Article

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Updraft Gasification of Mesquite Fuel Using Air/Steam and CO2/O2

Mixtures
Wei Chen,† Siva Sankar Thanapal,† Kalyan Annamalai,*,† Robert J. Ansley,‡ and Mustafa Mirik‡
†
Department of Mechanical Engineering, MS 3123, Texas A&M University, College Station, Texas 77843, United States
‡
Texas AgriLife Research, Vernon, Texas 76384, United States

ABSTRACT: Gasification of woody biomass is an environmentally promising technology that provides an alternative to the use
of fossil fuel. Typically, partial air oxidation is used to gasify biomass fuels, resulting in low-quality product gases due to dilution
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by nitrogen (N2) in air, which limits the application of the product gases for thermal power generation. The objective of this
study was to identify optimum conditions for producing gases from woody biomass with enhanced heating values. Air, air/steam,
and a carbon dioxide/oxygen (CO2/O2) mixture were used as gasification media for the gasification of pure mesquite (low-
quality fuel) and a blend of mesquite and coal (high-quality fuel) using a 10 kW adiabatic fixed-bed reactor. Thermogravimetric
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analysis (TGA) along with limited emission studies using Fourier transform infrared (FTIR) spectrometry were performed to
obtain basic kinetic data on raw mesquite pyrolysis. The effects of the steam-to-fuel ratio (S/F) and equivalence ratio (ER) on
the peak temperature (Tpeak) in the gasifier, product gas composition, and higher heating value (HHV) of the product gases were
investigated. It was found that Tpeak decreased from 1050 to 850 °C as S/F was increased from 0 to 0.45. However, the carbon
dioxide (CO2) and hydrogen (H2) concentrations increased and the carbon monoxide (CO) percentage decreased with the
introduction of larger amounts of steam. For air/steam gasification, the HHV of the producer gas was estimated to be in the
range of 2800−3800 kJ/Nm3. The highest HHV was obtained at S/F = 0.3 and ER = 2.7 (optimum). The HHV of the gas from
air/steam gasification was found to be almost the same as that produced from pure-air gasification (2800−4000 kJ), except for an
increased H2 yield for air/steam. However, the HHVs of the gases obtained from CO2/O2 (79:21 on a volume basis) gasification
(4000−6000 kJ/Nm3) were generally higher. Separation of CO2 from the product gases obtained using CO2/O2 gasification can
further enhance the heating value of the product gas such that the HHV of the resulting gas mixture is 40% of the HHV of
natural gas. Hence, the use of a CO2/O2 mixture as the gasification medium and of coal blended with raw biomass as the fuel is
the best method for upgrading the quality of product gases from the gasification of woody biomass.

1. INTRODUCTION Gasifiers can generally be classified into two different types:

Biomass is a renewable energy source that can be utilized to
help meet energy demands. Apart from being converted into a
vast array of chemical products, fuels, and fertilizers, it can also
be utilized to produce steam, power, and electricity.1 Efforts are
underway to extract the energy from abundant supplies of
biomass in developing countries to provide power to remote
villages.2 However, there are still some limitations that would
affect the wide application of biomass. These limitations are due
to the high cost of feedstock transportation and lower biomass
density in such areas. It therefore would be beneficial to
develop small-scale, less expensive, and localized conversion
facilities that require less feedstock and save on feedstock
transportation costs.3
Woody species (brush) growing on semiarid uncultivated
lands (rangelands) in the upper Midwest of the United States,
such as mesquite (Prosopis glandulosa), might have the potential
to be used as bioenergy feedstocks. It is estimated that mesquite
covers 21 million hectares (Mha) of land in Texas alone, about
20% (or 4.2 Mha) could be harvested for bioenergy needs.4,5 At
an average of 18 dry Mg/ha, this could amount to a total
available mass of over 75 Tg.6 This species can be used as a
feedstock to produce syngas and bio-oil in small-scale
gasification units.
Gasification is a thermochemical process that converts
biomass into combustible gases and other chemical products.
fixed-bed and fluidized-bed. For fixed-bed gasifiers, the flow
velocity is low, and ash is disposed through a grate at the
bottom of the gasifier. For fluidized-bed gasifiers, the flow
velocity is high, and there is no grate. Fixed-bed gasifiers can, in
turn, be classified as updraft, downdraft, and crossdraft. Updraft
fixed-bed gasifiers are also called counterflow reactors, as the
fuel is fed into the top of the reactor and the gasification
medium (air or steam) is supplied at the bottom. In a
downdraft fixed-bed gasifier, both fuel and gases flow in the
same direction. Fixed-bed gasifiers are well-suited for small-
scale applications (power < 10 MW).7 Fluidized-bed gasifiers
usually are large-scale size and are used for industrial
applications. Considering the different gasification configura-
tions, an updraft fixed-bed gasifier was used for the current
study because such gasifiers are easy to construct and operate
and have high thermal efficiencies. The temperature of gas
exiting the updraft gasifier was below 200 °C, resulting in a
higher energy efficiency when compared to a downdraft gasifier.
The results from the current study can also be applied to
agricultural residues available in large amounts all over the
world. Determination of the optimum gasification conditions
Received: August 8, 2013
Revised: October 25, 2013
Published: October 25, 2013

© 2013 American Chemical Society 7460 dx.doi.org/10.1021/ef401595t | Energy Fuels 2013, 27, 7460−7469
Energy & Fuels
will result in increased gasification conversion efficiency and
production of gases with good heating values that can be used
directly for different applications.
Air, pure oxygen, air/steam, supercritical water, and carbon
dioxide have all been used as media for biomass gasification.
Because air contains a high percentage of nitrogen, the heating
value of the gas obtained from air gasification is very low. The
heating value of the producer gas from the air gasification of
biomass is in the range of 3.5−7.8 MJ/Nm3.7 Oxygen-blown
gasification produces a syngas with a medium heating value, and
steam-blown gasification leads to the production of a syngas
with an acceptable higher heating value (HHV) of around 10−
16 MJ/Nm3.8 In addition to air and oxygen, steam can also be
mixed with air to promote the steam-reforming reaction to
produce H2-rich gas mixtures and lower the gasification
temperature to avoid ash melting, which causes agglomeration
and clogging in the bed.
2. LITERATURE REVIEW AND OBJECTIVE
Extensive studies have been carried out on biomass gasification
using different gasification media. Gordillo and Annamalai9
used air/steam mixtures as gasification media for dairy biomass
gasification in an updraft gasifier. They found that the peak
temperature (Tpeak) and CO concentration decreased, whereas
the H2 and CO2 concentrations increased with increasing
equivalence ratio (ER). Also, increased values of the steam-to-
fuel ratio (S/F) produced H2- and CO2-rich mixtures with low
CO concentrations. The effects of preheated air and steam as
the gasifying agent were studied by Lucas et al.,10 who found
that, in a high-temperature air/steam updraft fixed-bed gasifier,
the preheated air and steam maximized the gas yield due to the
high heating rates. Increasing the feed-gas temperature reduced
the production of tars, soot, and char residue and increased the
heating value of the producer gas. Overall, it was seen that the
yield of gas and the heating value of the dry fuel gas increased
with increasing gasification temperature.
Lv et al.11 studied the characteristics of biomass air/steam
gasification in a fluidized bed. Their results showed that the
introduction of steam improved the gas quality when compared
with that obtained by biomass air gasification. For air/steam
gasification, the lower heating value (LHV) of the gas decreased
with ER. The gas yield varied between 1.43 and 2.57 N m3/(kg
of biomass), and the LHV of the fuel gas was between 6741 and
9143 kJ/Nm3. It was concluded that higher gasification
temperatures contributed to more hydrogen production;
however, excessively high temperatures lowered the gas heating
value. In addition, excessive steam would lower the gasification
temperature and, hence, degrade the fuel gas quality.
Gasification of mesquite and juniper using air as the medium
was carried out by Chen et al.3 in an updraft fixed-bed gasifier.
They reported that the H2 and CO mole percentages decreased
with increasing ER, whereas the CO2 and N2 mole percentages
increased. Gao et al.12 investigated the hydrogen-rich gas
produced from biomass in an updraft gasifier with a continuous
biomass feeder. The results showed that hydrogen-rich syngas
with a high calorific value, in the range of 8.10−13.40 MJ/Nm3,
was produced and that the hydrogen yield was in the range of
45.05−135.40 g of H2/(kg of biomass). Higher temperatures
were found to favor the formation of hydrogen. When the
gasifier temperature was increased from 800 to 950 °C, the
hydrogen yield increased from 74.84 to 135.4 g of H2/(kg of
biomass). The LHV of the gas increased first and then
decreased as the ER was increased from 0 to 0.3. Furthermore,
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a steam/biomass ratio of 2.05 was determined to be the
optimum value in all steam gasification runs.
Thanapal et al.13 studied the effects of using enriched-air and
carbon dioxide/oxygen mixtures on the gasification of dairy
biomass. They observed that the nitrogen in air acted as a
diluent in reducing the heating value of the resulting gas
mixture. The use of carbon dioxide/oxygen mixtures for
gasification resulted in the production of gases with much
higher HHVs than those obtained using air, air/steam, and
enriched-air mixtures. Co-gasification of biomass with bitumi-
nous coal was experimentally studied by Gordillo and co-
workers13 in an updraft fixed-bed gasifier. The effects of the
equivalence ratio and steam/fuel ratio were studied using air
and air/steam as gasification media. It was observed that the gas
quality was much higher for the coal/biomass blend than for
the raw dairy biomass. Gasification of biomass with coal in an
oxy-co-combustion gasifier was modeled by Valero and Usón.14
Their model predicted the possibility of oxy-co-gasification of
different biomass materials along with coal with negligible
variations in gas quality despite varying gasification parameters.
Mathieu and Dubuisson15 analyzed the effects of different
parameters affecting the gasification efficiency using the ASPEN
PLUS process simulator. They noted that oxygen enrichment in
the incoming gasification medium and preheating of the
gasification medium improved the gasification efficiency from
77% to 80% for increases in the oxygen concentration from
21% to 40% and from 76.5% to 80% when the temperature of
the gasification medium was increased from 298 to 1098 K.
However, the effects of using different gasification media on
the gasification of woody biomass, such as mesquite, in a small-
scale gasification facility have not been analyzed. Even though
mesquite covers 21 Mha in Texas, its location is scattered in
this area. Hence, a portable gasification unit that can be moved
from one spot to another will be an ideal choice for
thermochemical energy conversion applications. Because the
costs of processing and transporting biomass are high,
identifying optimum gasification conditions for small-scale
gasification units will help to increase the efficiency of energy
extraction from the gasification process. The main objective of
this study was to investigate the effects of the gasification
media, equivalence ratios, and steam-to-fuel ratio on the
gasification temperature (i.e., Tpeak), gas yield, and quality (i.e.,
HHV) of the resulting gas mixture from mesquite gasification.
This will enable the determination of the optimum gasification
conditions for producing a gas mixture with a high HHV in a
portable gasification unit that can be used in gas turbines,
internal combustion engines, and other heating applications.
3. EXPERIMENTS
3.1. Thermogravimetric Analysis (TGA) and Fourier
Transform Infrared (FTIR) Spectrometry Tests. To obtain
the fuel pyrolysis characteristics, TGA and FTIR studies were
performed. Pyrolysis or thermal decomposition of biomass
using inert (e.g., Ar, N2) and noninert (e.g., air) gases is the first
step toward understanding fuel properties and energy
conversion processes such as gasification, liquefaction, carbon-
ization, and combustion.16 In this study, an SDT Q600 TGA/
DSC apparatus from TA Instruments was used to determine
the effects of temperature on the weight loss characteristics of
mesquite fuel under different environments. The different
environments included air (N2/O2), a carbon dioxide/oxygen
(CO2/O2) mixture with the same volume percentages as air
(79% CO2 and 21% O2), pure CO2, and pure N2. In these
dx.doi.org/10.1021/ef401595t | Energy Fuels 2013, 27, 7460−7469
Energy & Fuels
Figure 1. Gasification facility (adapted from ref 9).
experiments, around 10 mg of mesquite fuel was heated at a
heating rate of 20 °C/min from room temperature to 900 °C
using the above gases. Using the TGA−pyrolysis data from a
single point where the volatile release rate is a maximum [called
the single-reaction-model−maximum-volatile-release (SRM−
MVR) method], the kinetics were extracted in addition to
the global Arrhenius fit and parallel reaction models. SRM−
MVR data are particularly useful in determining the upper limit
to the torrefaction temperature of biomass fuels.17 Limited
studies were performed on the composition of the gases
liberated as a result of mesquite fuel pyrolysis (N2 as the purge
gas) using an FTIR spectrometer (MultiGas 2030). To avoid
condensation, a heated gas-transfer line was maintained at 200
°C by an external heater.18 The methodology is described by
Eseltine et al.19 The liberated gases such as CO, CO2, H2O, and
CH4 were measured for their compositions every 20 s by FTIR
spectrometry. A chemical formula for volatiles was determined
and is presented in section 4.3.
3.2. Gasification Facility and Procedure. The small-scale
(10 kW) batch-type fixed-bed gasifier employed for this
research is shown in Figure 1. The well-insulated gasifier had
an outer diameter of 24.5 cm and a height of 72 cm. More
details are provided elsewhere.9 The gasifier was also equipped
with an ash disposal system. A conical gyratory cast iron grate
drilled with large number of 6.4-mm-diameter holes was
coupled to a pneumatic vibrator of variable frequency that
vibrated the grate to remove the ash continuously from the bed.
The rate of ash removal was controlled by changing the
vibration frequency of the vibrator. The condensers were made
of stainless steel and installed right after the reactor to ensure
that the tar was collected by the condenser without sticking to
the piping.
At the beginning of each experiment, the empty bed was
preheated to 600 °C using a propane torch. After the
temperature had reached 600 °C, the torch was turned off,
and biomass samples were gradually added to the gasifier. The
addition continued until the bed height of the gasifier reached
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22 cm (8.5 in). Afterward, the fuel port was closed, and the
gasification medium, for example, air and steam, was sent into
this system at the desired rate. The same procedure was used
for different gasification media (air, CO2/O2 mixture) and fuel
blends (coal and biomass blend). For CO2/O2 gasification, a
mixture of CO2 and O2 gas in a ratio of 79:21 on a volume basis
(same as N2/O2 ratio in the air) was used. Carbon dioxide and
oxygen cylinders were used, and the gases were well mixed
before being sent into the gasifer.
The equivalence ratio (ER) used for the present study was
determined as17
stoichiometric number of moles of air
ER =
actual number of moles of air
(A/F)stoichiometric
=
(A/F)actual
Hence, an increase in equivalence ratio indicates less air being
sent into the gasifier for the gasification process. The steam-to-
fuel ratio (S/F) was determined as17
mass of steam
S/F =
mass of biomass (as‐received)
3.3. Steam Generation. The steam generator was made of
a 10-cm-diameter cylindrical vessel surrounded by a variable-
power (0.1−1.2 kW) tape-type heating element.7 The steam
generator was first calibrated to ensure that the desired flow
was supplied to the gasifier. The desired rate of steam leaving
the steam generator was equal to the rate of water entering the
vessel. The steam generation rate was adjusted by controlling
the power supplied to the heater. The steady state of the steam
generator was verified before each experiment.
3.4. Temperature Measurements. Eight K-type thermo-
couples were located 2, 4, 7, 10, 13, 20, 24, and 28 cm from the
bottom along the gasifier axis to measure the temperature in the
gasification chamber. The temperature inside the gasifier was
recorded every 60 s into a flash card.
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3.5. Gas Composition Measurements. A mass spec- Table 1. Properties of Mesquitea,b

trometer was used to measure the composition of the product
property value
gases. The gas was passed first through a condenser to remove
tar and condensable vapors and then through a series of filters As-Received Mesquite
to capture associated particles. A small amount of filtered gas content (%)
was then supplied to the gas analyzer. moisture 15.5
3.6. Uncertainty of Measurements. Variable-area flow ash 1.67
meters with an accuracy of ±3% were used to measure the flow VM 66.1
rate of the gasification medium into the gasification facility. The FC 16.7
K-type thermocouples used for temperature measurements had carbon 43.6
an accuracy of ±1.5 °C. The mass spectrometer was oxygen 33.6
precalibrated using a standard gas mixture (N2, CO, CO2, H2, hydrogen 4.98
C2H6, and CH4) of known composition and inert gas (helium) nitrogen 0.62
every 3 days to ensure accurate measurements. In limited cases, sulfur 0.03
particularly for experiments with air17 and CO2/O2 (ER = 2.7 HHV (kJ/kg) 16700
and 4.2), the experiments were repeated to check for the Dry, Ash-Free Mesquite
repeatability of the results. content (%)
moisture 0
4. RESULTS AND DISCUSSION ash 0
VM 79.8
4.1. Fuel Properties. A solid fuel generally consists of
FC 20.2
combustibles, ash, and moisture, and the combustibles contain
carbon 52.7
fixed carbon (FC) and volatile matter (VM). Ultimate analysis
oxygen 40.5
was performed to obtain the percentages of constituent
hydrogen 6.01
elements in the biomass. Table 1 provides the results of
nitrogen 0.75
proximate and ultimate analyses of the mesquite fuel. On a dry,
sulfur 0.04
ash-free (DAF) basis, the HHV of mesquite was found to be
HHV (kJ/kg) 20100
20128 kJ/kg (Table 1), which is a typical value for most
volatile HHV (kJ/kg)c 16900
biomass fuels on a DAF basis but is still less than the typical
chemical formula CH1.3582O0.5779 N0.0122S0.0003
DAF heating values of coals, 30000 kJ/kg . The empirical
RQd of mesquite21 0.95
formula for the mesquite sample was found to be
RQprocessinge of mesquite21 0.05
CH1.3582O0.5779N0.0122S0.0003. Mesquite biomass has a higher a
content of volatile matter (70−80%) than coal. Bituminous coal Adapted from ref 17. bSee TAMU Fuel data bank Web site24 for
has approximately 30−40% VM, and lignite has approximately properties of many coal and biomass fuel including sludge. cEstimated
using the relation HHVDAF = FCDAF × HVFC + VMDAF × HHVDAF.22
40−50% VM.20 It is also noted that the N content of mesquite d
RQ (respiratory quotient) is defined as the ratio of the number of
on a heat basis is almost same as that of coal, unlike for most moles of CO2 emitted to the number of moles of O2 consumed for the
biomass fuels. oxidation reaction of a fuel. RQ > 1 indicates higher CO2 emissions
4.2. TGA Tracing of Mesquite Fuel. Figure 2a shows potential from a fuel. eRQprocessing is an equivalent RQ value which
TGA traces of the mesquite fuel. It can be seen that all of the indicates the amount of CO2 released from the consumption of fossil
TGA trace curves exhibit the same trend. With an increase in fuels used for processing biomass. Assuming that mesquite is carbon-
temperature, the moisture is first liberated from the fuel, which neutral and that energy from fossil fuels is consumed only during the
contributes a 10% weight loss. Volatile matter starts to be harvesting stage.23
released from the mesquite at temperatures around 240 °C.
When the temperature reached the ignition temperature (the oxidation: rapid mass loss due to hemicellulose and cellulose
point where the trace obtained in air deviated from the N2 oxidation, followed by rapid mass loss due to lignin oxidation in
trace), the slope of the air tracing curve became sharper than air. Similar mass loss behavior was also reported by Ghetti et
that of the CO2/O2 curve. Thus, the fuel was oxidized more al.25 and Ergüdenler and Ghaly26 for different lignocellulosic
rapidly when air was used as the purge gas than when CO2/O2 biomass samples. The occurrence of these two steps depends
was used, especially when the temperature was above 350 °C. on the percentages of hemicellulose, cellulose, and lignin
This might be because of comparatively higher specific heat of contained in the biomass samples. However, with CO2, the rate
CO2 compared to N2, which results in some heat being carried of weight loss was lower because of the higher heat capacity of
away by the larger CO2 molecules. When CO2 was used as the CO2 and the reaction of carbon dioxide with carbon in the
purge gas, the mass loss rate was higher than that obtained biomass. As a result, the sample was relatively cooler, so that
using N2 as the purge gas, especially at high temperatures. This mass loss occurred over a wider temperature range during the
is because of the Boudouard reaction (e.g., CO2 + C → 2CO, ) second combustion step at T < 600 °C.
which occurs at high temperatures. It can be seen in Figure 2a 4.3. FTIR Analysis of Pyrolysis Gas Composition.
that, when the temperature reached 600 °C, more than 80% of Because of the complex structure of tar, it was not identified
the weight of the mesquite fuel (including moisture and volatile by FTIR spectrometry. Panels a−e of Figure 3 present the
matter) was liberated from the fuel on using nitrogen as the concentrations of CO2, CO, H2O, CH4, and formaldehyde,
medium, which means that, under pure pyrolysis condition, respectively, from mesquite pyrolysis. For CO2 and CO, peak
biomass will release more gas than coal. Figure 2b shows the emission was observed in the temperature range of 340−370
weight loss rate as a function of temperature under different °C as a result of the decomposition of cellulose and
environments. The weight loss curve for CO2/O2 was found to hemicellulose. Giuntoli et al.27 found that the release peaks of
be similar to that for air. In Figure 2b, there are two peaks with CO, CO2, and H2O occurred at temperatures between 300 and
7463 dx.doi.org/10.1021/ef401595t | Energy Fuels 2013, 27, 7460−7469
Energy & Fuels
Figure 2. TGA traces of (a) mesquite using air, CO2, N2, and CO2/O2
(sampler size, 10 mg; heating rate, 20 °C/min) and (b) rate of
mesquite weight loss using air, CO2, N2, and CO2/O2.
320 °C for the pyrolysis decomposition of untreated wheat
straw. In contrast to the wheat straw fuel, the main water
release peak from the mesquite fuel occurred when the
temperature was below 200 °C, and between 250 and 420
°C, its emission decreased almost to zero. This might be
because most of the cellulose and hemicellulose decomposed
into CO, CO2, and a small amount of formaldehyde .When the
temperature increased to 420 °C, H2O was released from fuel
as a result of the decomposition of lignin. In Figure 3c, it can be
seen that, when the temperature reached 350 °C, CH4 started
being released from the fuel as a result of the decomposition of
methoxyl groups in the lignin part of the biomass. 28
Formaldehyde (CH2O) is a colorless gas with a characteristic
pungent odor.27 In Figure 3e, it can be seen that formaldehyde
was released from the fuel in the temperature range of 380−750
°C, with a peak at ∼600 °C.
Neglecting nitrogen and sulfur in the biomass, the carbon-
normalized chemical formula for DAF mesquite fuel is
CH1.3582O0.5779. During pyrolysis, the mesquite fuel released
the volatile matter, and the fixed carbon remained unconsumed
in the char. This process can be represented as CH1.3582O0.5779
→ αCHhvOov + (1 − α)C(s), where the two terms on the right-
hand side represent the volatile matter (hv and ov represent the
number of hydrogen and oxygen atoms respectively in the
released volatile matter) and fixed carbon, respectively. From
the proximate analysis results in Table 1 (approximately 80%
VM and 20% fixed carbon on a DAF basis), one can express the
fixed-carbon content of the carbon-normalized fuel as (1 − α)
× (12.01/M) = 0.2, where M is the molecular weight of the
fuel. From this expression, the value of α was determined to be
0.62. Then, using an oxygen-atom balance, we obtained hv and
ov. Around 38% of the total carbon in the biomass was
estimated to remain in the char, whereas 62% was released as
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volatile matter when considered on a dry, ash-free basis.
However, char is not pure carbon, and if it contains H and O,
then for the same “fixed carbon” obtained in the proximate
analysis, less carbon would actually remain in char containing H
and O. The FTIR data were used to check the mass balance of
the total carbon in the raw biomass. From the data, it was found
that around 74% of the total carbon was released along with the
volatile matter and only 26% of the carbon was left in the char.
This is important in countercurrent gasifiers, where most
moisture leaves from the top of the bed. However, char still
contains H and O, and the water−gas shift reaction might also
occur.
4.4. Temperature Profile for Air/Steam Gasification.
Figure 4 shows the temperature profiles for mesquite
gasification at different steam/fuel ratios (S/F). The results
obtained from the TGA study (Figure 2a) on the pyrolysis of
mesquite samples can be used to determine the pyrolysis
starting point in the gasifier (Figure 4). The temperature
profiles for air/steam gasification exhibited the same trend as
that for air gasification (S/F = 0): The temperature first
increased and reached a peak value (Tpeak) and then decreased
along the axis of the gasifier. However, Tpeak was lower for air/
steam gasification than for air gasification. It was found that, for
air/steam gasification, Tpeak < 1000 °C in most cases. For air
gasification, Tpeak reached 1050 °C for ER = 2.7, whereas it was
only 1010 °C for air/steam gasification at S/F = 0.15 and ER =
2.7. The difference is due to both chemical effects, in that most
steam gasification reactions are endothermic processes, which
results in a lowering of the gasification temperature, and
physical effects, in that the specific heat at constant pressure
(Cp) of the steam and air mixture is higher than that of air.13
Typically, the peak temperature inside the gasifier exhibited the
following trend for air gasification: TER=2.7 > TER=3.2 > TER=3.7 >
TER=4.2.
From Figure 4, it can be seen that the peak temperatures of
the gasification temperature profiles follow the order TS/F=0 >
TS/F=0.15 > TS/F=0.30 > TS/F=0.45. A higher S/F ratio means that
more steam was sent into the gasifier, so that the endothermic
reactions and increased Cp lowered the temperature inside the
gasifier. The variation of peak temperature within the bed for
different steam/fuel ratios is shown in Figure 5. However, the
peak temperature was high for the gasification of the coal/
mesquite blend (Figure 6), because of the higher amount of
fixed carbon available in the coal, which resulted in the release
of a large amount of heat from the char oxidation process.
4.5. Temperature Profile for CO2/O2 Gasification.
When the carbon dioxide/oxygen mixture was used for
gasification, the peak temperature was much lower (870 °C
for ER = 2.7 with S/F = 0); in particular, for ER = 4.2, Tpeak
dropped below 750 °C. The lower peak temperature can be
attributed to the higher specific heat of carbon dioxide at higher
temperatures compared to that of nitrogen and the
endothermic Boudouard reaction. Figure 6 shows the variation
of temperature profile for different gasification conditions.
4.6. Gas Composition for Air/Steam Gasification.
Figure 7 presents the gas compositions (CO, CO2, H2, and
CH4) as a function of ER at S/F = 0.45. Increasing the ER at
constant S/F lowered the CO concentration while increasing
the CO2 percentage. Under a high-steam environment, a lower
gasification temperature favors the formation of CO2 and H2
while decreasing CO. These trends occur because higher
temperature shifts the equilibria of the endothermic reactions
(e.g., CO2 + H2 ↔ CO+ H2O) toward the products and those
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Energy & Fuels Article

Figure 3. Variations in the concentrations of (a) CO2, (b) CO, (c) H2O, (d) CH4, and (e) formaldehyde with temperature during mesquite
pyrolysis in N2.

Figure 5. Peak air/steam gasification temperature at different S/F

Figure 4. Temperature profile of mesquite fuel at ER = 2.7 for several ratios.
S/F ratios.
CH4 + H 2O ↔ CO + 3H 2 ΔH = 206 000 kJ/kmol
(2)

of the exothermic reactions (e.g., CO + H2O ↔ CO2+ H2) C(s) + CO2 ↔ 2CO ΔH = 172 320 kJ/kmol (3)
toward the reactants. As a result, a series of endothermic and
exothermic biomass gasification reactions can be used to C(s) + O2 ↔ CO2 ΔH = −393 180 kJ/kmol (4)
explain the gasification mechanism:29
C(s) + H 2O ↔ CO + H 2 ΔH = 131 160 kJ/kmol CH4 + 2H 2O ↔ CO2 + 4H 2 ΔH = 165 000 kJ/kmol
(1) (5)

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Energy & Fuels
Figure 6. Variation of Tpeak with gasification medium.
Figure 7. Gas composition for a typical experiment at S/F = 0.45 for
several ER values.
C(s) + 0.5O2 ↔ CO ΔH = −110 000 kJ/kmol
CO2 + H 2 ↔ CO + H 2O ΔH = − 16 180 kJ/kmol
Increasing the gasification temperature would result in the
equilibria of reactions 2, 3, and 6 moving forward, favoring the
formation of H2. Also, endothermic reactions 2−4 would
prevail over reaction 7, thus increasing the CO concen-
tration.17,29 Additionally, reaction 5 would be favored at low
temperature, and thus, more CO2 would be generated. The
CH4 percentage did not vary much within the range of ER
values investigated, and its concentration remained almost
constant at 1−2%.
Figures 8 and 9 present the CO2 and CO concentrations,
respectively, for different S/F ratios. At a constant ER,
increasing the S/F ratio led to an increase in the CO2
Figure 8. CO2 mole percentage vs ER for different S/F ratios.
Article
Figure 9. CO mole percentage vs ER for different S/F ratios.
concentration and a decrease in the CO percentage. As
discussed earlier, a lower gasification temperature and higher
steam concentration would shift the equilibrium of the water−
gas shift reaction toward the formation of CO2 and H2.
Figure 10 presents the effects of ER and S/F on the H2
concentration. It was found that increasing S/F increased the
(6)
(7)
Figure 10. H2 mole percentage vs ER for different S/F ratios.
H2 concentration in the product gas. At constant S/F,
increasing ER also resulted in an increase in the steam/air
ratio. The heterogeneous reaction of char with steam could
occur in a steam-rich environment, producing more H2.9 In
addition, the equilibrium of the water−gas shift reaction shifts
in the direction of the formation of H2 in a H2O-rich
environment.9 Moreover, an increase in S/F leads to more
steam being available to react with char to produce CO and H2.
For instance, the H2 concentration was less than 4% under
pure-air gasification (i.e., S/F = 0), increased to 4−7% for S/F
= 0.15, and reached the range of 7−10.5% for S/F = 0.3. The
highest H2 percentage was around 11%, which occurred at S/F
= 0.45 and ER = 4.2.
4.7. Gas Composition for CO2/O2 Gasification. To
obtain high-quality gas, CO2 was considered as an alternate
gasification medium to air and an air/steam mixture. The
composition of the producer gas obtained using a CO2/O2
mixture as the gasification medium is shown in Figure 11.
Because CO2 was used as the medium, the percentage of CO2
in the product stream was higher. It can be seen that CO
reached as high as 32% for CO2/O2 gasification, whereas the
maximum was 25% for air gasification, because the C + CO2
reaction occurs and the water−gas shift reaction favors the
direction CO2 + H2 → CO + H2O at high CO2 concentration,
7466 dx.doi.org/10.1021/ef401595t | Energy Fuels 2013, 27, 7460−7469
Energy & Fuels
Figure 11. Gas composition from the CO2 gasification process.
as evidenced by the lower H2 concentration for CO2/O2
gasification.
4.8. HHV of the Gas Mixture. Figure 12 shows the HHVs
of the gas mixtures produced during the gasification of
Figure 12. Gas HHVs for the steam gasification of mesquite biomass
at various S/F ratios.
mesquite at S/F = 0, 0.15, 0.3, and 0.45 on a dry, tar-free
basis. The heating value of the produced gas was determined in
each case from the gas composition measured using the mass
spectrometer and the known heating values of the constituents
of the gas mixture. The HHV of methane is 36264 kJ/Nm3, and
the HHVs of CO and H2 are 11550 and 11700 kJ/Nm3,
respectively.9 It was found that the HHVs of the gases
produced followed the order HHVS/F=0.45 < HHVS/F=0.15 ≈
HHVS/F=0 < HHVS/F=0.3. The HHV of the gas first increased
when S/F was increased from 0.15 to 0.3 because of the
increased amount of H2 produced by the water−gas shift
reaction. With the further increase in S/F to 0.45, the HHV of
the gas decreased, and its value was lower than that of the gas
obtained at S/F = 0.15. This is because, under high-S/F
conditions, the lower gasification temperature resulted in the
generation of less volatiles and more of the noncombustible gas
CO2 (water−gas equilibrium shift).
Figure 13 shows a comparison of the heating values of the
gas mixtures obtained using different gasification media for
gasifying pure mesquite and a blend of mesquite and coal. It
can be observed that the use of the air/steam mixture increased
the HHV of the gas mixture slightly when compared to the use
of pure air. Using carbon dioxide/oxygen mixture resulted in a
gas mixture with a high HHV in the range of 5500 kJ/Nm3 for
mesquite gasification. This high HHV is due to the Boudouard
reaction (CO2 + C → 2CO) taking place within the gasifier.
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Figure 13. Heating values of the gas mixtures obtained using different
gasification media and fuels.
Because the concentration of carbon dioxide was high when the
CO2/O2 mixture was used, the CO2 reacted with the fixed
carbon in the biomass to yield more CO, which increased the
gas HHV. However, at higher ER, the HHV of the gas mixture
obtained using the CO2/O2 mixture was lower because of the
lower Tpeak within the bed. Blending mesquite with sub-
bituminous Powder River Basin (PRB) coal in the ratio of
80:20 on a mass basis and gasifying the blend with air resulted
in a gas mixture with a much higher heating value because of
the presence of a higher amount of fixed carbon in the resulting
fuel blend.17 Gasifying the coal/biomass blend with the CO2/
O2 mixture further enhanced the HHV of the resulting gas
mixture.
Produced gas with a high HHV can be used as a fuel in gas
turbines. The effect of enhancing the heating value of the
produced gases in gas turbine applications has been reported
elsewhere.17 It was estimated that increasing the heating value
reduced the volumetric flow of the syngas into the gas turbine.
A 30% reduction in the volumetric flow of gases was achieved
when gases with a higher HHV were used. The gasification
conversion efficiency varies between 20% and 70% depending
on the equivalence ratio (ER) employed.7,17 The main
gasification products include gas, ash, and tar. A higher ER
value results in lower gas production because of reduced
amount of oxygen available for gasification. The lower the
amount of oxygen supplied to the gasifier, the lower the
gasification temperature, and thus, the less tar cracked into gas
and more unburned char remaining in the ash. Hence, the heat-
based gasification conversion efficiency30 decreases with
increasing ER.
Because of the higher percentage of N2 or CO2 in the
producer gas, the gas HHV is very low. Producer gas quality can
be further improved if CO2 and N2 are removed from the
producer gas. Also, the sequestered CO2 can be recycled for
gasification. It can be seen in Figure 14 that the HHV of the
producer gas can reach 36% of the natural-gas HHV for CO2/
O2 gasification, whereas it can reach only 26% of the natural-gas
HHV for air gasification. Thus, by using CO2/O2 as the
gasification medium, the HHV of the producer gas can be
further increased by 10% when compared to that obtained by
air gasification.
5. CONCLUSIONS
The effects of using different gasification media for gasifying a
woody species was studied using a small-scale fixed-bed
gasification facility, and the following conclusions can be
drawn from this study.
dx.doi.org/10.1021/ef401595t | Energy Fuels 2013, 27, 7460−7469
Energy & Fuels
Figure 14. Heating values of the gas mixtures obtained after removing
CO2 and N2 from the producer gas.
(1) Both the peak and average bed temperatures decreased
for air/steam gasification compared to air gasification. In
addition, increasing the S/F ratio and ER value decreased the
gasification temperature because of the endothermic char−
steam reaction.
(2) The main products for air/steam gasification were found
to be CO, CO2, H2, N2, CH4, and C2H6. Increasing the S/F
ratio led to an increase in the CO2 and H2 concentrations and a
decrease in the CO percentage. The HHV of the gas mixture
increased from 2800 to 3800 kJ/Nm3 when S/F was increased
from 0.15 to 0.45.
(3) Using a CO2/O2 mixture for gasification produced a gas
with a much higher HHV because of the Boudouard reaction
taking place under the CO2-rich conditions in the reactor.
Because CO2 separation technology has been developed, the
removal of CO2 from the product gas mixture in CO2/O2
gasification will increase the HHV of the product gases, and the
HHV can reach almost 36% of the HHV of natural gas.
(4) The optimum gasification conditions for gasifying
mesquite to obtain a gas with a higher HHV would be to use
an ER of 2.7 with a CO2/O2 mixture as the gasification medium
and blending coal with the biomass to increase the percentage
of fixed carbon in the fuel.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: kannamalai@tamu.edu. Tel.: +1(979) 845-2562. Fax:
+1(979) 845-3081.
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge financial support from Texas AgriLife
Research State Bioenergy Initiative Funding and the U.S.
Department of Energy-NREL, Golden, CO. The authors also
acknowledge ASME for their permission to publish this article.
■
ABBREVIATIONS
Cp = specific heat at constant pressure
DAF = dry, ash-free
7468
Article
ER = equivalence ratio
HHV = higher heating value
LHV = lower heating value
Nm3 = standard cubic meter
S/F = steam/fuel ratio
Tpeak = peak temperature
VM = volatile matter
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