed that the gas heat
value decreased up to 15% from 2.37 MJ/m3 with a 13% increase
in oxygen content and the average tar yield was 6.4%. For the
co‐gasification case, the average tar yield was about 2.9%, with
corresponding gas heat value of 5.19 MJ/m3 compared to the
biomass case under similar conditions. At the temperature of
700°C, the best ratio of the petroleum coke to biomass was 1:1 with
the oxygen content of 4%. The largest and smallest tar yields
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 445
obtained were for the gasification with petroleum coke alone, and
the co‐gasification case. They also observed that as the particle size
of petroleum coke increased, the tar decomposition rate gradually
decreased. Also, they reported that the tar yield decreased with the
temperature in all cases.
Wu et al.[50] presented potassium‐catalysed steam gasification of
petroleum coke for H2 production in a fixed‐bed system. The
particles with a diameter of <73 mm were used. The reactor was
operated at atmospheric pressure. The gasification reactivity,
selectivity for the catalytic gasification were investigated and
compared with the non‐catalytic gasification. It was observed that
as the gasification temperature increased to 1000°C, the non‐
catalytic gasification rate of petroleum coke was still very slow.
Whereas, the catalytic action allowed the petroleum coke to react
with steam vigorously even at a temperature as low as 750°C, and
the time taken to complete the gasification with catalysts was even
less than that without catalysts at 1000°C. This implies that
catalytic gasification could be used for effectively lowering the
gasification temperature. However, the catalyst was found to be
less effective below 750°C, implying that there existed a significant
change in the effect of the gasification temperature on the activity of
catalyst. The catalytic gasification could not only effectively
promote these reactions (the water–carbon reaction, the water–
gas shift reaction and the methane‐steam reforming reaction), but
also greatly elevate the gasification selectivity towards CO2 (a high
gasification selectivity towards CO2 meant a high H2 production).
They concluded that petroleum coke could be feasibly utilised as
the feedstocks for the catalytic steam gasification to produce gases
with high H2 (55.5–60.4%) and virtually no CH4 (below 0.1%).
Zhou[51] investigated the catalytic effects of iron species,
temperature, catalyst loading, composition of catalysts and
synergistic effect of calcium hydroxide and iron species on the
petcoke CO2 gasification. The catalytic activity of the iron species
was observed to be in the following order: FeCl3>Fe(-
NO3)3>FeSO4. An effective Fe(C) catalyst was prepared by
blending the petcoke with 5 wt % FeCl3 loading and Ca(OH)2.
Because of the high catalytic activity of FeCl3, the gasification was
found to be faster and complete. They found that the precipitation
method using Ca(OH)2 was suitable for preparing the chlorine‐
free, active iron catalyst from FeCl3 solution. Otherwise,
Cl containing compounds would eventually evolve during
gasification, and they may cause corrosion on various parts of
materials. It was observed that the gasification conversion at 950°C
was higher at any time than that at 1050°C without catalyst. This
means that the use of an iron catalyst could lower the gasification
temperature. They have also reported the decrease of the
gasification rate with the increase of conversion has been more
in the case of catalysed gasification as compared to uncatalysed
gasification. It was because of the specific surface area and pore
volume increase with gasification conversion below 50%, and after
reaching the maximum, they (surface area and volume) decrease
Table 5. Porosity state of petroleum coke with FeCl3 (C) at different
conversions; Zhou[51]
Samples BET surface area (m2/g) Pore volume (cm3/g)
Pure coke 1.63 0.0058
0% 5.71 0.050
30% 6.07 0.073
50% 7.37 0.074
70% 1.24 0.050
90% 0.93 0.025
446 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
with gasification conversion above 50%. The specific surface area
and pore volume have been particularly low when gasification
conversion reaches 90% (Table 5), which further led to the
reactivity decreasing markedly. With respect to catalyst loading
(FeCl3), authors found that 2 wt% was a saturation loading.
Regarding kinetic modelling, the shrinking core model,
integrated model, RPM and normal distribution function model
were used to fit the kinetic data of petroleum coke gasification with
CO2. It was found that the random pore volume among all other
models could best describe the variation of the gasification rate
with conversion.
A brief summary comprising the reaction conditions and the
findings of the investigators with regard to petcoke gasification is
given in Table 6.
QUALITATIVE DESCRIPTION OF DIFFERENT GASIFIERS
There are three technology variants, classified by geometrical
configurations of gasifiers according to their flow geometry, viz.
fixed bed, fluidised bed and entrained flow gasifiers. The fixed and
fluidised bed gasifiers appear to be unsuitable for the petcoke
gasification because of the following reasons:
1. The fixed/moving bed gasifiers are highly sensitive to the coal
reactivity as they favour the large size of feed coal particles
with highly reactive coals. To maintain the permeability of the
fixed bed, both physical strength and coking behaviour of coal
particles need to be considered. This sensitivity implies
stringent requirements on the coal specifications.
2. Fluidised bed gasifiers operate on a dry crushed feedstock at
low operating temperatures (550–1000°C) to avoid ash
agglomeration otherwise it leads to uneven bed fluidisation.
Therefore, the process coals must have an ash fusion
temperature (AFT) higher than the operating temperature of
the gasifier.
3. Since both the systems can operate at relatively low temper-
atures, they are suitable for reactive coals such as lignites and
brown coals or for coals containing potentially troublesome
volatile inorganic compounds (to avoid highly reactive and
corrosive vapours).
4. For lower reactivity petcoke fixed/moving and fluidised bed
gasifiers result in lower carbon conversion due to the lower
gasification temperatures.
5. Entrained flow gasifiers offer high output, high efficiency and
high carbon conversion efficiency than that of moving bed and
fluidised bed gasifiers.
Entrained Flow Gasifier
Entrained‐flow gasifiers operate with feed and blast in co‐current
flow. The residence time in these processes is short (a few
seconds). Given the short residence time, high temperatures are
required to ensure a good conversion, and therefore all entrained‐
flow gasifiers operate in the slagging range. The high temperature
operation creates a high oxygen demand for this type of process.
Entrained flow gasifiers do not have any specific technical
limitations on the type of feed used, although feed with a high
moisture or ash content will drive the oxygen consumption to
levels where alternative processes may have an economic
advantage.[52]
In a dry feeding mode, the feedstock is screw‐fed from lock
hoppers to burners where the gasification medium (air, oxygen or
steam) convey the feedstock at a velocity in excess of flame
VOLUME 92, MARCH 2014
 Table 6. Summary of the reported work on petcoke gasification

Refs. Experimental details Conclusions

[36]
Tyler and Smith Feed Petcoke The reaction rate was found to be similar for 2.9 and 900 mm

VOLUME 92, MARCH 2014

Reactor Fixed bed for petcoke particles, but that rates for the 220 mm particles
Amount (g) — are higher by about 25%
Particle size (mm) 220, 900, 2900 The pore diffusion was found to have no influence on the
Temperature (°C) 745–905 reaction rate, that is the chemical reaction alone controlled
Pressure (MPa) 0.1 the rate
Time (min) 0–300 The order of the rate with respect to carbon dioxide
concentration was found to be about 0.6, and activation
energy in the range of 203–237 kJ/mol for petroleum coke
Furimsky[26] Feed Delayed coke from Suncor Ltd. and fluid coke from Syncrude Ltd., Canada For both delayed coke (DC) and fluid coke (FC), the carbon
Reactor Fixed bed and fluidised bed conversion was found to increase with increase in
temperature
Delayed coke Fluid coke The bulk density of FC was found to be higher than that of DC,
when comparing 250–840 mm particles in fluidised bed and
Fixed bed Fluidised bed Fixed bed Fluidised bed 840–1400 mm particles in fixed bed, respectively
The fraction of carbon gasified by steam in 1 h was about
Amount (g) 50 50 50 50 11.2% at 930°C
Particle size (mm) 840 < dp < 1400 250 < dp < 840 840 < dp < 1400 250 < dp < 840 C þ O2 and CO þ O2 reactions were dominant in overall
Temperature (°C) 830–1010 815–980 855–1010 805–1020 carbon conversion
Pressure (MPa) — — — — CO2/CO ratios in fixed bed were consistently higher than
Residence time (min) 60 30 60 30 those in fluidised bed
The CO2 content in gases increased with increase in
temperature in the case of fixed bed reactor
Revankar et al.[37] Feed Petcoke For catalytic as well as noncatalytic gasification, for the same
Amount (g) 0.75–3.45 grain size, the rate constant was found increasing with
Particle size (mm) 37–590 increasing in grain size
Temperature (°C) 695–880 The activation energy was independent of particle size in
Pressure (MPa) 0.1 noncatalytic case
Time (min) 15–80 The reverse was observed for catalytic gasification
Reactor Tubular furnace
Watkinson et al.[28] Feed Delayed coke and fluid coke from Alberta oil sands, Canada At 950°C and 85% carbon conversion, a typical product gas
Amount (g) — contained about 34% H2, 24% CO, 39% CO2 and 3% H2S
Reactor Fluidised bed and spouted bed (dry basis)
Temperature (°C) 950 Fluid coke gasified in a fluidised bed with cyclone char recycle
Pressure (MPa) 0.1 yielded lower carbon conversion and heating values
Residence time (min) 0–480 vis‐à‐vis delayed coke
To attain carbon conversion above 80 wt%, temperatures in
excess of 1000°C are necessary
Sulphur in the product gases was reduced by up to 95% by
using beds of dolomite

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

(Continued)

447
 Table 6. (Continued)

448
Refs. Experimental details Conclusions

Nguyen and Feed Delayed coke and fluid coke derived from Athabasca bitumen, Canada Scanning electron microscopy, surface area analysis and
Watkinson[29] Reactor Stirred and fixed bed mercury porosimetry were employed to relate physical
Amount (g) 150 structure changes in the solids
Particle size (mm) 100–3500 Delayed coke and fluid coke are relatively unreactive to steam
Temperature (°C) 800–930 gasification below 850°C
Pressure (MPa) 0.1 As regards the particle size effect, it was found that it becomes
Residence time (min) 0–600 significant only above 1 mm
Zou et al.[13] Feed Petcoke, Jing ling refinery, China Higher temperature leads to the shorter gasification finishing
Reactor Thermo gravimetric analyser (TGA) time and the higher gasification rate of petcoke CO2
Amount (g) 0.01 gasification
Particle size (mm) 90–125 Gasification rate was found to increase with increase in
Temperature (°C) 975–1050 conversion and then decreases rapidly after reaching the
Pressure (MPa) 0.1 maximal rate
Time (min) 0–240 Activation energy and reaction order of petcoke CO2
gasification was found to be 198 kJ/mol and 0.54–0.88,
respectively
Fermoso et al.[42] Feed Petcoke, two coals and two samples of biomass Five different fuel chars were gasified at atmospheric pressure
Reactor Thermo gravimetric analyser (TGA) with steam at different temperatures

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

Amount (g) 0.006 The random pore model was found to be the most suitable
Particle size (mm) <150 model for predicting the behaviour of the char gasification
Temperature (°C) 725–1050 with steam
Pressure (MPa) 0.1 The reaction order was in the range of 0.4–0.7
Time (min) 0–220
Reactor Thermo gravimetric analyser (TGA)
Amount (g) 0.006
Particle size (mm) 73
Temperature (°C) 950–1000
Pressure (MPa) 0.1–3
Time (min) 0–180
Fermoso et al.[44] Feed Petcoke, two coals and two samples of biomass An addition of up to 10% biomass into the blend of coal and
Reactor Fixed bed pet‐coke (1:1) led to an increase in H2 and CO production
Particle size (mm) 75–150 However, beyond 10% biomass with coal and petroleum coke
Temperature (°C) 1000 blend did not yield any significant change in H2 and CO
Pressure (MPa) 1–1.5 production
Time (min) 0–220
Fermoso et al.[45] Feed Petcoke, two coals and two samples of biomass Regardless of coal rank, gasification at atmospheric pressure
Reactor Tubular yielded a greater amount of H2 and syngas than at 1.5 MPa
Particle size (mm) 75–150 The increase in pressure exerted a negative effect on the
Temperature (°C) 1000 gasification
Pressure (MPa) 1–1.5
Time (min) —
Zhan et al.[19] Feed Petcoke from Qi Lu Refinery and black liquor from pulp mill Black liquor can be used to catalyse petcoke gasification with
Reactor Thermo gravimetric analyser (TGA) appropriate loading varies from 1 to 15 wt%
Amount (g) 0.008 The gasification was found to be effected by different loading
Particle size (mm) 74–165 methods
Temperature (°C) 950–1400 Temperature, loadings and loading methods found to have
Time (min) 0–200 significant effect on the catalytic activity of black liquor on
Pressure (MPa) 0.1 the reactivity of petcoke

VOLUME 92, MARCH 2014

 Table 6. (Continued)

Refs. Experimental details Conclusions

Liu et al.[46] Feed Petcoke from Jinling Refinery plant and coal liquefaction It was found that alkali and alkaline‐earth‐metallic (AAEM)
residue from shenhua group species and iron‐sulphur species in coal liquefaction residue
Reactor Thermo gravimetric analyser (TGA) could be used to catalyse the petcoke gasification
Amount (g) 0.007–0.008 Similar to earlier findings both temperature and catalyst
Particle size (mm) 83–165 loading have significant impact on the rate and extent of
Temperature (°C) 900–1050 gasification

VOLUME 92, MARCH 2014

Pressure (MPa) 0.1
Time (min) 0–150
Malekshahian and Hill[47] Feed Petcoke from Suncor Energy Activation energies of petcoke CO2 gasification were found to
Reactor Thermo gravimetric analyser (TGA) be 260  24 kJ/mol at 0.1 MPa and 254  12 kJ/mol at
Amount (g) 0.015 1.4 MPa, respectively
Particle size (mm) 90 The reaction order of petcoke CO2 gasification was found to
Temperature (°C) 900–975 be 0.49  0.02 for the pressure range of 0.1–2.4 MPa at
Pressure (MPa) 0.1–2.4 950°C
Time (min) 0–600 Overall, it was found that the effect of total pressure was not
significant
Shen et al.[48] Feed Petcoke and two coals The slagging problem due to high ash content of
Reactor Pilot scale pressurised entrained flow gasifier subbituminous coal was improved when 70% or more
Fuel flow rate 35 kg/h petcoke was mixed with the coal
Particle size (mm) 74 Stable operation can be obtained by mixing petcoke with
Temperature (°C) 900–975 bituminous coal in any ratio because of its high moisture
Pressure (MPa) 0.1–2.4 and volatile matter and the low ash content
Xu and Sun[49] Feed Petcoke and Biomass In the case of biomass fuel gasification alone at 700°C, the gas
Reactor Fixed bed heat value decreased upto 15% from 2.37 MJ/m3
Fuel flow rate — For the co‐gasification case, gas heat value increased to
Particle size (mm) 74 5.19 MJ/m3
Temperature (°C) 900–975
Pressure (MPa) 0.1–2.4
Wu et al.[50] Feed Petcoke The potassium catalyst allowed the petroleum coke to react
Reactor Fixed bed with steam vigorously even at a temperature as low as
Amount (g) 1 750°C.
Particle size (mm) 73 The time taken to complete the gasification with catalysts was
Temperature (°C) 650–1000 even less than that without catalyst
Pressure (MPa) 0.1 The catalytic gasification elevates the selectivity towards CO2
Time (min) 0–200 (a high gasification selectivity towards CO2 meant a high H2
production)
Zhou[51] Feed Petcoke from Nanjin Jinling Refinery Plant The activation energy of petcoke CO2 gasification with 5 wt%
Reactor Thermo gravimetric analyser (TGA) FeCl3 was found to be 168 kJ/mol in the temperature range
Amount (g) 0.007–0.008 of 950–1100°C.
Particle size (mm) dp < 0.74 The catalytic activity of iron species was found to be more with
Temperature (°C) 1400–1500 FeCl3 than Fe(NO3)3 and least with FeSO4. Ca(OH)2
Pressure (MPa) 0.4–0.8 addition to the catalyst mixture was found to remove Cl,
Time (min) 0–150 therefore, less corrosion

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

449
Figure 1. Schematic diagram of entrained flow gasification system employing GE full heat recovery type gasifier (slurry feed entrained flow gasifier).
Furimsky.[35]

propagation rates into the reactor. Pumps are used for the injection Conoco Phillips E‐Gas Gasifier
of feed in a slurry mode. The coal fed systems for dry fed gasifiers The E‐GAS gasifier by Conoco Phillips, Figure 2 is a slurry‐feed,
are more complicated to build and operate than the slurry‐fed pressurised, up‐flow, entrained slagging gasifier whose two‐stage
devices. Because of this complication, dry fed gasifiers generally operation makes it unique. Slurry concentrations range from 50%
operate at lower pressures compared to slurry‐fed systems. The to 70% by weight, depending on the inherent moisture and quality
higher operating pressure is beneficial to increase reaction of the feed coal. About 75% of the total slurry feed is fed to the first
intensity and reduce gasifier size. The higher operating efficiency (or bottom) stage of the gasifier. This slurry is combined with
of dry‐fed gasifiers is challenged by simpler and cheaper design of oxygen in mixer nozzles and injected into the first stage of the
feeding systems and higher operating pressures of slurry‐fed gasifier. This stage is best described as a horizontal cylinder with
gasifiers. The operating temperatures are usually in the range of two horizontally opposed injectors. The hot raw gas from the first
1200–1600°C (above ash slagging temperatures) and pressures in stage enters the second (top) stage, which is a vertical cylinder
the range of 2–8 MPa. perpendicular to the first stage. The remaining 25% of the coal
All of the commercial entrained flow gasifiers are slagging slurry is injected into the hot raw gas. The endothermic
gasifiers. However, it may also be pointed out that such high gasification/devolatilisation reactions in this stage reduce the final
temperatures have an impact on burners and refractory life and
require the use of expensive materials of construction as well as the
use of sophisticated high temperature heat exchangers to cool the
syngas below the ash softening temperature so as to avoid fouling
and control the corrosion problems. Raw gas exiting the gasifier
usually requires significant cooling before being cleaned. There are
two main methods of cooling the gas: (a) high temperature syngas
cooler, which can also include recycling a portion of cooled gas to
the gasifier or introduction of feed slurry; (b) quenching the gases
with water.[33,35] Figure 1 shows a typical flow scheme for an
entrained flow gasifier.
Several types of commercial entrained flow gasifiers are
available for the selection of one which fulfils the desired features
of performance, economic and environmental requirements.
With respect to the gasification of refinery residues, the entrained
flow gasifiers are the gasifiers of choice. Some designs of dry
feeding entrained flow gasifiers are Shell, Uhde, Siemens and
TPRI gasifiers. Further, some designs of slurry feeding entrained
flow gasifiers are Texaco, GE and ConocoPhillips. High temper-
atures attained in these gasifiers make them suitable for the
gasification of less reactive feedstocks such as the petcoke and oil
sand coke.[35] A qualitative description of these gasifiers is given Figure 2. Schematic diagram of ConocoPhillips E‐gas gasifier (slurry feed,
below. two stage). Higman and Burgt.[52]

450 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, MARCH 2014
gas temperature to about 1000°C and add some hydrocarbons to
the product gas. Char is produced in the second stage. The char is
recycled to the hotter first stage. The 1000°C hot gas leaving the
gasifier is cooled in a fire‐tube product gas cooler (high temperature
heat recovery unit or HTHRU) generating steam. After cooling in
the HTHRU, particulates and chlorides in the syngas are removed
in char filter and wet scrubber and the char is recycled to the
gasifier where the carbon in the char is converted to syngas. The
syngas is then sent for downstream processing.
GE Energy Gasifiers
There are three types of commercial gasifiers from GE Technology,
Schenectady, New York. They are the Quench type Figure 3A,
partial heat recovery (PHR) type Figure 3B and full heat recovery
(FHR) type Figure 1. In quench gasifier design, the hot gas exiting
the reaction chamber is contacted with water via a quench ring
followed by immersion into the water in the lower portion of the
gasifier vessel. The cooled syngas by direct contact with water,
Figure 3. (A) Schematic diagram of GE gasifier of quench type. Higman and Burgt.[52] (B) Schematic diagram of GE gasifier of partial heat recovery (PHR).
Higman and Burgt.[52]
VOLUME 92, MARCH 2014
exits the gasifier saturated with water, and enters a scrubber for
particulate and soot removal. This design provides an effective
mechanism to add water to the syngas to promote the water–gas
shift reaction and maximise hydrogen production in downstream
processing. The quench design mode is often used to accommodate
heavy hydrocarbon feedstock. In the PHR type, the hot gas flows
downward into a radiant syngas cooler where high‐pressure steam
is produced. The syngas cooler is specifically designed to meet the
conditions of high thermal gradients and the ability to handle soot.
The syngas passes over the surface of a pool of water at the bottom
of the radiant syngas cooler and exits the vessel. The slag drops into
the water pool and is fed from the radiant‐syngas‐cooler‐sump and
exit to a lock hopper. The black water flowing out with the slag is
separated and recycled after processing in a dewatering system.
The slag is eventually removed through a lock hopper. This design
configuration maximises heat recovery for steam production, as
well as CO production, which is appropriate for an IGCC
application. In the FHR type a convective cooler is placed
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 451
Figure 4. Schematic diagram of Shell gasifier. Furimsky.[35]
downstream of radiant syngas cooler. Upon exiting the gasifier, a
water scrubber further cools and cleans the syngas, and the fine
particulate matter and char may be recycled to the gasifier.
Shell Gasifier
The Shell gasifier, as shown in Figure 4, is a dry‐feed, pressurised,
entrained flow slagging gasifier. The high‐temperature gasification
process converts the ash into molten slag, which runs down the
refractory‐lined water wall of the gasifier into a water bath, where
it solidifies and is removed through a lock hopper as slurry in
water. Some of the molten slag collects on the cooled walls of the
gasifier to form a solidified protective coating. The crude raw gas
leaving the gasifier contains a small quantity of char and about half
of the molten ash. To make the ash non‐sticky, the hot gas leaving
the reactor is partially cooled by quenching with cooled recycle
product gas. Further cooling takes place in the waste heat recovery
(syngas cooler) unit, where high‐pressure steam is generated. The
syngas passes through a hot gas filter for solid (fly ash) removal and
is further treated in a wet scrubber to remove soluble salts and finer
particles. The syngas is then treated to remove COS and hydrogen
sulphide.
Siemens Gasifier
Siemens gasification technology was originally developed in 1975
by DBI, the German Fuel Research Institute, primarily to gasify
lignite and subsequently modified for coal feed. The gasifier,
Figure 5 is dry feed, top fired, entrained flow slagging gasifier. The
gasifier can be divided in two parts viz. upper gasifier chamber and
lower gas cooling chamber. The gasifier chamber has a cooling
screen with pressurised water inside the tubes. The cooling screen
is protected by ramming mass. Molten slag flows across this mass
452 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
and forms a solid protecting layer on it. The hot raw synthesis gas
and molten slag leave the gasifier chamber and discharge directly
into the quench section. The raw gas is cooled down by water
spray. The liquid slag is cooled down in the water bath at the
bottom of the quench vessel. The raw syngas then passes through
ventury scrubber.
Thermal Power Research Institute (TPRI) Gasifier
Thermal Power Research Institute (TPRI) has developed two‐stage
dry pulverised coal gasifier (Figure 6) with syngas cooler process.
This has a cylinder structure with membrane water‐cooling wall.
There are two stages in the gasifier. Feed nozzles are distributed
horizontally and symmetrically in the first stage of the gasifier and
feed is also introduced through the second stage nozzles. During
the operation, the feedstock, oxygen and steam carried by carrier
gas are injected into the first stage of the gasifier. Hot raw syngas is
generated and flows upward and enters the second stage, while the
melting slag flows downward through the vertical water‐cooling
wall and is discharged from the bottom of the gasifier. After the
water quench process, the slag is solidified and turned into small
particles. It then flows to the slag removal system. When the syngas
enters the second stage of the gasifier, it is mixed and cooled by the
injected feedstock and steam, where the pyrolysis and gasification
reactions occur, generating an extra amount of syngas. The
unreacted carbon and fly ash are collected by the solid removal
system and are then circulated to the feedstock milling and drying
system. The produced syngas is cooled in a radiation heat
exchanging section at the top of the gasifier and then mixed with
the cool syngas from the wet scrubbing system and dry solid
removal systems. The temperature is then dropped to around 900.
Then, the cooled syngas moves to the syngas cooler for steam
VOLUME 92, MARCH 2014

Figure 5. Schematic diagram of Siemens gasifier. Higman and Burgt.[52]
generation. The cooled syngas then goes to the dry solids removal
unit and then to the wet gas scrubber.
Uhde Gasifiers
Uhde’s gasifier is the legacy design from Krupp‐Koppers, which
merged with Uhde in 1997. Uhde offers two types of gasifier design
viz. Prenflo steam generation (PSG) Figure 7A and Prenflo Direct
Quench (PDQ) Figure 7B. PSG has horizontal burners and a waste
heat boiler downstream of the gasifier. PSG design is suitable for
downstream production of power. PDQ is a downflow membrane
wall gasifier with a direct water quench system. PDQ design is
suitable for the downstream production of chemicals and
Hydrogen. Gasifier at Puertollano, Spain is a Uhde design, with
up to 50% petcoke feed.
Opposed Multi‐Burner (OMB) Gasifier
The OMB gasification technology of the East China University of
Science and Technology (ECUST) was first demonstrated in 2005
and has been selected for 20 projects that are either operating,
under construction, or in the development phase.[53] As a typical
VOLUME 92, MARCH 2014
entrained‐flow gasifier, the OMB gasifier (Figure 8) operates at
high temperatures (above ash slagging temperatures) to ensure
high carbon conversion and syngas free of tars and phenols. It can
accommodate either coal‐water slurry feeding, or dry‐feeding (via
N2 or CO2) applications. The OMB gasifier is featured with four
horizontal impinging burners, each pair is symmetrically opposed
and meet at 180°. This configuration is intended to intensify
mixing and improve residence time distribution. In OMB, the
syngas purification process consists of a mixer, a cyclone, and a
scrubber together. The existence of the cyclone improves the
purification effect and stabilises the system operation.[54]
MATHEMATICAL MODELLING
It is known that a good model helps to identify the sensitivity of the
performance of a gasifier to variations in the different operating and
design parameters. Therefore, the designers can speculate the
effects of many parameters even without any experimental data on
them. It may be noted that the application of mathematical
modelling in petcoke gasification is fairly new compared to that in
coal combustion process. This part of the review is intended to
focus on modelling aspects of gasification in general. It may be
noted that, most of the existing literature deals with the modelling
of various coals and biomass gasification and limited work has
been published on petcoke gasification. As it is well‐known, the
mathematical modelling consists of two important features: (a)
modelling of the flow and temperature pattern in the equipment;
(b) superimposition of specific kinetics on part (a) to describe the
complete performance of the gasifier. It may be pointed out that the
modelling of the flow and temperature pattern (mass, momentum
and energy balance) for fixed, fluidised and entrained beds is the
same as well as the chemical reactions of gasification are the same.
Only the actual kinetics of chemical reaction and the range of
the operating conditions depend upon the raw material such as
petcoke, coal, biomass, etc. Therefore, it was thought desirable to
make the subject of mathematical modelling of gasification
general.
It should be noted that differences in modelling techniques for
different gasifier types (as stated in the previous section) can occur
due to physical differences in the design and operating conditions,
for example in some fixed bed gasifiers gas flow is counter‐current
to coal feed so that oxygen is consumed during contact with char
and devolatilisation occurs at relatively low temperatures in a
reducing atmosphere. This form of gasifier should have different
modelling treatment for devolatilisation than entrained flow
gasifier where devolatilisation will generally occur at a high
temperature in an oxygen rich environment. Similarly, heat
transfer in the solid bed of a fixed bed gasifier could be considerably
influenced by conduction when in an entrained flow gasifier
radiation may dominate. This section first deals with a fixed or
moving bed and followed by fluidised bed and entrained flow
gasifiers, respectively.
Fixed or Moving Bed Gasifier
Most of the earlier generic models for fixed or moving bed gasifiers
assumed plug flow in both the solid and gas phases with variable
axial velocities. A number of assumptions are required to develop a
model that is both mathematically and computationally tractable.
Some major assumptions include a shrinking‐core model
(SCM)[55,56] for gas–solid kinetics, no axial dispersion of heat
and a homogeneous gas–solid temperature in the bed. The
equations resulting from the mass and energy balances were
solved numerically using suitable integration methods. Ergun’s
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 453
Figure 6. Schematic diagram of TPRI gasifier. Higman and Burgt.[52]
equation was used to calculate the friction factor and the bed void
fraction was assumed to be either constant or vary linearly between
the feed coal and the product ash void fractions. Turbulence was
not treated formally in the slowly moving bed with low gas
velocities, but was included implicitly through model correlations
such as the effective heat‐transfer coefficient.
Schaefer et al.[57] presented a model which elucidates the
phenomena which occur in moving bed gasifier. They incorporated
the reaction by an ignition temperature and by the heat generated
on a volume basis rather than complicated rate processes which
occur in the solid phase. The steady state problem has been solved
analytically and numerically. It was found that the dimensionless
numbers, viz. flow number (F), dispersion number (Y) and
Damkohler number (Da) along with the boundary conditions
describe the problem satisfactorily. The authors have illustrated
and discussed the dependence of multiplicity and the nature of the
solution on these parameters.
454 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
Yoon et al.[58] reported a steady state simulation of a moving bed
gasifier. The model reported describes the complex physical and
chemical processes taking place in the multiphase moving bed,
using mass and energy balances. It also takes into account the rates
of all the chemical reactions and the physical transport processes.
The model enabled the exploration and prediction of feasible and
economically attractive ranges of design and operation in terms of
the properties of the coal to be studied. The authors have divided
the gasifier reactor into four zones: viz. preheating and drying,
devolatilisation, gasification and combustion and ashing. It is in the
third zone, that is gasification, where carbon monoxide and
hydrogen are mainly formed by steam‐carbon reduction. The
exothermic combustion reaction provides the energy needed for
endothermic reactions such as gasification and drying. The reactor
was further divided into the adiabatic region and the boundary
layer region. With the assumption that solid and gas temperatures
are the same, and neglecting the heat loss from the adiabatic core to
VOLUME 92, MARCH 2014
Figure 7. (A) Schematic diagram of Uhde gasifiers (Prenflo Steam Generation). http://www.netl.doe.gov/technologies/coalpower/gasification/gasifipedia/
uhde‐prenflo.html (B) Schematic diagram of Uhde gasifiers (Prenflo Direct Quench). http://www.netl.doe.gov/technologies/coalpower/gasification/
gasifipedia/uhde‐prenflo.html

VOLUME 92, MARCH 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 455
Figure 8. Schematic diagram of opposed multi‐burner (OMB) gasifier. Zhou.[51]
the adjacent boundary layer, the energy equation for the adiabatic
core can be written as:
dT
ðH S  H G Þ ¼ r 1 DH 1 þ r 2 DH 2 þ r 3 DH 3 þ r 4 DH 4 :
dz
For the boundary layer, the inclusion of the heat loss through the
wall leads to the following energy equation:
dT
ðH S  H G Þ ¼ r 1 DH 1 þ r 2 DH 2 þ r 3 DH 3 þ r 4 DH 4 þ hAðT  T w Þ:
dz
It was also assumed that the gases leaving the adiabatic core and
the boundary layer are completely mixed at the top of the reactor.
The gasifier performance (Lurgi) was found to be sensitive to the
blast temperature.[58] Below a critical blast temperature (about
232°C) for combustion parameters assumed for the Wyoming coal,
the location of the combustion zone will be very high above the
grate, and carbon loss in the ash will be excessive. The overall
performance of the slagging gasifier is independent of coal
reactivity and can be determined from stoichiometric and
equilibrium calculations. The authors have pointed out that, at
carbon‐to‐oxygen feed ratios below a critical value that is close to
the optimum ratio, it may be necessary to operate with a very thin
coal bed to maintain the hot zone at the tuyer level.
Adanez and Labiano[59] developed a model for an atmospheric
countercurrent moving‐bed coal gasifier with air and steam as the
gasification medium. The model has been developed for adiabatic
reactors, although it could be used in those that have a water jacket
to generate the steam necessary for gasification. The shrinking
456 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
unreacted core model was used with the three resistances (external
and internal diffusion and chemical reaction) in series to describe
the solid–gas reactions. They have divided the gasifier into three
zones: ash zone or gas preheating zone, combustion‐gasification
ð8Þ
zone and pyrolysis‐solid preheating‐drying zone. A parametric
study was performed on the effect of reactivity with steam, CO2,
and O2, of particle size, and of the emissivity of the ash layer on the
longitudinal temperature profiles, the maximum temperature, and
the gas composition. To partially check the validity of the model,
the data predicted were compared with real data on the product gas
composition for various coals, and a good agreement was found in
all the cases. However, authors will agree that their conclusions
ð9Þ
need to be revisited due to the developments in the past 20 years.
Hobbs et al.[60] developed a comprehensive one‐dimensional
model. The model also considered simultaneous drying, devolati-
lisation, oxidation and gasification reactions of char. The heat
transfer coefficient for non‐reacting fixed beds was corrected using
a constant factor to account for the reactions. The bed void fraction
was varied linearly from the top to the bottom of the gasifier. The
predicted pressure profiles compared well with the experimental
data. However, the predicted tar yields were always higher than
the reported experimental values, and showed a significant
dependence on the potential tar forming fraction, which was a
user‐specified parameter. They recommended the use of a more
rigorous submodel, based on the structure of coal, to compute the
tar evolution rates. In addition, the simulations showed very fast
devolatilisation rates which resulted in steep temperature profiles.
Radulovic et al.[61] came up with an improved one‐dimensional
model for countercurrent oxidation and gasification of coal in fixed
or slowly moving beds. This model incorporated an advanced coal
devolatilisation submodel that could predict the evolution rates
and the yields of individual gas species and tar. A split, back‐and‐
forth, shooting method was implemented to satisfy exactly the
VOLUME 92, MARCH 2014
boundary conditions for both the feed coal and the feed gas
streams. An option to switch between the equilibrium and non‐
equilibrium gas phase composition has been added. The model
predictions were compared with the experimental data for two
coals: a Jetson bituminous coal and a Rosebud subbituminous coal.
Nagpal et al.[12] developed a mathematical model for the
simulation of moving bed gasifier with reference to the petcoke
gasification. The feed solid carbon was characterised by employing
a two‐compartment model. The feed solid carbon was divided into
fixed carbon and volatile carbon. The model components taken
into account were fixed and volatile carbon, ash and moisture.
It may be pointed out that the moving bed gasifiers involve
countercurrent flow of solids and gases. The model assumes that
solid and gas compositions and temperatures in the bed are radially
uniform. Axial dispersion was assumed negligible in both phases,
resulting in countercurrent plug flow. The geometry considered
was cylindrical. Particles were assumed to undergo devolatilisa-
tion, combustion and gasification simultaneously. The differential
equations describing this type of process represent a two‐point
boundary value problem. To solve the model equations, the
authors employed the method of orthogonal collocation on finite
elements. For steady‐state simulations, the model equations are
given below.
Material balance for gas and solid material flow rates gives:
dmi X Owing to the complex hydrodynamics and reaction kinetics,
0¼  At nij r i
dz
Energy balance for gas and solid temperatures gives:
X dT g X released species were modelled as the source term in the mass
0¼ mi cpi  At Ri DH i  At Ac kh ðT g  T s Þ  kq ðT g  T w Þ
iðgasÞ
dz
8 9
<X
4sAt T s 3 = dT s
0¼ mc þ  At Ac kh ðT g  T s Þ
:iðsolidÞ i pi ð2=ðe  1ÞÞ; dz
It is assumed that heat released/absorbed in various reactions is
in the gas phase. Heat exchange between gas and solid and
between gas and coolant in the reactor jacket is included in the
above equations. Energy balance for solids includes axial radiative
heat transfer between adjacent solid layers. The study revealed that
under slagging conditions, moving bed gasifiers can operate at very
high petcoke flux in excess of 4000 kg/m2/h, allowing these
gasifiers to be sized comparable to entrained flow gasifiers.
Murgia et al.[62] used MFiX CFD code to develop a comprehen-
sive computational fluid dynamics (CFD) model of an air‐blown
coal fired gasifier. Eulerian–Eulerian Multiphase model has been
used to model the gas and solid phases. The comprehensive 2D CFD
model was able to simulate and evaluate the dynamics of the
gasification process in an updraft airblown coal gasifiers.
Grieco and Baldi[63] described a model to calculate axial profiles
of temperature and composition along an up‐draft coal gasifier.
With respect to other models published in the literature, this model
has two main advantages: pyrolysis was modelled by taking into
account thermal gradients inside the particles and conservation
equations were solved by means of a stable and well conditioned
numeric method. The model was based on two different zones
defined in the gasifier: the lower one, where combustion and
VOLUME 92, MARCH 2014
gasification reactions take place and the upper one, where
pyrolysis reactions take place. Pyrolysis calculations were based
on a distributed parameters model for the single spherical particle.
Coupling between single particle and gasifier models was obtained
by means of an iterative calculation. Pyrolysis kinetics were
provided by a mechanistic pyrolysis model, chemical percolation
devolatilisation (CPD) was tested and other kinetics could also be
easily used. The model was validated by comparison with some
literature data of full scale coal gasifiers. The influence of some
important parameters on the model results was verified.
Sommariva et al.[64] published a comprehensive mathematical
model of a fixed bed gasifier. Both heat and mass transport
resistances and chemical kinetics were accounted for both at the
reactor and the particle scale. The devolatilisation models of solid
fuels have been also validated on the basis of TG experiments. This
model constitutes a prototype towards the characterisation of
complex multiphase and multiscale problem, where solid fuel
devolatilisation together with a detailed gas phase kinetic scheme
interact at the particle and the reactor scale. Some applications of
the model have been extensively discussed both at the level of a
single stage as well as at the scale of the gasifier unit. This work
summarises several facets of their modelling approach with
validations and examples.
Fluidised Bed Gasifier
ð10Þ
modelling of a fluidised‐bed gasifier is a relatively difficult task.
The two‐phase (bubble and emulsion) theory of fluidisation has
been widely used in the modelling of bed hydrodynamics in most of
the coal gasifier models. Based on the experimental data, the
conservation equations. The convective coefficients of mass and
heat transfer and the physical properties of gases were calculated
ð11Þ using diverse correlations taken from the literature.
Caram and Amundson[65] developed a comprehensive model for
the study of fluidised bed gasifier. They have used three fluidised
ð12Þ bed models for the description of hydrodynamics: (a) simple well
mixed reactor, (b) Davidson and Harrison[66] and (c) Kunni and
Levenspiel[67]. In all the cases the solids are assumed to be well
mixed and the bed at uniform temperature. The char was assumed
to be composed of fixed carbon and ash and the gaseous
components used were limited to CO, CO2, H2, H2O, O2 and
CH4. As oxygen and hydrogen were assumed not to coexist, the bed
was divided into a shallow combustion zone where carbon
combustion to CO2 takes place and a gasification zone where no
oxygen would be present. Under these conditions all chemical
changes in the gasification zone were described by three reactions:
(a) steam gasification, (b) carbon hydrogasification and (c) water
gas shift. They ignored the gas flow through the dense phase. No in‐
depth study was made on the reaction rates. They assumed that the
char has already been devolatilised and deactivated with respect to
rapid rate methanation. There was fair agreement between the
predicted and the calculated product gas compositions, except for
the hydrogen mole fraction that was predicted to be systematically
below the experiment levels. This was explained by the fact that
the hydrogen content was not considered in char feed and could be
corrected by this consideration. The carbon conversion for the
range of temperatures considered was found to be far from
equilibrium conditions and strongly dependent on the oxygen feed
and on the bubble‐cloud‐wake characteristics. They have studied
the effect of the size of the cloud wake comparing the Kunii and
Levenspiel model with a simplified version in which all diffusional
resistances are lumped between the bubble and emulsion phases.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 457
Because of the large resistance assumed between the cloud wake
and the emulsion phases, significant differences were found
between the two models. The carbon conversion for the range of
temperatures considered was found to be far from equilibrium
conditions and strongly dependent on the oxygen feed and on the
bubble‐cloud‐wake characteristics.
Sett and Bhattacharya[68] developed a mathematical model for
the behaviour of a fluidised‐bed charcoal gasifier, taking into
account the fluidised‐bed hydrodynamic conditions, the chemical
reaction rates, the mass diffusion rates, and the conservation of
mass and energy. The modified bubble assemblage model
developed by Kato and Wen[69] was assumed for the description
of hydrodynamics. Kinetic data for major combustion and
gasification reactions were taken from the literature for anthracite
char with a necessary temperature correction. The model was
solved numerically using an IBM 3083 mainframe computer.
Results obtained for the simulation showed qualitative resem-
blance to the amount of experimental data generated in their
laboratory.
de souza‐Santos[70,71] developed a comprehensive mathematical
model to use as a tool for engineering design and operation
optimisation. The two‐phase theory of fluidisation has been used in
the modelling of bed hydrodynamics. They incorporated a through
mass balance which considers that both drying and volatilisation
were not instantaneous. A more general treatment for the gas–solid
reactions that included drying and devolatilisation, combined with
a broader range of kinetics have been implemented. The convective
coefficients of mass and heat transfer and the physical properties of
gases were calculated using diverse correlations taken from
literature. Overall agreement between the model predictions and
the experimental data was found to be good. However, the volume
change of the gas due to reactions in a bubbling fluidised‐bed coal
gratifier needed to be included in the model.
Jiang and Morey[72] developed a one‐dimensional, steady state,
numerical model for a fluidised bed biomass gasifier. They have
used the SCM for gasification of wood and rice husk. In this model,
only external mass transfer and intrinsic kinetics around the core
surface were considered, because the severe attrition inside
fluidised bed seldom allows the carbonaceous solid particle to
retain the ash layer formed as the surface reactions proceed. The
gasifier model consists of a fuel pyrolysis model, an oxidation
model, a gasification model and a freeboard model. This model
predicted the fuel feed rate for steady state operation, composition
of the producer gas and fuel energy conversion. The gasifier model
was validated with the experimental results. The effects of major
mechanisms (fuel pyrolysis and the chemical and the physical rate
processes) were assessed in a sensitivity study of the gasification
model. A parametric study was also conducted for the gasifier
model.
Bi and Kojima[73] worked on steady‐state numerical simulation
model, which accounted hydrodynamics, mass transfer, heat
transfer and reactions. This model was proposed for the grid zone
of a jetting fluidised bed coal gasifier with a conical distributor. The
grid zone of the jetting fluidised bed was assumed to be divided into
two parts: the jet region and the annulus region. The gas introduced
from the nozzle with a high velocity forms the jet region; the gas
introduced from the cone shape distributor forms the annulus
region. The jet gas was presumed to be in the plug flow and has a
uniform lateral concentration distribution. The gas concentration
in the annulus was also assumed to be uniformly mixed along the
radial direction. Temperatures of the particle and gas in the jet,
compositions in the jet and the annulus as well as gas velocity,
particle velocity, particle hold‐up in the jet were calculated based
458 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
on this model. The results have shown that the calculated particle
temperature in the jet and compositions in the jet and annulus
coincide with the experimental data of laboratory scale jetting
fluidised bed gasifier.
Yan et al.[74] proposed a one dimensional steady state and
isothermal model incorporating a distinctive characteristic: a net
flow from the emulsion to the bubble phase in the conservation
equations. It is generated by devolatilisation, homogeneous and
heterogeneous reactions. They assumed all gases in both dilute and
emulsion phases were in the plug flow mode. The gas phase was
free of solids, and solids were well mixed within the emulsion
phase. They have added the jetting region (vigorous gas–solid
circulation) in the model which is immediately above the
distributor of the bed. The bed operating temperature was
predicted based on the overall energy balance around the
fluidised‐bed. The predicted fluidisation state, total carbon
conversion and gas composition have been compared favourably
with the available experimental data from an industrial fluidised‐
bed gasifier. They also performed simulation without the net flow
terms and it was observed that the simulations without the net flow
deviate significantly from the experimental results.
Later, Yan et al.[75] incorporated specification of the operating
temperature of the bubbling fluidised‐bed, as an energy balance
was not included in their previous model. Therefore, further
improvements were made to the previous model[74] by incorporat-
ing an energy balance in order to predict the operating temperature
and to use the new model to simulate coal gasifier at both pilot and
industrial scale.
Kim et al.[76] proposed a mathematical model to predict
gasification in an internally circulating fluidised bed reactor with
draught tube. The internally circulating fluidised bed is similar in
many ways to the traditional circulating fluidised bed. The main
differences are in the modes of solid circulation and fluidisation.
This model was based on hydrodynamics, reaction kinetics and the
empirical correlations for pyrolysis. The gasifier was divided into
two parts: (1) draught tube region (well mixed fluidised bed
reactor) and (2) Annulus region (plug flow moving bed reactor).
The model was developed for steady state and isothermal
conditions. The hydrodynamics of the draught tube region
(fluidised bed) were described by the two‐phase theory of
fluidisation. The bubble phase was plug flow without particles
and emulsion phase was completely mixed flow at the incipient
fluidisation conditions. Devolatilisation and drying were assumed
to occur instantaneously and uniformity in the distribution of the
products was assumed between these two regions.
Hamel and Krumm[77] presented a gasification model in a
pressurised fluidised bed gasifier. Their model included bed and
freeboard fluid dynamics, kinetics for drying, devolatilisation and
chemical reactions. The components of the reactor, such as the
cyclone, the gasifier and pipes, were divided in discrete segments
called cells, composed by bubble and emulsion phases. Using this
model, they simulated four reactors, from laboratory scale at
atmospheric pressure, to commercial scale at high pressures,
process brown coal, peat and sawdust with air, air/steam or
oxygen/steam as the gasification agent. The predicted overall
conversion, temperature and concentration of gaseous species
were validated with the published experimental data.
Sofialidis and Faltsi[78] model was based on the assumption of a
static isotropic porous media containing prescribed spherical
volumes to account for the presence of rising bubbles. The biomass
particles were modelled as Lagrangian particles. It has modelled
Drying, devolatilisation, heterogeneous reactions of char, and a
single reaction in the gas phase converting water and methane into
VOLUME 92, MARCH 2014
carbon monoxide and hydrogen. The predicted exhaust gas
concentration of a 3D gasifier was found to be in good agreement
with the measured data for H2, O2, CO2 and H2O but overpredicted
CO concentration.Hamel and Krumm[79] developed a mathemati-
cal model for the simulation of the gasification processes of solid
fuels in atmospheric or pressurised bubbling fluidised beds
incorporating bed and freeboard hydrodynamics, fuel drying and
devolatilisation, and chemical reaction kinetics was presented. The
model has been used to simulate four bubbling fluidised bed
gasifiers, described in literature, of different scales from atmo-
spheric laboratory scale up to pressurised commercial scale,
processing brown coal, peat and sawdust. The gasifiers have been
operated within a wide range of parameters using air, air steam or
oxygen steam as the gasification agent, operating with or without
recirculation of fines at operating pressures up to 2.5 MPa. The
simulation results for overall carbon conversion, temperature and
concentrations of gaseous species agreed sufficiently well with
published experimental data.
The main objectives of Chejne and Hernandez[80] were to
develop a model to account for the evolution of particles
distribution inside the gasifier from an initial Gaussian distribution
of the flow of coal fed into the gasifier. They used non‐linear
conservation equation in compact form to obtain an efficient
numerical solution with fast convergence and less numerical error.
This model could be able to predict temperature, converted fraction
and particle size distribution for the solid phase. For the gaseous
phase, it could predict the profiles of temperature, gas composition,
velocities. Experimental data from the Universidad de Antioquia
and Universidad Nacional‐Medellin have been used to validate the
model. They stated that this model could be used to optimise the
gasification process by varying several parameters, such as excess
air, particle size distribution, coal type and geometry of the reactor.
Ross et al.[81] improved their previous isothermal models of Yan
et al.[74,75] by accounting the non‐isothermal behaviour of the gases
and heat transfer mechanisms in the fluidised‐bed. They incorpo-
rated differential energy conservation equations for the bubble and
emulsion phases, heat transfer by convection and radiation and
amongst gas–gas and gas–solids in the fluidised‐bed. The
predictions indicate that comparisons of overall carbon conver-
sions, operating bed temperatures and individual gas species
predicted from both the non‐isothermal and the isothermal models
with experimental data were favourable. The temperature profiles
of the gas phase predicted from the non‐isothermal model follows
the trend of the bubble temperature due to a large majority of the
gas product flowing through the bed as bubbles. The temperature
of the cold feed gas was predicted to experience a heating up period
at the lower part of the bed and homogeneous combustion in the
gas phase results on a peak temperature in the gas phase. As a
consequence of the higher solid temperature predicted from the
non‐isothermal model than from the iso‐thermal model, the final
product gas molar flow rate and fractional carbon conversion due
to gasification predicted from the non‐isothermal model are all
higher giving better agreeing results compared with experimental
data than those predicted from the isothermal model.
de Souza‐Santos[82] published a review on their comprehensive
simulation program from fluidised bed equipment (CSFB). They
have clearly stated full details of their modelling approach,
progress, short comings and improvements over the years. In the
cases of bubbling fluidised beds, further reliable correlations for
bubble diameters have been applied. The author has improvised
their previous model for the computations of circulation rates.
Accurate models of pyrolysis or devolatilisation have been
implemented. Despite considering the kinetics of all the reactions,
VOLUME 92, MARCH 2014
the new version computes the limits of reaction progress through
the equilibrium relationships. Further, they have included
correlations to account segregation among solid phases. However,
the review was only limited to their work.
Yu et al.[83] presented a 2D Euler–Euler model for the numerical
simulation of coal gasification in a bubbling fluidised bed reactor of
2 m height and 0.22 m diameter. It has accounted for the (a)
pyrolysis of coal into char, tar, and volatiles, heterogeneous char
and (b) homogeneous gas phase reactions including simple
nitrogen chemistry. The char was modelled as a single solid phase
with a constant diameter. The predicted variation in the coal
feeding rate, air supply, steam supply and temperature were in
good agreement with the experimental data.
Sudiro et al.[84] developed a model for dual‐fluidised‐bed
gasification process to test several gasification alternatives in order
to improve the coal gasification process performances. Aspen
simulator has been used to model a combustor and a gasifier,
which have been thermally coupled by the circulation of an inert
solid. And to avoid the use of pure oxygen, to obtain a syngas free of
N2 dilution, and to reduce the overall CO2 emissions. The coal
gasification reactor is modelled, taking into account both the
chemical kinetics and mass transfer between the gas phase and the
char particles.
Deng et al.[85] developed a steady state Euler–Euler model for the
gasification of coal in a lab‐scale pressurised spout‐fluidised bed of
1 m height and 0.1 diameter. The kinetic theory of granular flow for
the particle dynamic was employed. A solid particle of uniform
size, a single‐step pyrolysis without tar and a homogeneous gas
phase chemistry with five reactions and five reactive species have
been considered. Quantitative results for the product gas
compositions are presented for CO, H2, CH4 and CO2 demonstrating
reasonable agreement with measurements. The influence of the
operating conditions bed temperature and pressure on product gas
concentrations are investigated and showed increased gasification
rates with increasing pressure and temperature.
Sudiro et al.[86] extended their previously proposed dual‐bed
gasification scheme for the petcoke gasification. A series sensitivity
analysis has been performed with regard to a conventional gasifier
fed by petcoke. The effects of residence time and oxygen/carbon
mass ratio in the feed have been investigated over various process
variables. Finally, the model has been extended for application to
the dual‐bed process. It was observed that when kinetics were
taken into account, a general decrease in performance was
observed; in particular, a higher heat input was required by the
gasification section.
Gerber et al.[87] simulated the gasification of wood in fluidised
beds. The model was based on an Eulerian multiphase approach.
The kinetic theory of granular material was used to model the
dispersed solid phase. Comprehensive models were incorporated for
pyrolysis, char gasification and homogeneous gas phase reactions.
Tang et al.[88] developed CFD model to simulate Peicheng natural
coke steam gasification in a fluidised bed. All the simulations have
been performed using commercial CFD software, ANSYS FLUENT.
This model consists of probability density function (PDF) method
for turbulent combustion reaction, the kinetics/diffusion limited
model for surface gasification of particles, two‐competing rate
model for devolatilisation, P‐1(simplest case of the more general P‐
N model) model for radiation heat transfer, discrete particle
method (DPM) model for two‐phase flows and std ke turbulence
model. Initially, this model has been verified by comparing with
the experimental data for the general bed case. Then, the
simulation of the improved fluidised bed was carried out to
show its advancement of the product effect and flow pattern.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 459
 Chejne et al.[89] modified their previous model[80] for high
pressure effects. The main objective of this work was to develop a
phenomenological model to predict the gasification behaviour in a
fluidised bed reactor operating at high pressures. A system of
several chemical homogeneous and heterogeneous reactions at an
elevated pressure is included. The drying, devolatisation and
limestone reactions are considered as instantaneous phenomena at
the feeding point. The specific heat, conductivity, viscosity and
binary diffusion coefficients for each component in the gases, have
been calculated as a function of temperature at each point and
corrected for high pressure operation, and the gas mixture
properties are then calculated.
Snider et al.[90] used computational particle fluid dynamics
(CPFD) approach to model the reacting thermal fluid–solid flows.
The CPFD numerical methodology incorporates the multi‐phase‐
particle‐in‐cell (MP‐PIC) method for calculating the dense particle
flows. The MP‐PIC method is a hybrid numerical method, where
the fluid phase is solved for using an Eulerian computational grid
and the solids are modelled using Lagrangian computational
particles. They have further extended the CPFD methodology to
include heat transport and chemistry with solid material pyrolysis.
A three‐dimensional example of a hot fluidised bed coal gasifier
was presented with homogeneous and heterogeneous chemistry.
The inter‐dependencies of fluidisation, thermal, and chemistry
behaviours in this complex three‐dimensional calculation were
presented.
Entrained Flow Gasifier
A number of models have been developed to simulate the entrained
flow coal gasification processes, many of them using simple
reaction kinetics and structural models. The initial entrained flow
gasifier models were based on the assumption of a complete plug
flow reactor (PFR). Therefore, neglected any mixing or turbulence
effects and later on axial mixing in one‐direction was added. Coal
properties were predicted through the use of correlations from a
variety of literature sources and others that were developed from
the experimental data in the literature. The models include single
coal particle gasification, one‐dimensional coal gasification and
CFD coal gasification.
Wen and Chaung[91] adopted a cell in series approach to describe
the mixing in a Texaco pilot plant downflow entrainment gasifier.
Each cell was treated as a perfectly stirred‐tank reactor for the gas,
while the solid phase was in plug flow throughout the whole
reactor volume. The velocity of the solid particles was modelled by
a stokes’s law approximation. The gasifier was fed with coal
liquefaction residues and coal water slurries. They divided the
gasifier into three zones: the pyrolysis and volatile combustion
zone, the gasification and combustion zone and the gasification
zone. In each zone, different controlling mechanisms have been
considered, so that the model could predict the real gasification
process better.
Govind and Shah[92] have refined the above model by including
momentum balances. The reaction kinetics for char gasification
with steam and carbon dioxide were extrapolated from low
pressure data. The shrinking core model was applied to the
modelling of char particle gasification. They performed parametric
studies to provide a better understanding of the sensitivity of
reactor performance to various operating conditions.
Soelberg et al.[93] and Smoot and Brown[94] studied the mixing,
reaction processes and controlling mechanism with in a laboratory‐
scale entrained coal gasifier at atmospheric pressure, through
analysis of experimental data. They observed the existence of three
regions of mixing and the reaction in the gasifier. The coal heat up
460 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
and devolatilisation occur rapidly near the coal inlet region.
Oxygen and volatile yielding out were consumed in this region in a
short time, producing a high gas temperature and high CO2
concentration. Heterogeneous coal char reactions were controlled
in this region through oxidiser diffusion to the char surface.
Outside this region, however, as the temperature declines, the
heterogeneous char‐oxidiser reaction near the particle external
surface becomes more important.
Celik and Chattree[95] used PCGC‐2 (pulverised coal gasification
or combustion) to study gasification of Montana Rosebud‐
subbituminous pulverised coal in an entrained‐flow reactor and
compared the results with experimental data. They found that
the particle residence times to be significantly different from the
commonly calculated gas residence times and suggested that the
use of gas residence time alone as a parameter might lead to
erroneous conclusions regarding char burnout.
Ni and Williams[96] developed a model for shell coal gasification
using simple kinetic parameters for approximately 16 reactions. It
was based on equilibrium, mass and energy balances. Equilibrium
reactions were considered in order to maintain a mass balance.
Vamvuka et al.[97] developed a model to predict the essential
features of gasifier behaviour as a function of steam:coal and
oxygen:coal rations and operating pressure, in terms of parameters
obtained from TG analysis. The two‐phase flow was assumed to be
steady‐state, one dimensional, with plug flow axially and complete
radial mixing. It had incorporated TG analysis data on a
bituminous coal. The model is based on mass and energy
balances, heterogeneous reaction rates and homogeneous gas‐
phase equilibria.
Vamvuka et al.[98] used the above developed model for
parametric studies to provide a better understanding of the reactor
performance in terms of coal conversion, product gas composi-
tions, heating values and temperature profiles throughout the
reactor under various operating conditions. Using the model
predictions the following qualitative understanding was devel-
oped. The critical parameters in gasification are the steam‐to‐coal
and oxygen‐to‐coal feed ratios and the gasifier pressure. It was
observed that the reactor temperature could be controlled by the
concentration of steam in the feed, but its location was strongly
dependent on pressure. Further, it was predicted that the gasifier
performance would be improved with lower steam and oxygen
feed rates and higher system pressure.
Chen et al.[99] developed a comprehensive three‐dimensional
simulation model for two‐stage entrained‐flow gasifier. They
applied an extended coal gas mixture fraction model with the
multi solids progress variables (MSPV) method to simulate the
gasification reaction and reactant mixing process. Four mixture
fractions were employed to separately track the variable coal off‐
gas from the coal devolatilisation, char‐O2, Char‐CO2, and Char‐
H2O reactions. Chen et al. performed a series of numerical
simulations for a 200 tpd two‐stage air blown entrained flow
gasifier developed for an IGCC process under various operation
conditions. To prevent sticky particles from moving toward the
reductor walls, they recommended a small swirl diameter for
the lower combustor burner and an intermediate swirl diameter for
the redactor burner. They reported that the Swirl number was the
most important hydrodynamic scaling law for multi‐stage injecting
swirl flow gasifiers. The predicted gas temperature profile and the
exit gas composition were in general agreement with the measured
data.
Liu et al.[100] developed a model for a pressurised entrained flow
coal gasifier to determine the effect of pressure, reaction kinetics
and char structure on the gasification reactions. It was also one
VOLUME 92, MARCH 2014
dimensional plug‐flow model. The temperature and gas composi-
tions were assumed to be uniformly dispersed across the reactor
(radially) and only change along the reactor (axially). The gas
turbulence was ignored. The model predictions were compared
with the published experimental data.
Chen et al.[101] developed a comprehensive three‐dimensional
model based on the previous numerical methods and the
submodels conventionally used for the pulverised coal combustion
modelling. An extended mixture fraction model with the MSPV
method was applied to simulate the gasification reactions and
reactant mixing process. Four mixture fractions were employed to
separately track the variable coal off‐gas from the coal devolati-
lisation, char‐O2, char‐CO2 and char‐H2O reactions. The influence
of turbulence on the gas properties was taken into account by the
PDF model with a clipped Gaussian distribution function. Various
cases have been simulated for 200 tpd two stage air blown
entrained flow gasifier. The predicted gas temperature profile
and the exit gas composition were in general agreement with the
measurements.
Chen et al.[102] used the above model for parametric studies to
provide a better understanding of two‐stage air blown entrained
flow gasifier. The coal conversion, product gas composition,
heating value and gas temperature profiles throughout the gasifier
were simulated. It was found that the coal devolatilisation and the
char oxidation were responsible for most of the carbon conversion
(up to 80%) in the two‐stage air blown entrained flow gasifier. The
predicted carbon conversion was independent of devolatilisation
rate, sensitive to the chemical kinetics of heterogeneous reactions
on the char surface and less sensitive to a change in coal particle
diameter.
Chen et al.[103] extended their previous model by adding
modelling of turbulent flow of gas and mixing of gaseous reactants,
entrainment of coal particles and their turbulence dispersion, coal
devolatilisation and volatile combustion, heterogeneous char
reactions including combustion and gasification, and convective
and radiative coal/char/ash particle heating/cooling.
Choi et al.[104] developed a CFD based model by dividing the
gasification process into several simplified stages such as slurry
evaporation, coal devolatilisation and two‐phase reactions coupled
with turbulent flow and two‐phase heat transfer. The ke
turbulence model was used for the gas phase flow while the
Random‐Trajectory model was applied to describe the behaviour of
the coal slurry particles. The unreacted‐core shrinking model and
modified Eddy break‐up (EBU) model, were used to simulate the
heterogeneous and homogeneous reactions, respectively. The
predicted carbon conversions have been found to be in agreed
with the measured data.
Liu et al.[105] developed a 3D model to investigate the effect of
mixture fraction fluctuations on the overall gasification character-
istics as a result of the turbulent flow. It was predicted that
turbulent fluctuation has a strong effect on the devolatilisation
process and char‐oxygen reactions, while the char reactions with
H2O and CO2 were not affected by the turbulent fluctuation
apparently.
Bockelie et al.[106] developed a CFD modelling capability for
entrained flow gasifiers that focus on two gasifier configurations:
single‐stage down fired system and two‐stage updraft system with
multiple feed inlets. The model was constructed using GLACIER,
an REI in‐house comprehensive coal combustion and gasification
tool. The basic combustion flow field was established by employing
full equilibrium chemistry. Gas properties were determined
through local mixing calculations and are assumed to fluctuate
randomly according to a statistical PDF which is a characteristic of
VOLUME 92, MARCH 2014
the turbulence. The gas‐phase reactions were assumed to be
limited by the mixing rates for major species as opposed to the
chemical kinetic rates. The gaseous reactions were calculated
assuming local instantaneous equilibrium. The particle reaction
processes include coal devolatilisation, char oxidation, particle
energy, particle liquid vaporisation and gas–particle interchange.
Vicente et al.[107] used Eulerian–Eulerian concept in their
numerical simulation of entrained‐flow gasifier. The model used
includes the coal particle processes, such as drying, volatilisation,
heterogeneous reactions of combustion and gasification, particle
drag and turbulent dispersion, as well as heat‐up. The model has
been applied to the investigation of the gasification of coal in a
commercial entrained flow gasifier. The predictions showed
good agreement for both the main and minor species, and
temperature.
Liu and Kojima[108,109] developed a three dimensional CFD
simulator to study hydrogen‐from‐coal (HYCOL) coal gasification
theoretically. They included the effect of various parameters in the
model such as coal properties, C/H ratio, C/O ratio, ash and volatile
matter content, heating value and particle size. They found that
the heating value had a strong influence on the gasification
characteristics of a HYCOL gasifier, whereas the influence of the
particle size was limited. Further, the same model has been used to
study the effect of the operating conditions. The carbon conversion
increased as the O2/coal ratio increased, whereas the cold gas
efficiency reached a maximum value as the O2/coal ratio increased.
The carbon conversion and cold gas efficiency decreased as the
load ratio of a gasifier increased, but with a limited magnitude. The
predicted results were in good agreement with the experimental
data obtained from 50 ton/day HYCOL pilot‐scale gasifier. The
simulations have shown that the O2 partition between the lower
and upper burners significantly influenced the temperature
distribution in a gasifier. Staged gasification not only enhanced
carbon conversion and cold gas efficiency, but also led to
favourable temperature distribution that suppresses ash slagging
in the gasifier.
Watanabe and Otaka[110] used CFX‐4 and user FORTRAN
interface to generate a three‐dimensional comprehensive coal
gasifier model. The reaction scheme was composed of three
processes: pyrolysis, char gasification and gas phase reactions. CFD
simulations were performed on the CREIPI 2 tons/day research
scale entrained coal gasifier. Influence of the air ration on
gasification performance, temperature distribution and product
gas composition were presented. There was a good comparison
between the predicted and experimental data.
Silaen and Wang[111] carried out a study that focused on the
effect of flow injection directions on the gasification performance
using the same generic two‐stage entrained flow gasifier as studied
by Chen et al.[101] and Bockelie et al.[106] The horizontal injection
direction was compared to downward and upward direction. The
results revealed that the horizontally tangential injection direction
gave the best gasifier performance in the range of design and
operating parameters covered in their work. Changing the
direction of the first‐stage injectors downward resulted in a carbon
fuel conversion reduction, but produced more H2. Changing the
direction of the second‐stage injectors, however, did little to affect
the overall flow patterns due to the smaller‐quantity of coal
injection (25%); therefore the gasifier performance was essentially
insignificantly affected.
Matsushita et al.[112] conducted numerical analysis of an
entrained‐flow gasifier. They reported that the CO mole fraction
in the upper part of the combustor is higher for the smaller gasifier
throat diameter.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 461
 Ajilkumar et al.[113] performed a numerical study of gasification
of Indian coal which has high ash content. They observed that, as
the ash content increases, the heat and mass transfer are affected
and the gasification performance decreases. They suggested that
this is attributed to the lower char reactivity due to thick ash layers
and lower oxygen and other gas diffusion rates. They also found
that increasing the temperatures of inlet air and steam reduces CO,
but increases H2, CO2 and carbon conversion. Steam addition
decreases the temperature but increases H2 production at the
expense of CO.
Dai et al.[114] published their work on the pulverised coal
gasification system model using Gibbs energy minimisation
principle. The main objective was to determine the optimum
operation conditions before the trial run of pilot plant, analyse the
reliability of the pilot‐trial data and design large‐scale pulverised
coal gasification demonstration plant. The model predictions were
in good agreement with the pilot‐trial data under different
operation conditions. They stated that this model could be used
for the design, assessment, and improvement of the entrained‐flow
coal gasification system.
An entrained flow gasifier model was developed by Biagini
et al.[115] by using AspenPlus. It was developed as a multizone
model by modelling each step of the gasification. The kinetics of all
the steps was incorporated and solved the heat balance by relating
the gasification temperature to the operating conditions. It could be
used for the quantification of by‐products and residual char.
The main objective of Wu et al.[43] was to do a systematic
analysis on the turbulent fluctuation effects and the controlling
mechanisms in an entrained flow coal gasifier based on
comprehensive numerical simulation and the turbulence theories.
A presumed probability‐distribution function (PDF) method was
used to describe the turbulent reaction and turbulent mixing
process of the gas phase in the gasifier. A realisable ke model was
used to calculate the turbulence information. Coal slurry particles
were tracked with the Lagrangian method. The particle‐source‐in‐
cell method was used to counter the gas–particle interactions.
One‐quarter of the gasifier was discretised using 16  31  160
body fitted hexahedral mesh elements. All the simulations have
been performed using Fluent CFD software. The length and time
scale distributions of large and small eddies were compared to the
characteristic time of homo and heterogeneous reactions. Turbu-
lent effects on reactions and coal gasification processes in different
regions in an entrained coal gasifier were studied.
Silaen and Wang[116] performed CFD simulations of the oxygen‐
blown coal gasification process inside a generic entrained‐flow
gasifier. The Eulerian–Lagrangian approach was used to solve the
Navier–Stokes equations and the particle dynamics. Seven species
transport equations were solved with three heterogeneous global
reactions and two homogeneous reactions. Finite rates were used
for the heterogeneous solid‐to‐gas reactions. Both finite rate and
eddy‐dissipation combustion models were calculated for each
homogeneous gas‐to‐gas reaction, and the smaller of the two rates
was used. Four different devolatilisation models were employed
and compared. Kobayashi et al.[117] model produces slower
devolatilisation rate than the other models. The constant rate
model predicted the fastest devolatilisation rate. The single rate
model and the chemical percolation model predicted moderate and
consistent devolatilisation rate. A slower devolatilisation rate
predicted a higher exit gas temperature and higher CO and CO2
mass fractions, but a lower H2 and heating value, and hence, a
lower gasification efficiency. The standard ke and the RSM
turbulence models among five (standard ke, kv, RSM, kv SST
and ke RNG) were found to give consistent results. The time scale
462 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
for employing stochastic time tracking of particles also affects the
simulated result.
Silaen and Wang[118] continued their previous studies[111,116] by
investigating the effects of different operation parameters on the
gasification process including coal mixture (dry vs. slurry), oxidant
(oxygen‐blown vs. air‐blown) and different coal distribution
between two stages. One‐stage operation yields higher H2, CO
and CH4 combined than if a two‐stage operation is used, but
with a lower syngas heating value. High heating value (HHV) of
syngas for the one‐stage operation was 7.68 MJ/kg, compared to
8.24 MJ/kg for two‐stage operation with 72–25% fuel distribution
and 9.03 MJ/kg for two‐stage operation with 50–50% fuel
distribution. Carbon conversion efficiency of the air‐blown case
was 77.3%, which was much lower than that of the oxygen‐blown
case (99.4%). The syngas heating value for the air‐blown case was
4.40 MJ/kg, which was almost half of the heating value of the
oxygen‐blown case (8.24 MJ/kg).
Chyou et al.[119] simulated oxygen‐blown coal gasification
process inside a cross‐type two‐stage (E‐Gas like) gasifier using
ANSYS FLUENT software. The objective of this work was to use
CFD simulation to improve understanding of the gasification
processes in the E‐gas like gasifier. In this model, the chemical
reaction time was assumed to be faster than the time scale of the
turbulence eddies. All the species were assumed to mix at the
intermolecular level. Species transport equations were solved
with the eddy‐breakup reaction model. It was predicted that under
the condition of feeding carbon being almost completely converted,
low slurry concentration was preferable over high concentration if
more H2 was wanted with lower syngas temperature; while higher
slurry concentration was preferable for producing more CO with
higher syngas temperature. The case of higher O2/coal ratio
resulted in more combustion and led to lower syngas heating
values and higher temperatures. Meanwhile, lower O2/coal ratio
involved more gasification reactions and results in higher CO
concentration and lower temperature. The single jet injection in
the second stage induced large recirculation regions, which caused
inefficiency and reduced syngas production by trapping a portion
of the flow, reducing the effective flow passage area, speeding up
the main flow and decreasing the residence time of main flow.
An alternate design of using multiple tangential jets injections
in the second stage or enlarging the throat diameter can be
considered.
Slezak et al.[120] developed a CFD model for commercial‐scale
two stage upflow and single‐stage downflow entrained‐flow
gasifiers to study the effects of simulating both the coal particle
density and size variations. The Fluent user‐defined function
(UDF) capability has been used for the feeding of 28 multiple coal
fractions into the gasifier, each at the appropriate mass flow rate
and chemical composition. Results have been obtained at a
typical operating condition using the published devolatilisation
chemistry model and the shrinking core char conversion models.
The model has been used to examine variability in the computed
gas phase average exit conditions (temperature and species volume
fractions), gas phase flow field contours, particle char conversion,
particle residence time and particle–wall impact velocity for the 28
varying particle density and size fractions.
Marin‐Sanchez and Rodrguez‐Toral[121] developed an equation
oriented approach model for the gasification of residual fuel from
petroleum refineries. It was based on chemical equilibrium. It was
developed to find the syngas and slag composition, taking into
account not only the effect of sulphur, but also nitrogen and metals
(Ni, Fe and V) not presented in previous reported models. They
stated that it could be used for other stages; like syngas clean‐up
VOLUME 92, MARCH 2014
and materials selection. And, also for the evaluation of different
scenarios, by selecting a variety of fixed and free variables.
Monaghan and Goniem[122] described the development of a
dynamic reduced order model (ROM) for entrained flow gasifiers.
Their main objective was to reduce the computation requirement
for modelling of a gasifier. Therefore, reactor network models
(RNMs) have been employed. A RNM consisting of three well‐
stirred reactors (WSRs), two PFRs and one integrated PFR–WSR.
The RNM employs five user‐defined, adjustable parameters that
approximate the complex mixing and recirculation processes that
take place inside gasifiers. This greatly reduces computational
expense when compared to more detailed CFD‐based models. This
model has been developed using Aspen custom modeller environ-
ment. Determination of these five RNMs parameters is difficult and
ultimately requires the use of detailed CFD simulation in order to
visualise the fluid flow field. The ROM also employs user‐defined
functions that account for design and operational characteristics
such as flow direction (up or down), feedstock delivery (slurry or
dry), injector configuration (axial or opposed/radial), oxidant (air
or oxygen), number of stages (one or two), wall lining (refractory,
membrane or heated) and syngas cooling (radiant, quench, both or
none). These switches enable simulation of any commercial or
experimental entrained flow gasifier design with one model. This
is the first gasifier model to have such a range of simulation
flexibility. At every point within the RNM, one‐dimensional
conservation equations for mass, energy, momentum and particle
loading are solved. These conservation equations calculate profiles
of mass fractions, temperatures and velocities for gas and solid
species. In addition, mass and energy conservation equations for
slag layers and energy conservation equations for wall layers allow
determination of accurate temperature boundary conditions.
Physical, thermodynamic and transport properties, source terms
and chemical reaction mechanisms are supplied to the conserva-
tion equations by detailed submodels. The ROM employs
submodels for the simulation of multiple feedstock physical and
thermodynamic properties, drying and devolatilisation, homoge-
neous and heterogeneous chemical reactions, viscous fluid–solid
interactions, nitrogenous and sulphurous pollutant formation, slag
behaviour and syngas cooling.
Monaghan and Goniem[123] validated the above model using
experimental data for the following four gasifier designs: (1) 2
metric tonnes‐per‐day (tpd) Mitsubishi Heavy Industries (MHI)
(Minato, Tokyo, Japan) lab‐scale gasifier, (2) 0.1 tpd Common-
wealth Scientific and Industrial Research Organisation of Australia
(CSIRO) lab‐scale gasifier, (3) 1 tpd Brigham Young University
(BYU) lab‐scale gasifier, and (4) 1000 tpd GE pilot‐scale gasifier.
They showed significant success in terms of the predictive
capability, its robustness and required computational resources
as compared to CFD.
From the above literature it is apparent that in the generic
modelling approaches, hydrodynamics have been calculated using
empirical correlations taken from literature, thus the solution of
the momentum equations was avoided. Some of them have been
based on single space dimension and a lot of empirical relations for
hydrodynamics, heat and mass transfer processes can be found.
Therefore, these models were not able to predict either temperature
profiles or the gas concentration inside the bed. On the other hand,
over the last few years researchers started using CFD simulations to
understand velocity and temperature distribution as well as syngas
composition in the gasifier. The following models have been used
in CFD, that is mixture‐fraction/PDF method for turbulent
combustion reaction, the kinetics/diffusion limited model for
surface gasification of particles, two‐competing rates model for
VOLUME 92, MARCH 2014
devolatilisation, simple model for radiation heat transfer,
Eulerian–Eulerian or DPM model for two‐phase flow and standard
or realisable ke equations for the turbulence model. CFD models
are showing some promise, for instance, turbulent fluctuations
affected the volatile and char‐oxygen reaction and significantly
influenced the temperature and gas composition. At the same time,
the multidimensional models for dealing with gas–solid hydrody-
namics, heat transfer and chemical reactions are becoming more
accessible. Experimental data for different types of carbonaceous
feedstocks are still needed to verify and refine the proposed models.
A comprehensive CFD model and the chemical sub‐models need to
be further developed and validated with more detailed experimen-
tal data.
FUTURE PROSPECTS OF PETCOKE GASIFICATION
The reasons for including a gasifier in a refinery stem from a
combination of crude oil quality trends and progressively
increasing severe restrictions on levels of sulphur dioxide
emissions from combustion of heavy fuels. High sulphur (5–7 wt
%) and high metal (300–500 ppm) content coke can no longer be
directly fired in boilers in many parts of the world. Firing in fluid‐
bed combustors often is not permitted because of limited sulphur
recovery and disposal problems with the heavy metals in the spent
bed.[124] The benefits of having a petcoke gasifier in the refinery are
financially as well as environmentally rewarding. Petroleum
refiners could be in a position to supply power in a deregulated
power supply scenario, if they have petcoke gasification plant. In
new grass roots refineries, a large part of the fuel needs can be
satisfied by gasification. The fact that about 15% of the planned
gasification projects[33] rests with petcoke as a feedstock is the
testimony to the growing interest in petcoke gasification. As
refiners are pushed towards producing cleaner, lower sulphur
transportation fuels from poorer quality crudes, gasification of
petcoke could be used to produce hydrogen[125] via synthesis gas
route. In fact, Gray and Tomlinson[126] have reported that the
process offers one of the most promising routes towards the
establishment of a hydrogen based economy. Other products viz.,
Fischer–Tropsch (F‐T) liquids, methanol, ammonia, etc. can also
be produced via synthesis gas route. F‐T liquids are zero sulphur,
paraffinic hydrocarbons that can be classified as ultra‐clean
transportation fuels. Zero sulphur, high cetane F‐T diesel could
be used as a blending stock to assist refiners in meeting ultra low
sulphur diesel specifications.[126] The addition of the gasification
process to the petroleum refinery does not require significant
modification of the refining cycle. Moreover, the electricity
generated can have a significant impact on the refinery product
slate. The emerging trends in petcoke gasification are expected to
give flip to the upgrading projects as regards the oil‐sands. It is
expected that the petcoke gasification will not only have bearing on
the petroleum refining and chemical industries, but also on the
electric utility, paper and pulp, fertiliser and steel industries. In a
nutshell, petcoke gasification is going to be an indispensable
activity in the petroleum refineries in future.
CONCLUSIONS AND SUGGESTIONS FOR FUTURE WORK
(1) The production of petcoke is peaking up at a brisk pace in
the petroleum refineries because of the progressively
heavier nature of crude oil and in turn renewed interest
in the delayed coking process. An additional capacity of
about 70 MMTPA petcoke is anticipated to be added to the
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 463
 existing worldwide capacity (150 MMTPA) by 2015. Hence,
the utilisation of petcoke to value‐added products has
become imperative in the current petroleum refining
scenario.
(2) Gasification of petcoke has emerged as a very attractive
option for the complete utilisation of the petcoke to value‐
added products and is gaining in increasing importance.
Almost 15% of upcoming gasification plants will be using
petcoke as the feed.
(3) Gasification of petcoke offers flexibility in the petroleum
refinery set‐up as it can produce a host of product slates viz.
steam, synthesis gas, hydrogen, electricity, liquid fuels and
chemicals (methanol, ammonia, etc.). The fact that the raw
material (petcoke) for gasification is available right in the
refinery site makes the case of petcoke as a gasification
feedstock more compelling and economical for the overall
refining business.
(4) It is apparent that there is extensive literature on the kinetics
of devolatilisation and gasification. Much of it is directed at
the moving bed and the fluidised bed gasifiers and therefore
is not directly relevant to entrained flow gasifiers that
involve higher temperatures and shorter residence times
than packed and fluidised bed gasifiers. Furthermore, some
of the gasification kinetics at high pressures have been
carried out on char samples generated at atmospheric
pressure or slow heating conditions and that are therefore
not representative of chars present in entrained flow
gasifiers.
(5) The kinetics pertaining to the gasification of petcoke may be
different depending upon coke quality in terms of ash,
volatiles, moisture, heating value and carbon and sulphur
content vis‐à‐vis coal. The future studies need to include a
systematic investigation of kinetics at high temperature and
also high pressure. The studies also need to include the
effect of initial particle size, consumption, morphology, etc.
(6) Entrained flow gasifiers appear to be an attractive choice for
the gasification of petroleum refinery residues. High
temperatures attained in these gasifiers make them suitable
for the gasification of less reactive feedstocks such as the
petcoke and oil sand coke.
(7) Ensuring the steady and smooth operation of an entrained
flow gasifier depends on the steady removal of slag through
a slap tap device. Therefore, a lot of research efforts are
needed to characterise the slag behaviour with respect to
various variables. Further, appropriate hardware develop-
ment is needed for the continuous removal of slag.
(8) Cogasification of petcoke and biomass is expected to make
headway as the latter can negate the negative influence
which the high sulphur, nitrogen and vanadium contents in
the coke can possibly have on the gasification process.
Extensive studies on the blends of these two feedstocks can
bring about some interesting results and a path forward to
an environmentally clean and safer gasification process.
(9) The existing literature on CFD modelling along with
experimental back‐up shows some promise in gaining the
understanding of gasifier performance.
(a) The importance of the sensitivity of the design
parameters such as the throat diameter ratio, the swirl
ratios of burner injections and flow injection directions
on the gasification performance.
(b) The effect of the average particle size.
(c) The influence of higher volatile matter contents.
464 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
(d) The effects of coal mixture (slurry or dry powder),
oxidant (oxygen‐blown or air‐blown), wall cooling and
various coal distributions between the two stages.
(e) The effect of system pressure and temperature.
From the foregoing it is clear that, additional efforts are
needed for extending the CFD simulation for the prediction
hold‐up profiles of particles, particle size distribution, mean
velocity distribution, turbulence characteristics, etc. The
CFD simulation should also include the coupling between
the hydrodynamics and kinetics. The following points
summarise the parameters that have been studied using
CFD simulation.
(10) The characterisation of the flow pattern in the gasification
equipment is important for reliable design and scale‐up. An
extensive experimental program is required for the following:
(a) Bubble size distribution in axial and radial direction for
the case of fluidised beds.
(b) Measurement of drag and lift forces.
(c) Rate of coalescence and break‐up in the fluidised bed
need to be measured under controlled conditions.
(d) Characterisation of turbulence.
(e) Measurement of axial and radial profiles of the solid and
gas phase fractions. It is known that the transverse
distribution of phase hold‐up has a diverse role in
controlling the overall flow pattern.
(11) The design procedures for gasification equipment have been
empirical because of the complexity of hydrodynamics. It
will be useful to make extensive measurements of:
(a) Three‐dimensional mean flow pattern.
(b) Characterisation of turbulence throughout the bed.
(c) Pressure drop characteristics and its relationship with
flow pattern.
(12) The modelling of the process equipment has received
attention of researchers and practitioners using CFD. The
CFD simulation of gasifiers provides several challenges.
First of all, for the validation of CFD simulations, we need
experimental data mentioned in the previous points.
Secondly, the simulations need to include particle–particle
interactions using Discrete Elemental Method (DEM).
Though excellent attempts have been made in the past
(see Mathematical Modelling Section), substantial additional
work is still needed to include:
(a) Wide range of particle size, shape, density, extent of
conversion, etc.
(b) Improved formulation of drag and lift forces at
interfaces. It will be useful to model the particle–fluid
and gas–fluid interactions by large eddy simulations
(LES) and in some cases (few particles) by direct
numerical simulation (DNS). This will enable the basic
understanding of the transfer of momentum, mass, and
heat across the interfaces. As a result, these simulations
will give reliable procedures for the estimation of drag
coefficient, lift coefficient, mass and heat transfer
coefficients across the particle‐fluid and fluid–fluid
interfaces. This micro‐scale modelling needs to be
combined with macro‐scale CFD modelling for getting
overall flow patterns. In this direction, some attempts
have been reported in the published literature.[127–137]
(c) Incorporation of population balance model (PBM)
along with CFD and DEM with good description of
VOLUME 92, MARCH 2014
 break‐up and coalescence phenomena. The future work Tw cooling water temperature (°C)
should also include the characterisation of flow and vi volatile carbon fraction
turbulent structures and their dynamics. This knowl- Y dispersion number
edge is expected to improve our understanding. Some z height above the grate (m)
published work[138–158] is expected to be useful in this DH heat of reaction (MJ/kmol)
direction. s Stefan–Boltzmann constant (kJ/m2/h/K4)
(13) The CFD‐DEM‐PBM should also include the understanding e emissivity of coke
of rate processes described in the section on reaction n stoichiometric coefficient
mechanism, typical product profile and kinetics.
(14) The transition from homogeneous to heterogeneous modes
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Manuscript received October 10, 2012; revised manuscript received

December 31, 2012; accepted for publication January 3, 2013.

468 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, MARCH 2014