International Journal of Emerging Technology and Advanced Engineering

Website: www.ijetae.com (ISSN 2250-2459, ISO 9001:2008 Certified Journal, Volume 3, Issue 12, December 2013)

Gasification of Petcoke and Coal/Biomass Blend: A Review

Morteza Khosravi1, Anil Khadse2
1

Department of Chemical Engineering, Bharati Vidyapeeth Deemed University, COE, Pune

2
Department of Petroleum Engineering, Maharashtra Institute of Technology, Pune

Abstract Gasification of carbonaceous solid fuels to

convert into syngas for application of power, liquid fuels and
chemicals is practiced worldwide. Coal, biomass and
petroleum coke (petcoke) are major feedstock for gasification.
Petcoke is a refinery product having high calorific value and
low reactivity. The concept of blending of coal/biomass to the
low reactive petcoke will make the gasification efficient and
profitable and alleviates the problems associated with petcoke
gasification. Co-gasification of petcoke with coal or biomass is
advantageous in order to obtain the highest value of products
as compared to gasification of petcoke alone. This article
reviews the availability of petcoke as gasification feedstock.
The challenges in petcoke gasification are indentified. The cogasification studies are analyzed to understand the advantages
of blending the petcoke with coal/biomass for gasification
feed. Further, based on gasifier type, co-gasification of
petcoke and coal/biomass is analyzed to understand the most
efficient process.
Keywords
Synthesis gas

Biomass,

Co-gasification,

Coal,

TABLE I
PLANNED PETCOKE BASED GASIFICATION PROJECTS [1]

Plant Name

Technology

Reliance Industries Ltd

ConocoPhillips

Bhatinda IGCC
Marifu IGCC plant
Lima Energy IGCC plant
Edison Mission Energy
Sweeney Gasification
Project
Mississippi Gasification
LLC
Valero Energy Corp.

Texaco
Texaco
ConocoPhillips
GE

Product
Electricity,
Chemicals
Electricity
Electricity
Electricity
Electricity

ConocoPhillips

Electricity

ConocoPhillips

Gaseous fuels

ECUST OMB

Gaseous fuels

Petcock is a product from the Coker unit in refineries

having high calorific value (15000 Btu/lb), high carbon
content; it is cheaper than coal and is abundantly available
[1]. However, it contains high amount of sulfur (5-7 wt %)
and vanadium (up to 500 ppm) which create corrosion and
are not approving environmentally especially for direct
combustion in boilers [2] [1]. Additionally, because of low
volatile matter in petcoke, it is difficult to ignite it [8].
Reactivity is still low in gasification process as compared
to coal and biomass. To increase reactivity of petcoke and
reduce CO2 emissions blending of the coal/biomass is
proposed in number of research studies [1] [4] [11].
Coal is the most abundant fossil fuel on earth, with the
estimates of more than 100 years of supply at the current
utilization pattern [3]. Gasification of coal has been studied
deeply, more than ever for the last decade [4] [5] [6].
Conventionally, use of coal involves emission of
pollutants; however, gasification allows the clean
conversion of coal to energy if coupled with clean coal
technology (CCT) in order to reduce CO2 emissions [7].
Coal will be readily available for blending to enhance
reactivity of petcoke. Another choice is biomass which is
one of the most promising energy resources. It is carbon
neutral and sustainable source of energy [14] [15]. Biomass
is the fourth largest energy resource after coal, oil and
natural gas and estimated as about 10% global primary
energy [16].

Petcoke,

I. INTRODUCTION
The production of petcoke has reached approximately
150 million metric ton per annum (MMTPA) for which the
United States alone is responsible for 47 % of total
production [1]. The petcoke production is anticipated to
rise by more than 70 MMTPA in 2015 [1]. On the other
hand, the demand for the petcoke is projected to reach
about 148 MMTPA till the same year [13]. Hence, there is
a challenge to create a technology that is economical and
environmentally benign to utilize the petcoke. Petcoke can
be directly utilized for power generation by combustion.
Also, petcoke can be converted into syngas by gasification
process. Gasification is the proved technology in order to
convert carbonaceous feed, such as coal, petroleum coke
(petcoke), heavy residual oil, wastes and biomass into
valuable products mainly via syngas (synthesis gas) route
[1][2]. Gasification of petcoke is a favorable technique
since it can capture most of the energy content and is
environmental friendly. Among all worldwide planned
gasification projects almost 15 % are based on petcoke as
their feedstock. Table I shows the planned gasification
projects coming up as petcoke for their main feedstock [1].

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The production of biomass is anticipated to be 134210
J in 2050, whereas its consumption is predicted to be
10411018 J in the same year [16]. The type of biomass
available will depend on location, and the crop pattern in
the region. Co-processing of these fuels- petcoke, coal and
biomass provides advantages in terms of efficiency and
green house gas reduction. Studies on the petcoke
gasification and co-gasification of petcoke and
coal/biomass are analyzed in this article to understand the
effect of blending of the gasification performance.

Addition of catalyst has a significant effect on the

petcoke gasification especially in lowering the gasification
temperature. Wu et al. (2011) studied the catalytic effect of
potassium on steam gasification of petroleum coke in a
fixed bed reactor [1]. They observed that the gasification
was vigorous by addition of the catalyst even at lower
temperature of 750C. Liu et al. (2011) examined the
catalytic effect of coal liquefaction residue (CLR) on
petcoke gasification [1]. They found that by adding 20 %
CLR to the petcoke, the reactivity was tripled at the
temperature of 1050C. This was due to the impact of
AAEM and transition metal which were present in the CLR
samples. In another study by Zhu et al. (2012) the transition
metal catalytic effect was confirmed [1]. In this study, they
examined the catalytic effects of iron species and found
that the gasification temperature was lowered by using iron
catalyst. However, this catalyst caused a decrease in the
gasification rate at high carbon conversion (above 50 %)
because of reduction in surface area and pore volume.
Thats why the loading of the catalyst should be optimized.
Deactivation of catalyst is another issue in case of
catalytic gasification. There is ample number of studies
regarding catalytic coal gasification whereas those of
petcoke are scarce. Jie et al. (2013) studied the effect of
addition of calcium species to promote potassium carbonate
catalytic activity on coal char samples [12]. They
concluded that the calcium species together with K2CO3
showed a synergistic effect for the gasification of char
samples.

18

II. PETCOCKS GASIFICATION

Petcoke introduces certain challenges to the gasification
process as compared to coal due to need of high
temperature gasifier, low reactivity of petcoke, low volatile
and high sulphur content of petcoke [2]. Blending of coal
and/or biomass with petcoke presents significant
advantages to the gasification process. Co-gasification of
petcoke with coal or coal and biomass blends has been
studied in different aspects such as; synergetic effects,
catalysis and parameter studies [2] [7] [8] [9]. Tyler and
Smith (1975) studied reactivity of petcoke to CO 2 at the
temperatures between 754-905C and pressure of 0.1 bars.
They concluded that the gasification rate increased by
reducing particle size of the petcoke [18]. Also they found
that chemical reaction was controlling the rate since pore
diffusion had no effect on the reaction rate at that
temperature.
Wu et al. (2011) investigated the catalysis effect of
potassium on gasification of petcoke in fixed bed gasifier
[19]. It was observed that, in the presence of the catalyst,
petcoke reacted vigorously with steam at even low
temperature of 750 C. Also H2 production increased as a
result of catalyst impact. However at the temperature of
1000C, the reaction was completed faster by addition of
the catalyst [19].

IV. CO-GASIFICATION OF PETCOKE AND BIOMASS BLEND

Biomass was found to have a positive effect on
gasification if blended with petcoke [8]. Vera et al (2013)
studied the co-gasification of biomass and petcoke in a
TGA as well as in a fluidized bed reactor; they found that
higher biomass content leads to shorter gasification time.
Fermoso et al. (2009) performed the co-gasification of
selected binary and ternary mixtures of biomass, coal and
petcoke in a highly pressurized fixed bed gasifier (15 atm).
They concluded that addition of a little amount of biomass
to coal (10 %) raises the cold gas efficiency and carbon
conversion. whereas addition of more than 10 % biomass
into the blend did not have any effect on the gas
composition [10]. In the same study, the influence of
different parameters was examined on the gas production.
It was found that the syngas production is highly altered by
variation of temperature and concentration of oxygen and
steam. But it is very less affected by pressure; there was a
slight decrease in CO and H2 production at higher pressure
[10].

III. CO-GASIFICATION OF PETCOKE AND COAL BLEND

In regards for synergetic effects of co-gasification, there
have been many investigations. Sang et al (2007)
investigated the co-gasification of low calorific value
anthracite coal with petcoke in a thermo gravimetric
analyzer (TGA) and confirmed the synergetic effects [2].
This is due to the catalytic impact of alkali and alkaline
earth metals (AAEM) that is in the coal structure. Liwei et
al (2011) studied the CO2 gasification of several coal and
petcoke samples in a fixed bed laboratory reactor. They
found that the rate constant of petcoke gasification was less
than that of coals verifying the effect of catalyst [7].
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TABLE II
SUMMARY OF GASIFICATION PARAMETERS STUDIED AND FEED

However, pressure can indirectly affect the gasification.

Maryam et al (2013) studied potassium catalyzed CO 2
gasification of petcoke in a TGA; it was found that
gasification rate increased by rising pressure since it
diminishes catalyst volatilization and enlarges the catalyst
distribution [11]. Hence the pressure does not have much
effect on reactivity. In the most recent study, Fermoso et al
(2012) investigated the synergetic effects of both copyrolysis and co-gasification [12]. There were no
interactions among the components of the blend during copyrolysis. On the other hand, gasification step showed
different behaviors as a result of change in the heating rate.
Table II summarizes the gasification parameters
investigations performed on each class of feedstock and
their blends.

Feed
Petcoke

Petcoke
Coal

Petcoke
Biomass
Petcoke
Coal
Biomass

V. GASIFIER REACTORS
A. Entrained flow gasifier
There are principally three gasifier types that can be
used in this regard, viz. entrained flow, fixed bed and
fluidized bed gasifiers [1]. Gasification of petroleum coke
is mostly favored in entrained flow gasifiers, because high
temperature operation can result in complete carbon
conversion [1]. However, high oxygen requirements,
significant outlet gas cooling, expensive materials of
construction and special heat exchangers are the drawbacks
of this type of gasifiers [6].

Gasification Parameters studies

Pressure, gasification rate and reactivity [20]
Gasification time and gas composition [19]
Temperature, conversion and gasification
time and rate [1]
Cold gas efficiency, Carbon conversion
and CO,H2 Production [22]
Calorific value, cold gas efficiency and
gas composition [9]
Temperature and reactivity [2]
Activation energy and reaction time [6]
Temperature, carbon conversion and
reactivity [8]
Product heat value [1]
Carbon conversion, cold gas efficiency
and Syngas production
Gas composition and O/C ratio [4]
Pressure and gas production [11]
Heating rate and gas composition [1]

Shen et al. (2012) performed a study on co-gasification

of petcoke and coal blends in a pilot pressurized entrained
flow gasifier. It was observed that addition of 70% or more
petcoke into a high ash coal can alleviate the slagging
problem of the coal gasification in this type of gasifier [1].
Lee et al. (2010) compared the gasification characteristics
of petcoke and its mixture with coal in a pilot (1T/d)
entrained flow gasifier at the temperature range of 14001600 C [4]. They observed that there was a considerable
increase in H2 and CO in the product gas when petcoke was
gasified with coal. Additionally, higher syngas heating rate
and cold gas efficiency was observed as compared to
gasification of petcoke alone.
Table III represents a summary of all the work done in
the literature regarding co-gasification of petroleum coke
with coal/Biomass in entrained flow gasifiers along with
their most significant results.

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TABLE III
ENTRAINED FLOW GASIFIER STUDIES [1] [9] [10] [22]

Gasifier

Feed

Gasifying
Agents
O2
Steam

Operating
Conditions
Mentioned
only High
temp.

Entrained
flow gasifier

Petcoke
Coal
Biomass

Entrained
flow gasifier

Oil sand
Coke
Coal
(Lignite,
Bituminous)

CO2
Steam

T=
12001400 C
P=750 kPa

Entrained
Flow
Gasifier
(1T/d)

Petcoke
Coal
(Lignite)

O2
Steam

T=
14001600 C

Entrained
Flow
Gasifier
(pilot)

Petcoke
Coal

O2

T=900975C
P=0.1-2.4
MPa

Study Remarks
Using biomass in the system decreases sulphur and ash content of the blend.
Also, decreases the steam demand.
Some types of biomass such as straw contain chlorine that causes corrosion.
Also, some biomass contains potassium or calcium that reduces ash fusion
temperature.
Blending of sub-bituminous coal with coke alleviated the slagging problem
associated with the coal gasification alone.
Blending Coke with Lignite increased carbon conversion and cold gas
efficiency as compared to coke gasification alone.
Steam had a considerable effect on CO and H2 production, but CO2 did not
have much impact on carbon conversion.
Gas composition was (22% H2, 39% CO and 34% CO2) in case of petcoke
gasification alone. But it was (25% H2, 43% CO and 27% CO2) for
gasification of the blend.
Calorific value and cold gas efficiency of blend were higher than those of
petcoke alone.
When more than 70% coke was mixed with the coal, the slagging problem
associated with the coal gasification was alleviated.

B. Fixed bed gasifier

Fixed or moving bed gasifiers are also favored for the
petcoke gasification processes. These gasifiers can operate
at high temperatures i.e. 1500-1800C in case of slagging
types and up to 1300C for dry ash types. Moreover, coals
with high ash contents can be processes by these gasifiers.
However, good bed permeability must be ensured to
avoid pressure drop.
Also the exit temperature from the top of the gasifier is
not high enough to break the tars and oils produced during
pyrolysis and they carried out of the gasifier.

Table IV shows a list of studies done in the literature by

a few researchers in fixed bed gasifier systems. All of the
gasifiers are laboratory reactors in which gasification
characteristics of binary or ternary mixtures of petcoke
with biomass and coal have been investigated. It is evident
that studies at higher temperatures are scarce in this type of
gasifiers.

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TABLE IV
FIXED BED GASIFIER STUDIES [1] [2] [4] [11] [21]

Gasifier

Feed

Gasifying
Agents

Operating
Conditions

Study Remarks

Pressurized
Fixed Bed
Gasifier

Petcoke
Coal
Biomass

O2
Steam

T=9501000 C
P=15 atm

Interactions between the components of the blends modified the gas

production.
Adding small amount of biomass (10 %) in coal and petcoke blends led to
an increase in syngas production, carbon conversion and cold gas
efficiency.

Stainless steel
tubular reactor

O2
Steam

T=8501000C
P=0.5-2
MPa

Rising temperature increased CO and H2.

Rising O/C ratio increased CO and CO2.
Rising steam increased H2 and diminished CO.
Small addition of biomass (10%) enhanced CO, H2 production.

Pressurized
Fixed Bed
gasifier

Petcoke
Coal
(bituminous)
Biomass (OS,
EB, AS)
Petcoke
Coal
Biomass

O2
Steam

T= 1000 C
P=1-1.5
MPa

Gasification of coal alone showed better H2 and syngas production at

atmospheric pressure than those of high pressure.
Gas production was modified in case of co-gasification of the selected
blends and showed synergetic effects.
Addition of a small biomass (up to 10%) resulted in more CO and H 2.

Drop-in-fixedbed Reactor

Petcoke
Coals

CO2
Steam

T=10001600C
P=1 atm

The temperature dependence of reactivity varied with the type of materials

(coals or petcokes)
Gasification reactivity was directly related to the physical structure of
samples. Petcoke was the least reactive because of its compact structure
Either the SCM or VRM models can be suitable for coals but not for
petcoke. A diffusion term associated with the carbon structure may be
needed to model the petcoke gasification behaviour.

Fixed Bed
Gasifier

Petcoke
Coal
Biomass

O2
Steam

T= 1000C

No component interactions during co-pyrolysis.

At high heating rates, individual fuels produce more H2 and there was a
rise in tar production in case of biomass. While at low heating rate,
components of the blends behaved independently and CO and CO2
increased since O2 was more available.

C. Thermogravimetric analyzer
Thermogravimetric analyzers are used as preliminary
study tools for gasification of carbonaceous solids and their
blends. Table 4 represents a few TGA studies on petcoke
and its blends with biomass and coal. TGA analyzers can
operate at high temperature and pressures [6] [8].
Parameters such as reactivity, gasification rate, activation
energy, heating rate and temperature have been studied
with this method as shown in the Table V. Hence, they are
excellent tools for understanding of gasification behaviors

D. Fluidized bed gasifier

Fluidized bed gasifiers have several advantages that
have made them one of the attractive choices for
gasification [17]. Advantages such as uniform temperature
distribution as a result of back mixing, low temperature
operation (below ash fusion) that avoids ash melting, good
sulphur recovery by using sorbents such as limestone and
lower temperature operation that allows using cheaper
equipments [6]. However, when it comes to petcoke
gasification, fluidized bed gasifiers are not normally
favored much due to the high temperature requirements.

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TABLE V
THERMOGRAVIMETRIC STUDIES [1][6] [8] [20]

Gasifier

Feed

Gasifying
Agents

Operating
Conditions
T= 11001400 C
P=1 atm

Study Remarks

TGA
Analyzer

Petcoke
Coal (Anthracite)

TGA

Petcoke
Coal liquefaction
residue (CLR)

CO2

T=9001050C
P=0.1 MPa

The AAEM and iron and sulphur species in the CLR could catalyse the
gasification of the petcoke.
They observed that both catalyst loading and temperature have a significant
effect on the gasification rate.

TGA

Petcoke
Coal (Lignite)

O2
CO2
Steam

T=1000 C

Pyrolysis behaviours in CO2 environment are same for both pure and the
blends up to 700c i.e. no synergy during pyrolysis.
Burning process is somewhat delayed in oxy fuel than in O2 environment.
In O2 rich conditions, characteristic temperatures decrease and rate of
weight loss increased.

TGA

Petcoke

CO2

T= 725825C
P=0.12.1 MPa

High pressure and K loading increased the gasification rate but not
reactivity. High pressure reduces catalyst volatilization hence rises reaction
rate.
K catalyst was less effective when loaded on the char than on the raw
petcoke.

Reactivity of petcoke was found lower than that of anthracite coal.

A synergetic effect was found that caused reducing activation energy and
reaction time during co-gasification.

Nemanova (2013) performed gasification of petcoke and

biomass in a bubbling fluidized bed gasifier, as
summarized in Table VI. They observed that biomass can
increase reactivity of the petcoke as a result of the catalytic

effect of biomass ash in the process [8]. More studies are

required in this matter since coupling biomass and petcoke
is a bit challenging because of their large gasification
temperature difference.

TABLE VI
FLUIDIZED BED GASIFIER STUDIES [8]

Gasifier

Feed

Bubbling
Fluidized
bed reactor

Petcoke
Biomass

Gasifying
Agents
O2
Steam

Operating
Conditions
T=9501200 C
P=0-1 bar

Study Remarks
By rising temperature carbon conversion will increase and tar formation in
the product will decrease.
Alkali and alkaline earth metals increase the petcoke reactivity during cogasification.

These improvements are due to the proven synergetic

effects that are taken place as a result of interactions among
components of the blends. All types of coals and biomass
can be used as a blending feedstock with petcoke. Biomass
that contains potassium and calcium can catalyze the
gasification process. However, there are some drawbacks
associated with blending like biomass that contains
chlorine will cause corrosion in the equipment. Low rank
coals having alkali and alkaline earth metals can catalyze
the petcoke reaction significantly in terms of temperature
reduction and rising gasification rate.

VI. SUMMARY
Due to low reactivity of petcoke, elevated temperature
demand and high sulphur content, the gasification of this
fuel becomes challenging and less efficient. However, high
calorific value and increasing production rate of petcoke
worldwide need an efficient utilization technology like
gasification.
Co-gasification of petcoke along with coal and biomass
is a favorable process since it brings about considerable
improvements in the gasification efficiency.
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[9]

Additionally, use of biomass as an environmentally

neutral source of energy causes reduction of CO2 in the
process.
Gasification parameters such as fuel mixture,
temperature, gasifying agent (C/O ratio), heating rate,
particle size and catalyst loading can dramatically affect the
co-gasification process. The rising temperature causes more
carbon conversion, higher reactivity and more (CO, H 2)
production, low heating rate increases CO and CO2 in the
product gas, higher catalyst loading increases the
conversion and reactivity and higher steam increases H2
and reduces CO production.
Kinetics of co-gasification reactions must be studied for
each system since each type of coal and petcoke and
biomass may contain diverse amounts of ash, volatiles,
moisture and calorific values. Kinetics at higher
temperatures is also scarce in the literature.
Gasifier considered for petcoke gasification is normally
entrained flow or moving beds since they can handle higher
temperature. However, other processes such as fluidized
bed reactors can be employed provided that lower
temperature will be required. Perhaps this can be achieved
by amalgamating co-gasification and catalysis effect.

[10]

[11]

[12]

[13]

[14]
[15]

[16]
[17]

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