Chemical Engineering Science 148 (2016) 14–31

Contents lists available at ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Review

Review of gasification fundamentals and new findings: Reactors,

feedstock, and kinetic studies
Nader Mahinpey n, Arturo Gomez
Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, Calgary, Canada AB T2N 1N4

H I G H L I G H T S

The presence of maximum gasification rate is not related to char surface morphology.

Activation energy estimated at different conversions suggests reaction mechanism.

Separation of pyrolysis and gasification experiments affects the kinetics.

Most important gasification variables are char surface area and alkali content.

The random pore model (RPM) does not represent the real gasification mechanism.

art ic l e i nf o a b s t r a c t

Article history: The purpose of this work is to comprehensively review recent findings on gasification kinetics related to
Received 19 October 2015 the reaction mechanism, the effects of the experimental procedure on the overall reaction, and methods
Received in revised form to evaluate kinetic models.
22 March 2016
Understanding the recent findings in gasification requires the presentation of selected publications
Accepted 24 March 2016
Available online 28 March 2016
that cover several potentially ambiguous concepts. Firstly, conventional reactor definitions are not suf-
ficient given that three reactions (combustion, pyrolysis and gasification) occur in an industrial gasifier.
Keywords: Secondly, variables affecting char reactivity during gasification show that the char surface area is the
Gasification rate most complex variable to analyze. Also, single-step kinetic models provide better descriptions of the
Kinetic model reaction mechanism assuming kinetic control of the overall reaction.
Random pore model
The new findings are related to the gasification reaction mechanism and the interpretation of kinetic
Mass transfer
results: (a) the maximum gasification rate observed is a consequence of the gas concentration devel-
Char surface development
Activation energy
opment upon changing the inert gas for the gasifying agent, and not due to changes in the char surface
during gasification, as proposed by Bhatia and Perlmutter in 1980; (b) increasing the time of holding the
char at the reaction temperature in an inert gas decreases the gasification rate; (c) char micropore surface
area and alkali content are the two most important variables affecting the gasification rate; and,
(d) laboratory studies may not represent the real gasification mechanism under kinetically controlled
conditions due to the presence of mass transfer limitations from interparticle diffusion. Therefore, the
acceptance of intrinsic kinetics reported in the literature should be revalidated.
& 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2. Gasification process and reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1. Gasification applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.2. Gasifying reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3. Gasifier types and stream configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Abbreviations: EFR, entrained flow reactor; FBR, fluidized-bed reactor; ICM, integrated core model or power-law model; LH, Langmuir–Hinshelwood; NDF, normal dis-
tribution function model; SCM, shrinking core model; TGA, thermogravimetric analyzer; RPM, random pore model; VM, volumetric model
n
Corresponding author.
E-mail address: nader.mahinpey@ucalgary.ca (N. Mahinpey).

http://dx.doi.org/10.1016/j.ces.2016.03.037
0009-2509/& 2016 Elsevier Ltd. All rights reserved.
 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31 15

2.3.1. Downdraft and updraft configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

2.3.2. Feedstock distribution into the reactor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3.3. Solid by-product disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3. Variables affecting char reactivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.1. Reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.2. Total pressure and gasifying agent partial pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.3. Pyrolysis and char surface area development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.4. Mineral content and composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4. Kinetic studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.1. CO2 gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.2. Steam gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.3. Assumptions and simplifications within the literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.3.1. Mass transfer limitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.3.2. Char synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
4.3.3. Existence of a maximum reaction rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.4. Chemical reaction kinetic models for char gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.5. Langmuir–Hinshelwood kinetic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5. New findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.1. Real nature of the maximum gasification rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
5.2. Effect of the isothermal pyrolysis in char reactivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
5.3. Most significant variables affecting char reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5.4. Estimation of kinetic parameters independent of the kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
5.5. Reduction of interparticle diffusion in experimental studies. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

1. Introduction IGCC technology involves two major processes: coal gasification

The instability of oil prices has motivated research into the use
of coal and other solid carbonaceous feedstocks as energy sources.
Current coal combustion technology was developed for high-grade
coals (related to high heat content per kg of coal) and is still the
dominant process for thermal power generation. However, its use
has been restricted worldwide due to its higher impact on an-
thropogenic emissions causing global climate change (Matthews
et al., 2009) and environmental concerns, such as high particulate
matter and sulfur dioxide (SO2) pollution. On the other hand, high-
grade coals are not abundant and technologies to obtain ash-free
coal, such as solvent extraction, are necessary (Rivolta Hernandez
et al., 2012). In spite of these concerns, coal accounts for a major
share of the electrical power generated in the western and central
provinces of Canada (Thibault, 2012).
The terminology used for coal has been extended to encompass
all solid carbonaceous feedstock, including non-conventional fuels,
such as petroleum coke (petcoke). There has been an increase in
petcoke production in Alberta, which has been generated as a by-
product of oil sands upgrading. Petcoke may be used as feedstock
to replace natural gas in oil sands extraction and upgrading
(Cousins et al., 2012). Other solid fuels with high ash contents and
similar or lower heat capacities are low-grade fuels, such as bio-
mass. High-quality coals are commonly associated with high car-
bon and low mineral contents (O'Keefe et al., 2013). Low-rank
coals exhibit a broad spectrum of properties directly associated
with less maturity and higher inorganic matter (Bielowicz, 2012;
Cousins et al., 2012; O'Keefe et al., 2013). The coal rank is de-
termined by carbon, moisture, volatile matter content, and ca-
lorific value; and, the general rule is that high-rank coals are
harder materials with less moisture, less volatile matter, and
higher calorific values (Schweinfurth, 2009).
The utilization of low-grade feedstocks is possible using gasi-
fication instead of combustion; however, industrial-scale im-
plementation poses challenges (NETL, 2002). The most successful
demonstration of gasification is the use of the integrated gasifi-
cation combined cycle (IGCC) in power generation. The established
and combined cycle energy generation (Hoffmann and Szklo,
2011); however, its feasibility is significantly affected by the con-
sumption of natural gas.
Coal and natural gas are the two major fossil fuels used in
electricity generation; therefore, an increase in the consumption of
one means a decrease in the consumption of the other, when there
is a surplus of these fuels. In the spring of 2012, natural gas prices
dropped to historically low levels, which led to a significant in-
crease in natural gas-fired generators being used over coal-fired
generators. In early 2013, coal regained market share after natural
gas prices rose, which led natural-gas-fired plants to losing their
competitive advantage (EIA, 2013). Natural gas consumption also
has two peaks each year: the first one is during the winter, when
cold weather increases the demand for natural gas heating; and,
the second peak is during the summer, when hot weather creates
demand for air conditioning (EIA, 2011). Significant uncertainty
remains about the future prices of coal and natural gas. None-
theless, higher prices of coal give natural-gas-fired plants a com-
petitive advantage and vice versa (EIA, 2013).
Gasification is an alternative for generating a clean fuel for
heating purposes. The first industrial application was the pro-
duction of syngas for lighting in 1792; by the late 1920s, there
were more than 1200 operational gasification plants in the United
States (Rezaiyan and Cheremisinoff, 2005). Plasma gasification is
useful in the treatment of municipal solid waste, and it can be
integrated with power generation using a combined cycle (IPGCC)
(Materazzi et al., 2014; Ruj and Ghosh, 2014). It also serves as an
alternative for producing syngas, which is the feedstock for syn-
thetic fuel manufacturing and hydrogen production for refinery
and fuel upgrading (Cousins et al., 2012; Dermot, 2013).
Researchers around the world have been investigating the ki-
netics of gasification in order to increase the gasification rate at
lower temperatures, which is critical to its implementation.
However, experimental results have not shown uniform trends,
and it is difficult to compare kinetic parameters of the same
feedstock produced from different experimental setups. The di-
verse information presented in the literature with inconsistent
16 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
Nomenclature
EA activation energy (kJ mol  1)
f(X) function of the conversion in a general rate law
(dimensionless)
G(X) integrated form of dX/f(X) (dimensionless)
ΔHR, i heat of reaction ‘i’ at reaction conditions (kJ mol  1)
k rate constant (min  1)
ko frequency factor (min  1)
kM rate constant for the particular kinetic model ‘M’
(min  1)
ma mass of ash (g)
mo initial mass of char (g)
mt mass of char at the particular time ‘t’ (g)
n reaction order for the integrate core model
r reaction rate (min  1)
criteria makes it difficult to extrapolate results or correlate in-
dependent studies. In contrast, the scientific community has been
more focused on theoretical research, particularly chemical reac-
tion models with non-unique trends on the estimation of kinetic
parameters (Di Blasi, 2009). These gaps must be addressed to
consistently use the results of laboratory-scale kinetic studies for
the design of industrial gasifiers.
The goal of this review is the clarification of gasification topics
that have been ambiguously mentioned in the literature. This re-
view includes recent findings about gasification experimental
studies and kinetic modeling, which may help researchers to
comprehensively understand gasification with a minimum
amount of assumptions. New concepts clarify why the separation
between gasification and pyrolysis can induce misinterpretations
about the reaction mechanism.
2. Gasification process and reactors
Gasification is the thermochemical conversion of a carbon-
based feedstock into a combustible product gas with the use of a
gasifying agent or agents, such as steam and carbon dioxide (CO2)
(Ma et al., 2011). The main product gases – carbon monoxide (CO)
and hydrogen (H2) – are used to produce heat and electricity or are
converted into liquid hydrocarbons (Bremaud et al., 2005; Coda
et al., 2007). The non-reactive components, called ash, are not
totally inert, because they can change their properties due to solid-
phase changes and partial oxidation or reduction.
Industrial gasification consists of three important processes
(Fermoso et al., 2008; Qian et al., 2013; Zhao et al., 2009):

Pyrolysis reactions: This set of complex reactions involves
heating solid fuel, usually up to 700 °C, to produce char and
release volatiles. Tars may also be produced when volatiles li-
quefy at low temperatures.

Oxidation reactions: Char and volatiles are combusted with
oxygen (O2) to produce the necessary gasifying agents (steam
and CO2) and CO. This reaction is exothermic, and the released
heat is used for reduction reactions.

Reduction reactions (mainly gasification reactions): Char, tar,
and hydrocarbons are gasified with CO2 and steam to produce
synthetic gas (syngas), which is mainly composed of CO, H2, and
CH4. These reactions are endothermic and require the heat
produced from the prior oxidation reactions. Steam promotes
the steam reforming (endothermic) of char and tar, as well as
water–gas shift reactions (exothermic) (Hernandez et al.,
R ideal gas law constant (kJ mol  1 K  1)
S specific surface area (m2 g  1)
t time (min)
T temperature (K)
X conversion (dimensionless)
Greek letters
α intercept of the logarithm of time (min) versus re-
ciprocal of temperature (K  1)
π mathematical constant, approx. 3.14159
Δ gradient of a determined variable
ψ parameter of the random pore model describing char
surface (dimensionless)
2012a). The reduction of water (H2O) in steam gasification is the
most effective way of increasing H2 production (Kim et al.,
2014). CO2 promotes the Boudouard reaction (endothermic) to
produce CO (Hernandez et al., 2012b). CO2 may also be recircu-
lated with O2 within oxy-fuel combustion/gasification (Gil et al.,
2012).
Some limitations of incineration include harmful emissions of
acidic gases and volatile organic compounds, as well as the pro-
duction of toxic wastes, such as dioxins, which contribute to air
pollution (Ma et al. 2011). Compared with incineration and com-
bustion of the solid fuel, the use of syngas produces less solid
waste and emits fewer harmful gases into the environment
(Duchesne et al., 2012). Syngas combustion is an efficient and
clean technology due to low emissions of mono-nitrogen oxides
(NOx) and sulfur oxides (SOx) and has a high rate of energy re-
covery (Hernandez et al., 2012c; Ma et al., 2011). Gasification, on
the other hand, allows the installation of small, low-cost, efficient
reactors to reduce storage and transport costs. It allows the re-
covery of available energy from low-value materials, such as bio-
mass wastes and low-rank coals, reducing disposal costs and en-
vironmental concerns (Hernandez et al., 2012c). Gasification also
provides an alternative for solid animal waste disposal through
manure-fuel gasification (Pian, 2002).
2.1. Gasification applications
There are various advantages to gasifying low-grade fuels over
conventional processes and fossil fuels. Gasification processes can
be applied to convert wastes to valuable forms of energy. These
wastes range from any type of biomass and forestry residues to
petcoke. This ability to convert waste is beneficial for the en-
vironment by preserving lands and providing an economic ad-
vantage in terms of saving storage costs, because gasification uses
straw, agricultural waste, and other products that cannot be eco-
nomically processed using other technologies.
Gasification can be combined with power generation using IGCC
power plants to efficiently and cleanly generate energy. Large
companies, such as Siemens, GE, ConocoPhillips, and Shell, have
built IGCC facilities around the globe (Hoffmann and Szklo, 2011).
IGCC plants are designed with sulfur and CO2 capture systems to
remove most of these harmful constituents from the produced gas.
As shown in Fig. 1, one of the possible gasification routes is power
generation using different feedstocks; however, chemical synthesis
is also achievable with syngas through the use of the Fischer–
Tropsch (FT) process (Bremaud et al., 2005; Coda et al., 2007).
 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
Coal
Lignite
Feedstock
Petcoke
treatment
Biomass
Municipal waste
Gasifier
Recycled CO2 Gasifying
Superheated Steam agent
and
Air reaction
O2 medium
Ash
Fig. 1. Possible plant configurations for different gasification applications.
A general view of this technology implies an understanding of
the following:

Raw materials: gasification is a technology that can be im-
plemented with liquid feedstock; however, this provides no
economic advantage. Solid fuels are the cheapest fuels, but their
transport is expensive; therefore, they can be easily handled if
they are converted into a gas stream.

Gasification process: there are two important elements that
constitute the baseline for all possible configurations:
– Reactor type: the reactor influences the way that the solid is
held in the reaction chamber and the direction of the gas flow
with respect to the feed of the solid. There are multiple chemical
reactions taking place in an industrial gasifier, where the se-
quence of reactions is determined by the reactor configuration.

Heat transfer and heating sources: the main mechanism is ra-
diation, because gasification is a set of endothermic gas–solid
reactions occurring at temperatures above 500 °C. For this rea-
son, indirect heating is not efficient when the size of the reactor
increases. The most common gasifiers are directly heated by
overheated steam and partial combustion of the feedstock.

Syngas quality: tar and other compounds must be removed to
use the syngas (mainly CO and H2). Without syngas cleaning,
there are no environmental advantages to gasification with re-
spect to direct combustion. The main advantage of gasification
is the ability to use smaller equipment since this is a pre-
combustion treatment.

Final application: IGCC technology is the best practical example of
gasification implementation. There are other options, such as che-
mical synthesis, where the most important factor is the CO/H2 ratio.
2.2. Gasifying reactions
The gasifying agent is the gas that is required to perform ga-
sification reactions. This gas reacts with chars, tars, and gases to
produce syngas. Some researchers have referred to air, O2, steam,
and CO2 as gasifying agents. However, only steam and CO2 are
used in gasification reactions; oxygen (O2) is applied in the com-
bustion step to provide the required energy for the endothermic
reactions. As the heat source is an important attribute at industrial
scale, the configuration of reactor becomes an essential factor
when O2 is used as oxidizing agent.
Steam and CO2 have their own advantages in gasification.
Steam promotes the steam reforming (endothermic reaction) of
char and tar, as well as the water–gas shift reaction (exothermic)
(Hernandez et al., 2012a). The reduction of H2O in steam gasifi-
cation is the most effective way of increasing H2 production (Kim
17
Tar
removal IGCC
FT
CO shift
Syngas Synthesis
Sulfur Methanol
removal Synthesis
CO2 Ammonia
removal Production
et al., 2014). CO2 promotes the Boudouard reaction (endothermic)
to produce CO (Hernandez et al., 2012b). CO2 may also be com-
bined with O2 for oxy-fuel combustion prior to the gasification
stage, which is a more efficient process than using air as an oxi-
dant due to reduced nitrogen (N2) dilution (Gil et al., 2012).
The most important reactions considered for kinetic studies,
excluding combustion, are presented in Eqs. (1)–(5) at standard
conditions, indicating which reactions are reversible in the tem-
perature range for which gasification is kinetically controlled. The
Boudouard reaction is the controlling step at low gasification
temperatures during CO2 gasification (lower than 1000 °C)
(Ahmed and Gupta, 2011; Tremel and Spliethoff, 2013).
C þCO2⇆2CO ΔHR1 ¼ 172.5 kJ/mol (1)
C þH2O-H2 þCO ΔHR2 ¼131.3 kJ/mol (2)
COþH2O⇆H2 þ CO2 ΔHR3 ¼  41.2 kJ/mol (3)
C þ2 H2-CH4 ΔHR4 ¼  74.5 kJ/mol (4)
CH4 þH2O⇆COþ 3 H2 ΔHR5 ¼205.8 kJ/mol (5)
Above 700 °C, the Boudouard reaction takes place, i.e., gasifi-
cation in Eq. (1). If the heating rate is higher than 200 °C/min,
there is no weight loss difference during the pyrolysis step, re-
gardless of the sweeping gas used (Silbermann et al., 2013). The
concept of the introduction of an isothermal step to separate
pyrolysis from gasification is not the best solution, as pyrolysis is
much faster than gasification and significantly affects char re-
activity (Tremel and Spliethoff, 2013; Zhu et al., 2008).
CO2 gasification and steam gasification (Eqs. (1) and (2), re-
spectively) are endothermic reactions; when they are combined,
they improve the H2 yield at higher temperatures. The water–gas
shift reaction (Eq. (3)) increases the H2/CO ratio in the final mix-
ture, but does not greatly affect the heating value of the syngas
because H2 and CO combustion heats are almost identical on a
molar basis. The variation of the heat of reaction under various
gasification temperatures is smaller than 5 kJ/mol for all hetero-
geneous reactions; on the other hand, both the homogeneous re-
actions of, water–gas shift (Eq. (3)) and steam methane reforming
(Eq. (5)), change from  41 kJ/mol and 206 kJ/mol at standard
conditions to  33 kJ/mol and 227 kJ/mol at 900 °C, respectively.
Combustion is important; however, under low air intake or pure
O2 for oxy-fuel systems, the gasifier operates under reduction con-
ditions. CO2 is usually produced in situ by partial combustion of the
char, but its gasification efficiency is low when using an entrained
flow reactor (EFR), because residence time in the order of a fraction
of a second is not sufficient to ensure that the Boudouard reaction
takes place. Industrial gasifiers can be ideally considered as three
18 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31

reactors connected in series for combustion, pyrolysis, and gasifica- reactions is part of the model and when kinetics is considered in-
tion; however, the complexity increases when the sequence of these stead of thermodynamic equilibrium.

2.3. Gasifier types and stream configurations

The sequence of reactions, gasifying agents, and stream con-

figurations determine the type of reactor. The main difference
between reactor types is the sequence of reactions for solid and
gas species within the gasifier. For some gasifier types, the steps
for solid feed are drying, pyrolysis, char gasification, and ash
melting. Fig. 2 shows a schematic of the plasma gasification pro-
cess, which has the same elements as conventional gasification
with the addition of continuous melting of the ash (Zhang et al.,
2013).

2.3.1. Downdraft and updraft configuration

When flow configuration is considered, co-current and counter-
current reactors are the equivalents of downdraft and updraft gasi-
fiers, respectively. The sequence of reactions presented in Fig. 2 is one
of many possible configurations, given the position of the feedstock
and gasifying agent inlets. Fig. 3 presents only the main set of gas–
solid chemical reactions that occur in a gasifier according to the
stream configuration: combustion, pyrolysis, and gasification.
Fig. 3 illustrates that the order of the chemical reactions de-
pends on the position of the gas or solid inlet. The position has
important consequences:

Tar formation is reduced using a downdraft reactor, because

combustion follows pyrolysis (Ruiz et al., 2013). This result is
impossible to achieve in an updraft reactor, and tar removal is
required prior to the use of gas products.

Residence time is shorter in the downdraft reactor, because
solids move faster due to gravity and drag force being aligned in
the same direction. Lower carbon conversion is achieved in this
configuration compared with a similar size updraft reactor. This
may be a problem if the solid product is not treated or if the
reactor size is not increased. If the reactor is packed, its con-
version can be the same or higher as that of the updraft reactor;
however, the heating value of the gas products is reduced
compared to other configurations (Kihedu et al., 2014).

Fig. 2. Schematic of plasma gasification process (Reprinted with permission from

2.3.2. Feedstock distribution into the reactor
Zhang et al. (2013)).
Fixed and fluidized bed reactors are the most common reactor

(a) Downdraft Gasifier (b) Updraft Gasifier

Feedstock
Feedstock Gasifying agent + Gas products
+ catalyst ?
catalyst? (1) Pyrolysis (3) Pyrolysis

(2) Combustion

(2) Gasification

(3) Gasification

(1) Combustion
Gas products
Gasifying agent
Ash / slag Ash / slag
Fig. 3. Configuration of gasifiers according to direction of the feed streams: (a) downdraft, (b) updraft. Three sets of chemical reactions occur in a gasifier: (1) combustion,
(2) pyrolysis, and (3) gasification.
 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
Counter-currrent Co-ccurrent
(Downdraaft) (U p
pdraft)
Fig. 4. Fixed bed reactor configurations. (Reprinted with permission from War-
necke (2000)).
types, but other types, such as the EFR, have been widely used for
gasification.
2.3.2.1. Fixed bed reactor. Fixed bed reactors are sometimes called
moving beds, due to the slow motion of the solid with respect to
the gas (Ruiz et al., 2013). Fig. 4 illustrates the two possible con-
figurations for this reactor type: updraft (co-current) and down-
draft (counter-current) reactors (Warnecke, 2000). The particular
type of reactor is determined by the relative position of the intake
for the solid feedstock and gasifying agent.
In the downdraft configuration, there is a lower content of tar
(Ruiz et al., 2013) and a reduction in the heating value of the
product gas (Kihedu et al., 2014) than with the updraft reactor. In
addition, the downdraft configuration is less flexible than updraft
reactors, due to the lack of operational versatility of different
feedstocks (Ruiz et al., 2013).
The most significant advantage of fixed bed reactors is their
high conversion rate for a given volume of reactor; however, they
are usually limited to operations at temperatures below 1000 °C
(Warnecke, 2000).
2.3.2.2. Fluidized bed reactor. Fluidized bed reactors (FBRs) have
been extensively applied in coal gasification for several years
(McKendry, 2002). However, their application is limited, due to
low carbon conversion (Tremel et al., 2013). This reactor type is
continuously fed close to the bottom, and the gasifying agent flows
in continuously from the bottom. The main advantage of FBRs is
better distribution, thereby reducing heat and mass transfer lim-
itations. However, this reactor type is equivalent to a combination
of downdraft and updraft reactors, and the associated problem of
low tar cracking must be considered when using an FBR.
As shown in Fig. 5, there are two common types of FBRs: the
bubbling fluidized bed, and the circulating fluidized bed reactor.
The bubbling type consists of one single reaction chamber and
fluidization control may be a problem. A major disadvantage of
this reactor type is that O2 is trapped in the bubbles, and com-
bustion may take place anywhere in the gasifier, which reduces
the efficiency of the gasifier (Ruiz et al., 2013). In the circulating
design, solids move in a cycle between the reactor vessel and a
cyclone separator, where ash is removed and the remaining char
19
Fig. 5. Fluidized bed reactors used for gasification. (Reprinted with permission
from Warnecke (2000)).
and bed material are returned to the reaction vessel. In contrast to
the bubbling design, the circulating fluidized bed has a very high
gas velocity and can recycle very large amounts of solids; there-
fore, it is capable of handling large feed throughputs (McKendry,
2002). Bubbles do not exist in the circulating design; hence, oxy-
gen cannot be trapped and efficiency does not decrease (Ruiz et al.,
2013).
The operating temperature of FBR gasifiers ranges from 800 to
1000 °C, which prevents the buildup of ash. Therefore, these re-
actors have no limitations in processing feed with high ash content
in this temperature range (Ruiz et al., 2013). The main operational
difficulty is the potential of slagging at low temperatures when
using biomass, which contains ash that melts at temperatures
below 1000 °C (McKendry, 2002; Warnecke, 2000). The main
consideration is the removal of ash from this type of reactor, which
has mostly been ignored in the reported gasification studies with
bubbling FBRs but its effects have been reported in recent studies
about agglomeration and defluidization in FBRs (Datta et al., 2015;
Lu et al.; 2015; Serrano et al., 2015).
2.3.2.3. Entrained flow reactor (EFR). Different authors have con-
sidered the use of EFRs in coal gasification (Collot, 2006; Tremel
et al., 2013). Gasification with an EFR has advantages such as
flexibility, low tar content of the gas product, and high char con-
version. These benefits are the reasons they are the most widely
used type of gasifier; over 75% of the 160 gasification projects in
2005 used EFR (Minchener, 2005). In EFR gasifiers, usually both
the feed powders (less than 75 μm) and gasifying agents enter
from the top of the gasifier. The speed of the gas through the re-
actor is fast enough to entrain all the feed particles.
As the EFR requires a very small particle size, grinding and
achieving the appropriate feed size is critical and can sometimes
be challenging. This reactor normally operates at temperatures
between 1200 °C and 1600 °C and at pressures between 2 and
8 MPa (McKendry, 2002; Minchener, 2005). The carbon conversion
is higher due to the high operating temperature (Ruiz et al., 2013);
however, the gasifier is restricted with respect to the material of
construction. It is vital to implement an effective cooling technique
for the produced syngas for sulfur removal and gas handling im-
provement. A detailed comparison of these three types of gasifiers
is presented elsewhere (McKendry, 2002).
The heat transfer mechanism is usually ignored since the en-
ergy required by the endothermic gasification reactions in all
20 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
gasifiers is directly provided by the reaction gases produced after
partial combustion, which is one reason the heating rate in in-
dustrial gasifiers is much faster than in any laboratory kinetic
study using indirect heating (Tremel et al., 2013).
2.3.3. Solid by-product disposal
There are two operational types of flow gasifiers: slagging and
non-slagging. In slagging types, the operating temperature is
above the melting temperature of the contained ash; and, the
molten ash flows down the wall of the gasifier and forms a solid
slag layer. The slag layer protects the wall material from further
corrosion. In non-slagging types, the operating temperature is
below the melting temperature of the produced ash; therefore, no
solid slag layer is formed. The non-slagging gasifier is more sui-
table for raw materials with lower ash contents (Tremel et al.,
2013).
This classification of flow gasifiers is well known for EFRs. Fixed
and fluidized bed reactors do not operate at high temperatures;
therefore, only non-slagging reactors are considered. An exception
is the plasma gasification reactor that uses fixed or fluidized
plasma gasification (Materazzi et al. 2014; Ruj and Ghosh, 2014).
The plasma gasification reactor is also the best example of a
slagging reactor, because plasma torches can easily melt any bio-
mass or coal slag (Rutberg et al., 2011).
The selection of either a slagging or non-slagging reactor is not
an easy task; however, it is important to distinguish whether there
will be slag formation under specific conditions or not. This aspect
is emphasized in this review, as many authors mention the use of a
catalyst and its regeneration; however, the recovery of a catalyst is
impossible under slagging conditions.
A summary of slagging and non-slagging characteristics is
presented in Table 1. The two most important parameters in the
prediction of slag formation are temperature and mineral com-
position, because they determine the slag flow parameters, such as
viscosity. Slag must remain in the fluid phase throughout the ga-
sifier and be removed continuously at the bottom for proper op-
eration of a slagging reactor. Various sources suggest different slag
viscosities varying from 8–15 Pa.s (Coda et al., 2007) to 1–10 Pa s
(Wang et al., 2005). Low viscosity increases slag velocity; there-
fore, the insulating layer that protects the wall gasifier may be lost
(Schrober et al., 1985). However, the slag viscosity must not exceed
25 Pa s (Duchesne et al., 2012; Kong et al., 2012; Schrober et al.,
1985) for a successful slagging operation.
The composition of the ash greatly influences its melting
temperature. Alkali metals and carbonates, such as sodium and
potassium carbonates (Na2CO3 and K2CO3), are contained in the
Table 1
Summary of slagging and non-slagging characteristics.
Characteristics
Slagging ■ Ash melts at a high temperature
■ Slag protects the gasifier wall from corrosion
■ Operating temperature is greater than ash melting
temperature
■ Slag temperature  1300 to 1500 °C

Slag viscosity ■ Must be less than 25 Pa s
■ If too low, slag velocity increases and insulation may be lost
■ If too high, slag may accumulate on the walls

Ash composition ■ Alkali compounds, like sodium carbonate (Na2CO3), lower
the melting point of silica
■ Lime (CaO) also lowers the ash melting temperature
■ Potassium, particularly potassium oxide (K2O), may be lost
through evaporation at high slagging temperature
Non-slagging ■ Reactor walls are kept free from slag
■ Operating temperature is less than ash melting
temperature
■ Operates at 800–900 °C
ash and react with other ash components, such as silica, to form
low melting point silicates (Kosminski et al., 2006a). The ash
melting behavior may be due to calcium silicate compounds and
additives rich in the silicate mineral, quartz, which lower the
melting temperature (Coda et al., 2007).
Potassium is beneficial in lowering the melting point of silica;
however, it has disadvantages at certain slagging temperatures.
Since alkali compounds have high vapor pressures, they tend to
suffer losses due to sublimation under high gasifier temperatures
(Jones et al., 2006; Nzihou et al., 2013). If the slagging temperature
can be maintained below 1260 °C, potassium oxide (K2O) losses
can be minimized to about 30% with the addition of rice straw ash
(Thy et al., 2005). A gasifying agent has been found to influence
the melting point of Na2CO3. Steam is effective in lowering the
melting temperature of Na2CO3 and, consequently, the formation
temperature of liquid sodium disilicate (Kosminski et al., 2006a,
2006b). In a steam atmosphere, Na2CO3 melts at a lower tem-
perature than its standard temperature of 851 °C (Kosminski et al.,
2006b).
The selection of the right gasifier type is ultimately linked to
the mineral composition of the feedstock; extrapolation from
high-grade coal to low-grade coal or biomass is inconvenient.
Moreover, slagging is usually ignored in kinetic modeling, and the
assumption of constant alkali content may not be accurate at high
temperatures.
3. Variables affecting char reactivity
Temperature and pressure are the controlled operation vari-
ables during gasification and are directly associated with re-
activity. The gasification rate increases at higher temperatures,
regardless of the gasifying agent used (Hernandez et al., 2012a).
During pyrolysis, temperature and heating rates significantly in-
fluence char gasification reactivity more than pressure (Kajitani
et al., 2001). However, increasing these variables decreases the
thermal efficiency of the process and can be economically un-
feasible. Char surface area and total mineral content play im-
portant roles in gasifier selection, since they are not constant
properties. The transformation of the feedstock to char is a critical
factor, with major differences in the reported kinetic results be-
tween laboratory studies and industrial gasifiers.
3.1. Reaction temperature
The choice of the reaction temperature to produce syngas can
be viewed from two perspectives: energy efficiency and fuel uti-
lization. If energy efficiency is the priority, a relatively low tem-
perature and minimum oxygen input should be used (Qin et al.,
2011). However, an emphasis on fuel utilization may require a high
temperature (about 1350 °C) and a suitable excess air ratio (ap-
proximately 0.35) to produce desirable yields of H2 and CO and to
lower soot and tar yields (Qin et al., 2011). The optimal tempera-
ture for gasification for high carbon conversion and gas yield is at
least 900 °C (Zhao et al., 2009). A wide range of temperatures
should be considered in determination of the effect on produced
syngas (as outlined below), the reaction rate, residence time, and
surface area.
At temperatures below 1000 °C, CO yield decreases and H2
yield increases with increasing temperature (Chhiti et al., 2011;
Zhao et al., 2009; Zhao et al. 2012). This occurrence indicates that
water–gas shift (WGS) reactions are more dominant than the
Boudouard reaction (Chhiti et al., 2011). For air-steam gasification,
the H2/CO ratio increases from 0.2 to 1 with increases in tem-
perature, specifically from 750 to 1150 °C (Hernandez et al.,
2012b). Steam enhances WGS and steam-reforming reactions
 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
(Hernandez et al., 2012b; Senapati and Behera, 2012). In contrast,
the CO/CO2 ratio decreases from 1.2 to 1.1 when the temperature
decreases from 1150 °C to 750 °C (Hernandez et al., 2012b). The
balance between CO-producing (Boudouard, steam reforming) and
CO-consuming (WGS) reactions is critical (Hernandez et al.,
2012b).
The reaction rate is slower at low temperatures and takes
longer to achieve high conversion (Tremel et al. 2011). Tar and
volatile compounds that condense at low temperatures may also
be produced, resulting in wall deposits and clogging of pipelines
(Hernandez et al., 2012a; Zhou et al., 2009).
At temperatures above 1000 °C, both CO and H2 yields increase
with increasing temperature (Qin et al., 2011; Tremel et al., 2012;
Yoon et al., 2009), due to enhanced Boudouard, steam reforming
and WGS reactions. CH4 decreases due to its consumption in the
steam-reforming reaction (Qin et al., 2011; Tremel et al., 2012;
Yoon et al., 2009). For air-steam gasification, the H2/CO ratio in-
creases from 0.6 to 1 when the temperature increases from 1000
to 1200 °C and then remains constant up to 1350 °C (Chhiti et al.,
2011). Tars decrease at high temperatures, due to thermal cracking
and steam reforming (Hernandez et al., 2012a). Above 1000 °C,
cold gas efficiency is improved (Zhou et al., 2009), and higher
reaction rates and carbon conversion have been observed (Qian
et al., 2013).
At very high temperatures (1400–1500 °C), both H2 and CO
yields decrease. In this temperature range, the reaction shifts to
the combustion region from the gasification region (Yoon et al.,
2009). Pore size is reduced and particles fuse together due to the
diffusion of atoms to the char surface at very high temperatures,
which is known as sintering (Jones et al., 2006). At very high
temperatures, less syngas is produced as a result of the lower
surface area, even at high residence times (Tremel et al. 2012).
Table 2 presents a summary of the effects of temperature on
syngas production, considering the corresponding reactions and
reactivity.
3.2. Total pressure and gasifying agent partial pressure
Several works have reported changes in the partial pressure of
the gasifying agent by varying the proportion of gasifying agent
with respect to the inert gas used as a carrier gas (Ahmed and
Gupta, 2011; Chhiti et al., 2011; Fermoso et al., 2008, Gil et al.,
Table 2
Summary of the effects of increasing temperature on syngas production and re-
action rate.
Temperature Characteristics
Low (o 1000 °C) – CO decreases, H2 increases, WGS reactions more
dominant than Boudouard reactions
– H2/CO ratio increases for air-steam gasification due to
WGS and steam reforming reactions
– CO/CO2 ratio decreases due to a balance between CO-
producing and CO-consuming reactions
– Slower reaction rate
– Longer residence time to achieve high conversion
– Tars may be produced
High ( 4 1000 °C) – CO and H2 increase due to Boudouard, steam reform-
ing and WGS reactions
– CH4 decreases due to steam reforming
– H2/CO ratio increases for air-steam gasification
– Tars decrease due to thermal cracking and steam
reforming
– Improved cold gas efficiency (CGE)
– Higher reaction rates and carbon conversion
Very high (  1500 °C) – H2 and CO decrease due to sintering
– Reaction shifts to combustion from gasification region
– Particles collapse and shrink
– Lack of surface area
21
2012; Hernandez et al., 2012b; Kajitani et al., 2001; Kim et al.,
2014, Qin et al., 2011; Senapati and Behera, 2012; Tremel and
Spliethoff, 2013; Zhao et al., 2009; Zhao et al., 2012). The effects of
total pressure (Fermoso et al., 2010; Senapati and Behera, 2012;
Tremel and Spliethoff, 2013; Wall et al., 2002) have shown inverse
effects between thermodynamics (maximum conversion) and ki-
netics (Wall et al., 2002). Boudouard and steam gasification reac-
tions have a net increase in gas molecules (Eqs. (1) and (2), re-
spectively), and an increase in total pressure decreases the yield of
gas products. However, an increase in total pressure increases
concentration and, theoretically, should increase gasification rates,
if the final conversion is lower than the equilibrium conversion.
For example, Fermoso et al. (2010) reported that atmospheric ga-
sification produces higher H2 and CO yields with better cold gas
efficiency (CGE) than gasification at 15 atm, indicating that the
syngas yield was limited by the thermodynamic equilibrium.
Table 3 shows a summary of the effects of oxygen partial
pressure and total gasification pressure as presented by Wall et al.
(2002). In general, it is accepted that the effects of pressure are not
significant compared with other variables, such as temperature
and mineral composition; however, other technical problems re-
lated to slag formation are affected by total pressure. Some mi-
neral components that melt at low temperatures are transformed
under high pressure into minerals with high melting points, such
as mullite and sanidine. On the other hand, minerals with sig-
nificant contents of iron reduce the melting point of the ash (Jing
et al., 2013).
3.3. Pyrolysis and char surface area development
The way that the char is usually produced is not considered
during experimental kinetic studies (Ahmed and Gupta, 2011;
Fermoso et al., 2008; Fermoso et al. 2010; Gil et al., 2012; Her-
nandez et al., 2012a; Hernandez et al., 2012b; Kim et al., 2014;
McKendry, 2002; Ochoa et al., 2001; Rutberg et al., 2011). How-
ever, the experimental procedure can affect the char reactivity
during gasification, because the most common gasification pro-
cedures follow the proximate analysis protocol using CO2 or steam
in the last step, instead of air or oxygen as indicated by the ASTM
D5142 standard. There is no consensus and accurate information
about the relationship between pyrolysis and gasification in the
literature; therefore, it is difficult to find a comparison of the
Table 3
Summary of the effects of oxygen partial pressure and total gasification pressure
(Reprinted with permission from Wall et al. (2002)).
Coal chemical/physical Effect of pressure on the process
process
Char combustion Rate ↑ with increasing O2 partial pressure at a
fixed total pressure
Char combustion Rate first ↑ and then ↓ with increasing total
pressure at fixed O2 mole fraction
CO/CO2 ratio Rate ↓ with increasing O2 partial pressure
Char temperature ↑with increasing O2 partial pressure at a fixed
total pressure
Char gasification Rate ↑ with increasing reactant gas pressure
Pyrolysis volatile yield ↓with increasing total pressure
Char reactivity ↓with increasing pyrolysis pressure
Swelling property First ↑ and then ↓ with increasing pyrolysis
pressure
Average char porosity ↑with increasing total pyrolysis pressure
Initial char surface area ↓with increasing total pyrolysis pressure
Heat transfer No effect of total pressure ( o20 atm) on gas
conductivity
Homogeneous reaction Rate ↑ with increasing total pressure
Bulk diffusivity ↓with increasing total pressure
Knudson diffusivity No effect on total pressure
22 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
results of chars produced with different methods as presented by
Silbermann et al. (2013).
Senneca et al. (1997) provided an explanation for the reactivity
differences of char produced with different holding times before
the gasification and proposed a correlation between deactivation
of char surface and its exposure to high temperatures and pres-
sures. The introduction of the thermal annealing concept to ex-
plain changes in the properties of char surfaces was very im-
portant; however, the theory is still incomplete, and no experi-
mental tests to correlate surface area and reactivity reduction have
been performed in further studies about thermal annealing. Other
authors have found that there is no agreement between the ex-
perimental results and the expected activity of a specific char if the
history from coal to char is omitted (Ochoa et al., 2001; Tremel and
Spliethoff, 2013).
If pyrolysis is considered as a part of the whole gasification, as
shown in Fig. 3, its residence time in industrial gasifiers is ne-
cessarily lower than the residence time of gasification, because
pyrolysis is much faster than gasification, irrespective of the ga-
sifying agent. However, when pyrolysis and gasification are per-
formed in different reactors or intentionally separated, the pyr-
olysis residence time is significantly increased, and the produced
char is less reactive (Ochoa et al., 2001; Senneca et al., 1997;
Senneca and Cortese, 2014). Unfortunately, recent works do not
consider this important aspect of gasification, since the total time
that the sample is held at high temperatures is not controlled and
not negligible with respect to the total residence time. Therefore,
kinetic studies do not model the exact industrial scale behavior.
Regardless of the solid feedstock (e.g., coal, biomass, petcoke),
the controlled gasification variable associated with pyrolysis is the
heating rate. As the heating rate increases, the char becomes more
reactive (Di Blasi, 2009; Tremel et al., 2011; Tremel et al. 2012),
which is a well-known limitation of many experimental setups,
such as thermogravimetric analyzers (TGAs). To overcome this
situation, some researchers have used a drop furnace reactor
(Kajitani et al., 2001; Umemoto et al., 2013), an EFR (Tremel et al.,
2011; Tremel et al., 2012) and other reactor setups (Umeki et al.,
2012a) to produce char, subsequently performing char gasification
in batch reactors with TGA or gas product analyses.
An unusual influence of the heating rate on the char surface
was reported by Seo et al. (2011); they showed that the pore
surface area exhibits a maximum for a particular heating rate. This
phenomenon was quantified using the Brunauer–Emmett–Teller
(BET) method at different heating rates; however, it may be a
consequence of heat transfer limitations. Control of the heating
rate is only possible if gasification and pyrolysis occur in different
reactors, which is not an economical option; hence, there is no
reason to reduce the heating rate.
The EFR has been used to produce char and minimize the
changes on the char surface at the laboratory and bench scales
(Kajitani et al., 2006; Tremel and Spliethoff, 2013); however, re-
spective gasification kinetic studies were performed in a different
reactor, i.e., a high-pressure TGA, which is a semi-batch reactor.
Complete kinetic studies of direct gasification without separating
pyrolysis from gasification using an EFR have not been conducted,
as this technology is only operational in power plants fueled by
coal (IGCC). It is now evident that the understanding of the reactor
configuration and the sequence of reactions taking place are cri-
tical to the performance optimization of industrial gasifiers.
3.4. Mineral content and composition
In some circumstances, low-rank coals (rank is associated with
morphological changes from peat to anthracite) are considered the
same as low-grade coals (grade is associated with high ash con-
tent). The reactivity of low-rank coals is generally higher than
high-rank coals with similar ash contents (Di Blasi, 2009; Irfan
et al., 2011); however, reactivity also depends on the amount of
alkali and alkaline earth metals.
Reactivity is reduced when ash-free coal is gasified, which can
be observed by comparing the gasification of the parent coal and
its respective ash-free coal (Kong et al., 2014; Kopyscinski et al.,
2013; Kopyscinski et al., 2014a; Kopyscinski et al., 2014b). Different
authors have presented alternative methods to obtain ash-free
coal (Rivolta Hernandez et al., 2012; Kong et al., 2014); however, it
is important to determine whether it is beneficial to remove the
ash and, in a further step, add an alkali-based catalyst. It is im-
portant to understand the effect of the mineral content as a cat-
alyst and the advantage of low-grade coals in implementing
gasification.
The total mineral content is determined using the ASTM D5142
standard and is equivalent to the ash content determined in the
proximate analysis. This general classification is useful in com-
bustion; however, it is incomplete for gasification, since inorganic
species act as a catalyst for the reaction. High ash content mate-
rials are definitely less desirable for combustion, but their gasifi-
cation reactions are much faster than those feedstocks containing
low ash (Di Blasi, 2009; Irfan et al., 2011); therefore, co-feeding
with low-grade coal or biomass is an alternative to improve the
overall gasification process.
The mineral composition determined by the ash analysis is
usually performed using the ASTM D3682 standard, with ash ob-
tained at 750 °C. This analysis is usually accurate for gasification at
low temperatures; however, potassium can evaporate (Kopyscinski
et al. 2013) or produce low melting point slag in the reaction
temperature range (Tafur-Marinos et al., 2014). Therefore, extra-
polation of results at high temperatures must be analyzed in detail
to avoid overestimation of the active mineral amounts. On the
other hand, the comparison of kinetic parameters at low tem-
peratures is not easy if the reaction is not chemically controlled
and free of thermodynamic limitations; for example, a comparison
of activation energies (EA) between CO2 gasification (Kopyscinski
et al., 2013) and steam gasification (Kopyscinski et al., 2014b) using
the same ash-free coals yields unpredicted results, such as EA of
CO2 o EA of steam.
There are different types of raw materials that can be used as
feedstock for gasification, and their ash analysis is performed as
described for coal. The most common feedstock materials are coal,
biomass, and petcoke, which can be used as raw material for ga-
sification if its low reactivity can be enhanced, thereby reducing
problems related to petcoke's disposal and improving the energy
balance in oil sands upgrading (Duchesne et al., 2012; Lee et al.,
2012). Biomass is beneficial to the environment, because it is CO2
neutral when using straw and other non-edible materials (Chhiti
et al., 2011). Biomass has high reactivity, due to its high contents of
volatiles and alkali compared with coal (Chhiti et al., 2011; Qin
et al., 2011; Roll and Hedden, 1994).
The key factor is the balance between the price of the raw
material and the reactivity of the feedstock. The reactivity is di-
rectly related to the surface area and alkali content Hattingh et al.,
(2011). Alkali and alkaline earth metals undergo different catalytic
activity to promote CO2 gasification (Mitsuoka et al., 2011; Umeki
et al., 2012a) and steam gasification (Coetzee et al., 2013; Sharma
et al., 2008), with an effectiveness order of potassium
(K) 4sodium (Na)4 calcium (Ca) 4 magnesium (Mg) (Huang et al.,
2009). Wang et al. (2009) reported a reduction in CH4 formation
when potassium carbonate (K2CO3) was added to the feedstock.
4. Kinetic studies
This section provides an explanation for the differences be-
tween single-step kinetic models and multi-steps kinetic models,
 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
such as the Langmuir–Hinshelwood models. The reaction me-
chanism for gas–solid reactions indicates that multiple steps
should be considered; however, an exact reaction sequence is
implied or a reaction mechanism is assumed in order to determine
kinetic parameters. Therefore, a single-step kinetic model can be
used if the reaction takes place in the temperature range where
the reaction is chemically controlled (Khalil et al., 2009).
The selection of a particular chemical reaction model depends
on the observed trend of the experimental information since ex-
perimental data are fitted to the selected model by square least
regression. It is important to avoid misinterpretation of the kinetic
results due to competitive steps in catalytic gasification integrated
with the effects of mass and heat transfer. The number of refer-
ences related to CO2 gasification is significantly higher than steam
gasification, due to the technological challenges when dealing
with steam at high temperatures; however, there are no consistent
criteria in the literature, and results for the kinetic parameters vary
among authors (Di Blasi, 2009).
4.1. CO2 gasification
Different studies related to CO2 gasification have been reported
using TGA (Coetzee et al., 2013; Gil et al., 2012; Huang et al., 2009;
Kajitani et al., 2001, 2006; Khalil et al., 2009; Kopyscinski et al.,
2013; Kopyscinski et al., 2014a; Ochoa et al., 2001; Senneca et al.,
1997; Silbermann et al., 2013; Zhu et al., 2008) or other methods to
determine the progress of the reaction, such as gas analysis using
gas chromatography (Ahmed and Gupta., 2011; Hernandez et al.,
2012c; Kajitani et al., 2006; Wang et al., 2009; Zhao et al., 2009,
2012). The main reason for the use of TGA is the continuous
readings and more accurate information when data are recorded
along the reaction progress (Wall et al., 2002). However, one dis-
advantage is that selectivity of competitive reactions cannot be
analyzed; only global kinetics may be estimated. Thus, TGA ex-
perimentation for CO2, with its lower uncertainty, is utilized more
often than other product analysis techniques.
The most common kinetic methods are related to isothermal
batch experiments, since only one experimental run is required to
obtain the rate constant and reaction order for a particular com-
bination of temperature and pressure values (Fogler, 2006). Single-
step models are an extension of coal combustion to gasification
and use the same assumptions about changes on the char surface
area with respect to the grade of conversion (Loewenberg and
Levendis, 1991; Su and Perlmutter., 1985).
There is an overlap between pyrolysis and gasification when
they are sequentially carried out in the same reactor, because the
sample should be heated from ambient conditions to the reaction
temperature; however, this overlap is not significant, and different
experimental methods can be compared by changing the time the
sample is held at the reaction temperature before the inert gas is
replaced by the gasifying agent (Silbermann et al., 2013). Alter-
natively, the experiment can be evaluated in two stages: char
synthesis and char gasification, e.g., producing char in an EFR and
performing kinetic studies with TGA (Kajitani et al., 2006). An
important flaw is that any thermal treatment at high temperature
induces changes in the char surface area (Ochoa et al., 2001;
Senneca et al., 1997; Senneca and Cortese, 2014).
At the temperature range between 650 °C and 750 °C, the
Boudouard reaction is thermodynamically limited (Smith et al.,
2005); and, a comparison of EA at different temperature ranges is
not appropriate.
4.2. Steam gasification
When using the same feedstock, the steam gasification rate is
significantly slower than the combustion rate. Steam is highly
23
corrosive under reaction conditions (Marrone and Hong, 2009;
Tomlinson and Cory, 1989); therefore, it is not possible to perform
steam gasification using the conventional setup used for CO2 ga-
sification. Different authors have presented specific setups, such as
batch reactors (for the analysis of the product gas) (Ahmed and
Gupta, 2011; Nipattummakul et al., 2010; Su and Perlmutter, 1985;
Umeki et al., 2012b), TGA (Coetzee et al., 2013; Fermoso et al.,
2011), and flow reactors (Hernandez et al., 2012b; Detournay et al.,
2011); however, experimental procedures are not standardized,
but are similar to those used for CO2 gasification.
Kinetic modeling of steam gasification is usually reported using
single-step reaction models, similar to those used for CO2 gasifi-
cation (Ren et al., 2013; Silbermann et al., 2013; Zou et al., 2006).
In the literature, intrinsic kinetic studies have revealed that the
particle size and gas flow rate limit the overall reaction rate. In
contrast, the amount of the sample is usually disregarded, and
there are studies that have used samples of less than 15 mg (Fer-
moso et al., 2011; Silbermann et al., 2013; Zou et al., 2006) and
others with samples of more than 100 mg (Ahmed and Gupta,
2011; Nipattummakul et al., 2010; Su and Perlmutter, 1985; Umeki
et al., 2012b), without considering the mass transfer effects.
Steam gasification is much faster than CO2 gasification when
compared under the same experimental conditions (Ahmed and
Gupta, 2011; Marquez-Montesinos et al., 2002; Ren et al., 2013);
and, steam has a lower EA with respect to the CO2 gasifying agent
(Marquez-Montesinos et al., 2002; Ren et al., 2013). Fig. 6 shows
the comparison between CO2 and steam gasification rates of
woodchips char at different gasifying agent partial pressures, de-
monstrating that steam gasification is much faster than CO2
gasification.
4.3. Assumptions and simplifications within the literature
A challenge in gasification research is that many of the as-
sumptions in kinetic modeling have not been clearly presented,
and the understanding of the implicit considerations of every
single model is an onerous task. Three implicit assumptions must
be reviewed in order to improve kinetic analysis: mass transfer
limitation, char synthesis, and existence of a maximum reaction
rate.
4.3.1. Mass transfer limitation
Below 1000 °C, the chemical reaction is the controlling step;
and, it is assumed that mass transfer does not have a significant
effect (Ahmed and Gupta, 2011; Khalil et al., 2009). This assump-
tion must be revised, because it can affect results and is only re-
lated to intrapore diffusion (Fogler, 2006). However, particle size
information has been omitted, and chemical control is considered
for experiments with samples of more than 1 g (Ahmed and
Gupta, 2011; Gil et al., 2012). Interparticle diffusion also plays an
important role that cannot be overlooked (Mandapati et al., 2012)
and is dependent on the internal geometrical configuration of the
reactor.
4.3.2. Char synthesis
The char synthesis methodology is usually ignored or at least
not mentioned in technical reports or related literature. Most of
the kinetic studies performed in an EFR have been designed to
reduce the effect of a low heating rate (Chhiti et al., 2011; Her-
nandez et al., 2012b, 2012c; Kajitani et al., 2006; Senapati and
Behera, 2012; Tremel et al., 2012; Zhao et al., 2009, 2012), with
further analyses at low temperatures using TGA (Kajitani et al.,
2006; Tremel et al., 2012); however, cooling down and reheating
the sample may induce changes on the char surface that cannot be
easily detected.
Comparisons of different experimental works are difficult,
24 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
(a)
1.5 bars
(c)
0.9 bars
Fig. 6. Comparison of CO2 and steam gasification rates at different gasifying agent partial pressures: (a) 1.5 bars, (b) 1.2 bars, (c) 0.9 bars, (d) 0.5 bars (Modified with
permission from Ahmed and Gupta (2011)).
because the way that char is produced is not well explained and
not all elements are considered (Di Blasi, 2009; Ochoa et al., 2001).
The main assumption in most kinetic studies is that the pyrolysis
step yields a unique char (using the same temperature, sweeping
gas, and heating rate). It is also assumed that char surface char-
acteristics are not affected by chemical treatments; however, Kong
et al. (2014) have presented that the coal surface area is affected by
acid treatment, and reactivity of ash-free coal is extremely low and
almost the same regardless of the raw feedstock.
4.3.3. Existence of a maximum reaction rate
For most related studies, it is implicitly accepted that the ex-
istence of a maximum reaction rate at the beginning of the gasi-
fication is a consequence of changes on the char surface. One ex-
ception is Silbermann et al. (2013). This assumption is emphasized
when kinetic models are compared either for CO2 or steam gasi-
fication to fit the experimental results (Ahmed and Gupta, 2011;
Bhatia and Vartak, 1996; Bhatia and Perlmutter, 1980; Fermoso
et al., 2008, 2011; Gil et al., 2012; Kajitani et al., 2001, 2006; Ko-
pyscinski et al., 2013; Mandapati et al., 2012; Malekshahian and
Hill, 2011; Ochoa et al., 2001; Singer and Ghoniem, 2011; Su and
Perlmutter, 1985; Umemoto et al., 2013; Zou et al., 2006).
The char synthesis and maximum reaction rate assumptions
are implicit, and there is a lack of consensus in the scientific
community on the differences of reported kinetic parameters (Di
Blasi, 2009).
4.4. Chemical reaction kinetic models for char gasification
Single-step chemical reaction models are the simplest expres-
sions representing the kinetic behavior of gas–solid reactions if
adsorption and desorption are not considered or if they can be
assumed as not limiting factors for the overall reaction. Single-step
reaction models can be considered a good representation of the
gas–solid reaction if the temperature range of the reaction takes
place below 1000 °C, where the chemical reaction is the
(b)
1.2 bars
(d)
0.5 bars
controlling step and mass transfer does not have a significant ef-
fect (Khalil et al., 2009; Tremel and Spliethoff, 2013). Brief de-
scriptions of the most common single-step chemical reaction ki-
netic models are as follows.

The volumetric model (VM) is the simplest model describing a
gas–solid reaction. It assumes that the reaction takes place
uniformly within the volume of the particle. The volumetric
model is given by:
dX
= k VM (1 − X )
dt (6)

The shrinking core model (SCM) assumes that the reaction oc-
curs only on the surface of a shrinking carbon core. The main
assumption is that the reaction moves from the surface towards
the interior of the particle. The model is described by:
dX
= kSCM (1−X )2/3
dt (7)

The integrated core model (ICM) considers n as a parameter
related to the reaction order. This is also known as the power-
law model, and it is one of the most widely used kinetic models
for gas–solid reactions. The reaction order can be associated
with the stoichiometric coefficient for elementary reactions.
However, for heterogeneous reactions, it can also be interpreted
as a form factor for different particle geometries, if the diffusion
of the gasifying agent controls the overall gasification rate. For
spheres, n ¼2/3; cylinders, n ¼1/2; and flat plates, n ¼0.
 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31 25

dX RPMs. Modeling improvement is commonly attached to an in-

= kIM (1−X )n
dt

VM, SCM and ICM are unable to describe a maximum value of
reaction rate. This disadvantage led different authors to con-
sider the random pore model (RPM) as the best kinetic model
(Ahmed and Gupta, 2011; Bhatia and Perlmutter, 1980; Bhatia
and Vartak, 1996; Fermoso et al., 2008; Fermoso et al., 2011; Gil
et al., 2012; Kajitani et al., 2001; Kajitani et al., 2006; Ko-
pyscinski et al., 2013; Mandapati et al., 2012; Malekshahian and
Hill, 2011; Ochoa et al., 2001; Singer and Ghoniem, 2011; Su and
Perlmutter, 1985; Umemoto et al., 2013). The RPM considers two
competing effects of structural changes during the reaction.
There is a growth of accessible pores in the initial state of
gasification and the coalescence or overlapping of neighboring
pores’ surfaces, which reduces the area available for reaction
(Bhatia and Perlmutter, 1980; Bhatia and Vartak, 1996). The
overall reaction rate is given by:
dX
= kRPM (1 − X ) 1−ψ ln (1−X )
dt
where ψ represents a parameter that describes the internal
structure of the non-converted particle char. The definition of ψ
is given by:
4ΠL 0 (1−ε0 )
ψ=
S02
(8) crease in the number of fitting parameters; however, these im-
provements do not necessarily translate to a better understanding
of the reaction mechanism.

The normal distribution function (NDF) is able to describe the
gasification rate, even if the maximum is at X¼0 (Zou et al.,
2006). Parameters are estimated by using nonlinear regression
instead of a determined conversion assumption, which makes
this model easier to implement. The reaction rate can be
expressed as a function of the intrinsic rate of reaction multi-
plied by a normal probability density:
⎛ − X − X 2⎞
r=
dX
=kNDF⋅exp ⎜⎜
( m)
⎟
dt α ⎟
⎝ ⎠ (13)
where α is a fitting parameter associated with the width ( w ) of the
r vs. X curve. At the reaction rate of r = rm/2, Zou et al. (2006)
consider α = 2w 2.
For all of the aforementioned models, the rate constant (kmodel)
is considered as a parameter at isothermal conditions. This para-
(9) meter is a function of the reaction temperature as stated by the
Arrhenius equation. In addition, the effect of the total pressure is
included in this term, but it can also be an independent function if
the total pressure is not constant along the reaction progress.
4.5. Langmuir–Hinshelwood kinetic models
(10)

where S0 is the pore surface area per volume, L 0 is the pore length
per volume, ε0 is the solid porosity, and ψ is a structural parameter
calculated using a reduced quantity, such as t/t0.5 (Malekshahian
and Hill, 2011):
t 1−ψ ln (1−X ) −1
= use LH models under these conditions, these models may fit the
t0.5 1−ψ ln ( 1−X 0.5 )−1
The method described by Eq. (11) to estimate ψ is not re-
presentative of the reaction mechanism if r versus X is not linear or
shows a maximum. A different approach has been presented
elsewhere (Bhatia and Perlmutter, 1980 and Zou et al., 2006),
where ψ is determined with known experimental information
when a maximum reaction rate ( Xm ) is observed:
ψ =2 ( 1 − ψ ln (1 − Xm ) )
Langmuir–Hinshelwood (LH) kinetic models were developed
based on adsorption/desorption theories, and they are widely
adopted if there is competition between species (Umemoto et al.,
2013). If the reaction temperature increases, the controlling step is
intrapore diffusion. Even when there is no theoretical reason to
(11) experimental results better due to a higher number of regression
parameters. For this reason, some authors consider the extra-
polation of LH kinetic data at higher temperatures, as proposed by
Kajitani et al. (2006) for CO2 coal gasification.
Using a simplified version as presented by Umemoto et al.
(2013), the elementary reactions are:
i1
→
(12) CO2 ← ( CO2 )

When a maximum is not observed, rm is given at Xm ¼0, and i2 (14)

the value of ψ in Eq. (12) is equal to 2, which is the minimum value
of this parameter if a maximum really exists (Bhatia and Perl- i3
mutter, 1980). This result is very important since many authors →
CO ← (CO)
using this model are reporting values of ψ lower than the stated
minimum value (Ahmed and Gupta, 2011; Fermoso et al., 2011; i4 (15)
Kajitani et al., 2006; Kopyscinski et al., 2013; Mandapati et al.,
2012; Umemoto et al., 2013), which contradicts its theoretical i5
C + ( CO2 ) → 2CO (16)
nature. In fact, if the model is considered with a maximum rate, ψ
should be higher than 2 (Gomez and Mahinpey, 2015b; Silber-
mann et al., 2013; Zou et al., 2006). i6
→
The RPM has been widely accepted due to its nonlinear de- H2 O ← ( H2 O)
pendence on char surface, which can predict a maximum reaction
i7 (17)
rate as observed experimentally since Bhatia and Perlmutter pro-
posed it in 1980, with a modification (Bhatia and Vartak, 1996) for
gas–solid reactions. Different modifications of the original model i8
and their applications to fit experimental data have been reported; →
H2 ← ( H2 )
for example, some of the most recent works present extended
i9 (18)
(Kopyscinski et al., 2013) and adaptive (Singer and Ghoniem, 2011)
26 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31

i10
C + H2 O → CO+H2 (19)

Without considering the reduction in char area, LH models for

CO2 gasification and steam gasification are expressed in Eqs. (20)
and (21), respectively:
k11P CO2
r=
1+k12 P CO2 + k13 PCO (20)

k21P H2O
r=
1+k22 P H2O + k23 P H2 (21)

The complete expression, including the change on char surface,

is obtained using two factors: one corresponds to an LH model,
and the other corresponds to the intrinsic kinetic model without
the rate constant. For example, when the RPM is considered, Eq.
(22) shows a simplified model proposed by Kajitani et al. (2006),
obtained by substitution of Eq. (20) with the rate constant from Eq.
(9):
k11P CO2
r= (1 − X ) 1−ψ ln (1−X )
1+k12 P CO2 + k13 PCO (22)

Adsorption and desorption are less significant at high tem-

peratures, since the heat of adsorption is at the same magnitude as
the heat of condensation (Fogler, 2006); therefore, many of the
advantages of using LH models at high temperature lack theore-
tical support. These models present a better fit, because they have
more regression parameters; however, more parameters do not
necessarily offer a better explanation for the gasification Fig. 7. Comparison of three experimental methods on gasification rate and ex-
mechanism. istence of a maximum rate: (a) experimental method, (b) gasification rate vs.
Steam gasification occurs much faster than CO2 gasification, but conversion. Genesee coal gasification at 900 °C. (Adapted with permission from
Gomez et al. (2014)).
there is no comprehensive study in the literature that indicates the
relative conversion rates of both reactions. A few studies have
Coal Gasification: Including initial gas mixing time
compared these two reactions under similar conditions (Ahmed
1.20
and Gupta, 2011; Marquez-Montesinos et al., 2002; Ren et al.,
2013), showing that steam gasification rate is more than twice the
1.00
CO2 gasification rate, as shown in Fig. 6.
0.80
dX/dt

5. New findings 0.60

Authors commonly propose kinetic models with a higher 0.40

number of fitting parameters and a better coefficient of determi-
nation (R2) (Kopyscinski et al., 2013; Singer and Ghoniem, 2011), 0.20
but these models may not be necessarily related to the reaction
mechanism. Kinetic parameters should be theoretically in- 0.00
dependent of the kinetic model; however, there is evidence that 0.0 1.0 2.0 3.0 4.0 5.0 6.0
the EA (activation energy) estimation is correlated with the se- time [min]
lection of a particular kinetic model (Hernandez et al., 2012a, Gil BD Steam Genesee Steam BD CO2 Genesee CO2
et al., 2012; Khalil et al., 2009; Kopyscinski et al. 2013; Malek-
Fig. 8. Conversion rate vs. conversion of two Alberta coals (Boundary Dam “BD” and
shahian and Hill, 2011; Silbermann et al., 2013). This correlation Genesee) using steam and CO2 as gasifying agents at 900 °C. (Adapted with per-
contradicts the Arrhenius equation; therefore, the conventional mission from Gomez and Mahinpey (2015c)).
approach of selecting kinetic models by comparing their R2 is no
longer valid (Gomez and Mahinpey, 2015b). This may be critical if kinetic model?
the estimated EA is different from the real EA. (4) Are all assumptions correct about the existence/absence of
Most of the experimental studies and kinetic models used for mass transfer limitations at low temperatures?
gasification have implicit assumptions. Reported kinetics cannot
be considered as intrinsic kinetics if the following questions are 5.1. Real nature of the maximum gasification rate
not sufficiently answered:
Bhatia and Perlmutter (1980) explained that when the gasifi-
(1) How does the experimental procedure influence the interpretation cation rate is plotted against conversion, the maximum rate ob-
of the reaction mechanism? served is associated with changes in char surface. The maximum
(2) What are the most significant variables affecting the gasifi- gasification rate depends only on the structural parameter ψ as
cation rate, regardless of the feedstock? presented in Eq. (12), and for the same reason, it is independent of
(3) What is the real EA if the result is affected by the selected other variables such as the gasifying agent's partial pressure.

However, there is a deviation of the experimental results with
respect to their theory because the conversion to achieve the
maximum gasification rate is not constant. The maximum rate
occurs at a lower conversion when the reaction temperature (Irfan
et al., 2011; Kopyscinski et al., 2013; Mandapati et al., 2012; Mal-
ekshahian and Hill, 2011; Umeki et al., 2012a) or partial pressure of
the gasifying agent (steam or CO2) (Ahmed and Gupta, 2011)
decreases.
Different studies explaining this situation have been reported
in the literature, e.g., the non-uniform pore distribution condition
(Singer and Ghoniem, 2011). However, the time it takes to observe
a maximum gasification rate is constant, independent of the par-
tial pressure (Ahmed and Gupta, 2011), reaction temperature (Ren
et al., 2013), gasifying agent (Ahmed and Gupta, 2011; Gomez and
Mahinpey, 2015c), steam-to-fuel ratio (Nipattummakul et al.,
2010), and addition of a catalyst (Wang et al., 2009). This is shown
in Fig. 6, where the dotted line confirms that the time to observe a
maximum is constant at different partial pressures as presented by
Ahmed and Gupta (2011).
The observation of a maximum gasification rate is associated
with the experimental procedure, as presented for the first time by
Silbermann et al. (2013) and evaluated by Gomez et al. (2014) for
CO2 gasification in a TGA at atmospheric pressure and coal of
particle size o90 mm. This is shown in Fig. 7, which shows three
experimental methods (Fig. 7A) and compares their gasification
rates as a function of the conversion (Fig. 7B). The initial time of
the gasification for methods 1 and 2 is when the system reaches
the reaction temperature and for method 3 is after 60 min of
reaching the isothermal condition (the time at the reaction tem-
perature in an inert atmosphere is denominated isothermal pyr-
olysis). Method 1 is performed under CO2 atmosphere during
pyrolysis and gasification, showing the highest conversion rate
and without indicating a maximum rate; methods 2 and 3 present
a maximum rate; however, method 3 shows the lowest gasifica-
tion rate.
The existence of a maximum rate has been proven to be asso-
ciated with the dispersion of the gases into the reactor, i.e., when
the inert gas is replaced by the reaction gas (Gomez et al., 2014).
The experimental methods presented by Gomez et al. (2014) were
based on the perturbation of a reaction system considered in
steady state. This experiment revealed that the time to observe a
maximum rate is constant and related to the reactor volume and
volumetric flow rate. Three different tests were designed to prove
this hypothesis for CO2 (Gomez et al., 2014) and steam–coal gasi-
fication (Gomez and Mahinpey, 2015c); in general, it can be
New experimental gasification method
1 1000
0 separate pyrolysis and gasification during experimentation, as
0 5 10
-1
Weight loss [mg]
-2 Non-isothermal pyrolyis
Gas: N₂
-3
-4
-5
-6
-7
-8
Gasification ends when weigh reading is constant
t [min]
Fig. 9. New experimental gasification method considering the starting point of the
gasification when 95% of the inert gases have been replaced by the gasifying agent.
Genesee coal gasification at 900 °C. (Adapted with permission from Gomez and
Mahinpey (2015c)).
N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31 27
Coal gasification rates with new experimental method
1.80
1.60
1.40
1.20
1.00
dX/dt
0.80
0.60
0.40
0.20
0.00
0.0 1.0 2.0 3.0 4.0 5.0 6.0
time [min]
BD Steam Genesee Steam BD CO2 Genesee CO2
Fig. 10. Application of the new experimental method proposed to correct gasifi-
cation rates showing a maximum rate (Fig. 8). Genesee coal gasification at 900 °C.
(Adapted with permission from Gomez and Mahinpey (2015c)).
extended to any gas–solid reaction when changing the reaction
medium. Fig. 8 shows the comparison of two different coals from
Western Canada using CO2 and steam as gasifying agents with a
conventional experimental method (heating with nitrogen and
changing it for the gasifying agent at the reaction temperature),
proving that the time to observe a maximum rate is independent
of the gasifying agent and type of coal and is just related to the
residence time distribution of the gases within the reactor.
Proof that there is no maximum gasification rate associated
with the reaction mechanism is a breakthrough in gasification,
because the amended maximum rate has been considered as an
inherent part of gasification modeling even in the most recent
papers (Rollinson and Karmakar, 2015; Zoulalian et al., 2015). This
finding explains why kinetic studies in continuous reactors do not
show a maximum rate, which can be attributed to the non-se-
paration between pyrolysis and gasification. The most important
result is that kinetics modeling becomes simplified, with classic
kinetic models, such as power-law and first-order kinetic models,
able to be used to fit experimental results more precisely than
complex models (Gomez et al., 2014; Silbermann et al., 2013).
5.2. Effect of the isothermal pyrolysis in char reactivity
Char mesopore surface area decreases during isothermal pyr-
olysis (Gomez et al., 2014), and it decreases more rapidly as the
reaction temperature increases. This decrease in surface area is
associated with the non-existence of a maximum gasification rate,
because isothermal pyrolysis is introduced as an additional step to
900
15 20 25
800 presented in Fig. 7 (Method 3). Ordinarily, the duration of the
time to replace N₂ by isothermal pyrolysis is not considered as a variable affecting char
Temperature [ºC]
700
Steam or CO₂
600
reactivity, which is one of the reasons accounting for the differ-
ences between laboratory studies and industrial gasifiers.
500
Some authors show different reactivities of chars exposed to
Isothermal gasification
400 different isothermal pyrolysis; however, the explanation has been
Gas: Steam or CO₂ 300 linked to thermal annealing (Senneca et al., 1997; Senneca and
200 Cortese, 2014), even if there is no temperature gradient. The char
surface area increases with increasing temperature during non-
100
isothermal pyrolysis (Tremel et al. 2011) and decreases during
0
isothermal pyrolysis (Gomez et al., 2014), which explains the re-
activity differences among chars synthesized from the same raw
material under different experimental conditions.
The experimental procedure proposed by Silbermann et al.
(2013), using CO2 for pyrolysis and gasification, minimizes the
effects of the experimental procedure in gasification kinetics
28 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
studies (Gomez et al., 2014). This particular method has demon-
strated that direct gasification (without switching gases) is suffi-
cient to evaluate CO2 gasification; however, it cannot be extended
to steam gasification because pyrolysis and gasification overlap
between 450 °C and the gasification temperature. A new general
experimental method proposed by Gomez and Mahinpey (2015c),
as presented in Figs. 9 and 10 for CO2 gasification in a TGA at at-
mospheric pressure (coal particle size o90 mm and heating rate
4100 °C/min), indicates higher gasification rates than the con-
ventional method already illustrated in Fig. 8 for the same ex-
perimental setup.
The new method does not consider the time required for the
concentration development of the gasifying agent; therefore, the
char converted between the initial gas change and the maximum
is not considered. For this reason, the gasification rates are higher
and there is no induced maximum conversion rate. This procedure
can be used to correct gasification rate data showing a maximum
conversion rate, provided there are no mass transfer limitations.
5.3. Most significant variables affecting char reactivity
The char pore surface area has been identified as one of the
most important variables affecting gasification rate (Adschiri et al.,
1986; Tremel et al., 2012); however, consistent trends between
reactivity and micropore char surface area at different levels of ash
content have not been reported. Another limitation is the indirect
measurement of char mesopore and micropore surface areas, be-
cause BET and Dubinin–Radushkevich (DR) characterizations are
carried out at  197 °C and 0 °C, respectively. The char micropore
surface area can be associated with its respective parent coal, and
a consistent trend between gasification rate and micropore area
can be observed at different levels of ash content, if the micropore
surface area is based on carbon content instead of coal content
(Gomez and Mahinpey, 2015a).
The alkali content affects the coal reactivity during gasification.
Due to the catalytic nature of alkali and alkaline earth metals, the
gasification rate of different feedstock mixtures cannot be con-
sidered as the linear contribution of the raw species gasification
rates (Gomez and Mahinpey, 2015a), as reported in the literature
(Fermoso et al., 2008; Gil et al., 2012). The catalytic effect of alkali
and alkaline earth metals can be quantified for a broad range of
ash contents and for different feedstocks considering alkali con-
tent equivalents; it was reported that CO2 gasification is catalyzed
above 0.025 equivalent moles of alkali per gram of coal (Gomez
and Mahinpey, 2015a).
Consideration should be given as to whether or not the ash
should be removed and, in a further step, to add a catalyst, as
usually proposed in ash-free coal gasification studies This is an
important factor to be considered since many authors are pro-
moting ash-free gasification, which is equivalent to non-catalytic
gasification. Thus, the co-gasification of low-grade coal and/or
biomass with high-grade coal offers more advantages than ash-
free coal with catalyst.
5.4. Estimation of kinetic parameters independent of the kinetic
model
The question remains as to which kinetic model should be used
to estimate kinetic parameters and to accurately model gasifica-
tion kinetics after presenting new gasification concepts. In kinetic
studies, the experimental information is fitted to a particular
equation by least squares regression. There are different criteria to
determine the best fit, with R2 being the most widely reported.
The conventional approach to estimate EA requires the previous
determination of the rate constant at different reaction tempera-
tures; this process involves the selection of a kinetic model to fit
isothermal experimental data (Fermoso et al., 2008; Gil et al.,
2012; Khalil et al., 2009; Kopyscinski et al., 2013; Kopyscinski et al.,
2014b; Mandapati et al., 2012; Malekshahian and Hill, 2011; Ren
et al., 2013; Silbermann et al., 2013; Zou et al., 2006). However, the
assumption is that the particular kinetic model correctly re-
presents the reaction mechanism. Therefore, it is important to
estimate the kinetic parameters independent of the kinetic model,
but using the same experimental information used in kinetic
modeling. A theoretical deduction to estimate EA (De Micco et al.,
2012; Gomez and Mahinpey, 2015b) and the frequency factor
(Gomez and Mahinpey, 2015b), independent of the kinetic model,
has been reported. The validation of a set of kinetic models can be
done by comparing their kinetic parameters with those calculated
from the free-model approach.
The estimation method of EA proposed by De Micco et al. (2012)
and Gomez and Mahinpey (2015b) are based on cumulative vari-
ables (residence time and conversion) instead of differential vari-
ables (conversion rates); therefore, the solution is robust, and
small variations at the beginning of the experimental procedure do
not affect significantly the estimation of the kinetic parameters. A
simple method to estimate the range of the frequency factor for
gasification has also been presented by Gomez and Mahinpey
(2015b). These are theoretical approaches based on a general rate
law, Eq. (23), and the Arrhenius equation, Eq. (24):
dX
r= =k (T ) f (X )
dt (23)
k = k o e−EA /RT (24)
where r is the reaction rate (expressed as conversion rate); k is the
rate constant; ko and EA are the frequency factor and activation
energy (kinetic parameters of the Arrhenius equation), respec-
tively; and, f(X) is a term related to the reaction mechanism.
Combining (Eqs. (23) and 24), integrating for a particular con-
version and assuming the reaction mechanism does not change
along the conversion range yields Eq. (25) as presented elsewhere
(Gomez and Mahinpey, 2015b):
EA E
ln ⎡⎣ tX (T ) ⎤⎦ = ln [G (X )]−ln ⎡⎣ k o ⎤⎦ +
{ } =α + A
RT RT (25)
where tX (T ) is the residence time to achieve a particular conver-
sion (X) at the reaction temperature (T), and G(X) is the integrated
form of f(X). For gasification, the term ln [G (X )] can be considered
negligible for 0.5 rXr0.8, therefore, the range of frequency factor
values can be estimated. EA can be accurately estimated at any
particular conversion over a broader conversion range
(0.1r Xr0.9).
Eq. 24 indicates that the EA is independent of the reaction
mechanism, since the reaction mechanism affects the intercept
and not the slope. Therefore, a kinetic model does not represent
the real reaction mechanism if the EA estimated in the conven-
tional way (using rate constants) is different than the one esti-
mated independent of the kinetic model. Different gasification
study cases show that VM and ICM fit the experimental results
better with consistent kinetic parameters (Gomez and Mahinpey,
2015b).
These new elements on the fundamentals of chemical reaction
engineering are very important to determine the validity of the
kinetic studies assumptions, e.g., if the RPM really represents the
reaction mechanism of gasification. It is very common to find new
papers where the novelty is the use of nonlinear kinetic models
such as RPM (Kopyscinski et al., 2013; Rollinson and Karmakar,
2015; Singer and Ghoniem, 2011; Zoulalian et al., 2015); however,
deep analysis of the model validity is not presented anywhere.
 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
5.5. Reduction of interparticle diffusion in experimental studies
Many researchers consider the chemical reaction as the con-
trolling step in kinetic studies using a single-step kinetic model at
temperatures lower than 1000 °C (Ahmed and Gupta, 2011; Di Blasi,
2009; Fermoso et al., 2008; Gil et al., 2012; Kopyscinski et al., 2013;
Nipattummakul et al., 2010; Ren et al., 2013; Silbermann et al.,
2013; Tremel et al., 2011). These studies assumed that there are no
associated mass transfer effects, regardless of different sample sizes
used in experiments, i.e., 10 mg or less (Fermoso et al., 2008, 2011;
Gil et al., 2012; Gomez et al., 2014; Huang et al., 2009; Khalil et al.,
2009; Kopyscinski et al., 2013, 2014a; Marquez-Montesinos et al.,
2002; Mitsuoka et al., 2011; Silbermann et al., 2013; Umemoto et al.,
2013), 11–100 mg (Hattingh et al., 2011; Kong et al., 2014; Malek-
shahian and Hill, 2011; Ren et al., 2013; Senneca and Cortese, 2014;
Sharma et al., 2008; Tremel et al., 2011; Umeki et al., 2012a,, 2012b;
Zou et al., 2006), and more than 1 g (Ahmed and Gupta, 2011;
Coetzee et al., 2013; Nipattummakul et al., 2010). Most of these
investigations considered intrinsic kinetics if the particle size was
below 90 mm (Kong et al., 2014; Malekshahian and Hill, 2011;
Sharma et al., 2008; Silbermann et al., 2013); however, even at low
temperatures and small particle sizes, there is interparticle diffusion
(Gomez and Mahinpey, 2015c; Mandapati et al., 2012).
Experiments comparing a commercial TGA with a modified
TGA (home-built quartz crucible and reactor) showed that the
sample amount affected the gasification rate. The results demon-
strated that the most important variable associated with inter-
particle diffusion is the thickness of the feedstock sample (Gomez
and Mahinpey, 2015c; Mandapati et al., 2012), which depends on
the geometry of the crucible or sample holder. Most mathematical
models consider one single particle with a particular shape, and
just negligible diffusion can be if there is a monolayer of solid
particles. This brings another question for future studies as: Are
the effectiveness factor and Thiele module enough to determine if
a system is mass transfer limited (considering that the reaction
mechanism is unknown and there are many particles)?
Steam gasification is faster than CO2 gasification; thus, mass
transfer effects are more significant for steam gasification at the
same temperature since the limiting step corresponds to the
slowest process. The EA estimated from conventional gasification
experiments is significantly smaller than the one calculated if in-
terparticle diffusion is minimized (Gomez and Mahinpey, 2015c).
This situation has been termed falsified kinetics (Fogler, 2006) and
indicates that the assumption of intrinsic kinetics is not possible
for steam gasification using conventional methods, even at low
reaction temperatures. A new proposed experimental procedure,
with negligible interparticle diffusion and without inducing a
maximum gasification rate in CO2 and/or steam gasification, is an
alternative to conduct more precise gasification kinetic studies
(Gomez and Mahinpey, 2015c). This is presented in Fig. 9, where
consideration of the right crucible size and sample amount will
ensure existence of mono- or bi-layer solid particles within the
crucible, thereby minimizing the mass transfer effect.
6. Conclusions
The correct interpretation and modeling of the gasification
mechanism cannot be achieved without incorporating new con-
cepts, experimental techniques, and fundamentals in chemical
reaction engineering:

The maximum gasification rate observed when the conversion
rate is plotted against conversion is not a consequence of
changes in char surface during gasification as proposed by
Bhatia and Perlmutter (1980). It has been demonstrated that the
29
maximum rate is a consequence of different gasifying agent
partial pressures during the stabilization time after the inert gas
is replaced with the reaction gas (Gomez et al., 2014).

An increase in the time that the char is held at the reaction
temperature with an inert gas (isothermal pyrolysis) decreases
the gasification rate (Gomez et al. 2014). This indicates the
importance of the thermal history of the char and explains the
differences between laboratory and industrial gasifier kinetics
(Gomez et al., 2014; Senneca et al., 1997).

The char micropore surface area and the catalyst content are the
two most important variables affecting the gasification rate.
Above 0.025 equivalent moles of alkali per gram of coal, cata-
lytic gasification with CO2 becomes dominant, therefore, a
higher content of alkali reduces the gasification activation
energy.

The comparison of the kinetic parameters obtained from a
particular kinetic model with those calculated from the free-
model approach is a validation tool to determine whether or not
the kinetic model represents the reaction mechanism of a par-
ticular reaction.

The main assumption during kinetic studies at low tempera-
tures (below 1000 °C) is that the chemical reaction is the con-
trolling step (Ahmed and Gupta, 2011; Di Blasi, 2009; Fermoso
et al., 2008; Gil et al., 2012; Kopyscinski et al., 2013; Ni-
pattummakul et al., 2010; Ren et al., 2013; Silbermann et al.,
2013, Tremel et al., 2011); however, experiments with small
particle size (90 mm) and small sample amounts (10 mg) ex-
hibited interparticle diffusion limitations due to the thickness of
the sample (Gomez and Mahinpey, 2015c; Mandapati et al.,
2012). It has been proven that the reported EA of steam
gasification is usually underestimated (Gomez and Mahinpey,
2015c), as a result of mass transfer limitations, specifically
interparticle diffusion.

The summary of findings presented in this review allows for the
conclusion that the most popular kinetic model used for gasi-
fication and combustion – the random pore model (RPM) – does
not represent the real reaction mechanism and that the use of
RPM may mislead researchers in their interpretation of kinetic
analysis.
The new findings presented in this review provide elements to
improve kinetic analysis, because the most used kinetic model –
the random pore model – cannot be considered as an accurate
representation of the gasification mechanism. The error incurred
by the separation of pyrolysis and gasification affects most of the
experimental works reported in the literature. Therefore, it is ad-
visable to encourage other researchers to conduct experiments,
accounting for the findings presented in this review, even stan-
dardizing the experimental procedure at the laboratory scale.
While kinetics can now be studied with simpler kinetic models,
challenges remain, such as the determination of the real CO, CO2,
and H2O concentrations on the char surface due to the water–gas
shift reaction. Small sample sizes help to reduce mass transfer
effects, but increase data dispersion, which make it almost im-
possible to determine gas concentrations in real time.
Efforts in catalytic gasification, by eliminating the ash and,
subsequently, adding a specific catalyst, should be reconsidered.
Ash-free feedstock (especially coal) is a great alternative for
combustion, but it is not favorable to reduce the feedstock surface
area and remove the catalyst in an acid leaching process for the
further addition of a more expensive catalyst. Reuse of the ash
is a promising alternative; therefore, studies in non-conventional
reactor configurations will help to increase raw feedstock gasifi-
cation efficiency.
30 N. Mahinpey, A. Gomez / Chemical Engineering Science 148 (2016) 14–31
Acknowledgments
The authors are thankful to the Natural Sciences and En-
gineering Research Council (NSERC) of Canada for funding this
study.
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