Proceedings of International Symposium on EcoTopia Science 2007, ISETS07 (2007)

Parameters Influencing Clean Syngas Production from Biomass, Solid

Wastes, and Coal during Steam Gasification

K. Sangtongam1, J. Gmurczyk1 and A. K. Gupta 1

1. Department of Mechanical Engineering, University of Maryland, College Park, MD 20742, USA

Abstract: High temperature steam gasification of paper, yellow pine woodchips and Pittsburgh black coal
was investigated in a batch type flow reactor at temperatures in the range of 700 °C to 1200 °C at two
different ratios of steam to feedstock molar ratios. Hydrogen yield of 54.7% for paper, 60.2% for
woodchips and 57.8% for coal was achieved on a dry basis, with a steam flow rate of 6.3 g/min at steam
temperature of 1200°C. The yield of both the hydrogen and carbon monoxide increased while carbon
dioxide and methane decreased with the increase in gasification temperature. A tenfold reduction in tar
residue was obtained at high temperature steam gasification, as compared to low temperatures. Higher
steam to feedstock molar ratio increased the amount of hydrogen in the syngas. However, increase in the
steam flow rate resulted in decreased hydrogen content and increased carbon dioxide in the syngas
produced. Thus the gasification temperature can be used to control the amounts of methane or hydrogen
produced from the gasification process. The syngas produced can be further processed to produce pure
hydrogen. This also provides mean to produce hydrocarbon rich syngas, which can then be processed to
produce liquid hydrocarbon fuel. The biomass fuels are good source of renewable fuels to produce
hydrogen or liquid fuels using controlled steam gasification.

Keywords: Steam Gasification, Hydrogen from Wastes and Biomass, Ultra-high Temperature Steam
Gasification, Biomass

1. INTRODUCTION
The increased energy demand and dwindling fossil fuel
reserves necessitate the development of alternative and
sustainable fuel options that can be used in current as
well as future energy conversion systems. Crude oil,
natural gas and coal reserves are estimated to last for
about 30, 50 and 250 years, respectively [1]. It is
recognized that future fuel discoveries may extend this
time duration. Furthermore, at present oil and natural gas
together constitute almost 50% of the world’s energy
source. This then suggests that one can anticipate facing
to replace almost half of our energy production with
alternative sources of energy in the near term.
One of the attractive alternative fuels, which have been
given considerable attention, is hydrogen. Despite being
considered the cleanest fuel, hydrogen is still produced
through processes which pollute the environment, such as
methane-steam reforming, which produces substantial
amounts of carbon dioxide and uses useful energy
resources, such as hydrocarbon fuels. Gasification, a
process of converting solid fuel into gas under
oxygen-starved conditions, has been known as a
promising technology capable of producing
hydrogen-rich fuel from solid feedstock, such as, biomass,
municipal and industrial solid wastes and coals [1-16].
The syngas produced is of low to medium calorific value
and is rich in hydrogen and carbon monoxide [2]. The
gasification technology can greatly reduce tars and
organic material in the residue and also minimizes the
production of carbon dioxide and hydrocarbons which are
directly responsible for the global warming from this and
other greenhouse gases as well as depletion of ozone.
Wei, et al. [3] has shown that temperature is the most
important factor in increasing hydrogen yield and
reducing tars and that the use of steam as the gasifying
agent also improves the quality of the syngas. Pinto, et al.
[4] obtained up to 50% hydrogen in their syngas by
gasifying pine woodchips mixed with plastic wastes.
Franco, et al. [5] achieved almost 35% of hydrogen in
their syngas from the gasification of pine wastes in a
fluidized bed, while maintaining methane and carbon
dioxide levels at about 10-15%. Although the research
results shown by the above investigators have shown a lot
of promise for clean syngas fuel conversion of solid fuels
and wastes, no data are available at temperatures
exceeding 900°C. It has been shown, however, by
equilibrium calculations that gasification at temperatures
above of 900°C can produce syngas with hydrogen
concentrations well in excess of 50% [6].
This study focuses on the high and ultra-high
temperature steam gasification of paper, woodchips and
coal to produce hydrogen-rich syngas while minimizing
pollutant emissions, hydrocarbons, tars and solid residue
by-products. Pure steam gasification was chosen over
steam/air or steam/oxygen gasification (also called
“unbound oxygen” gasification), because it was shown in
previous studies [7] that it can maximize hydrogen yield
while keeping carbon dioxide content to a minimum.
Furthermore, the use of ultra-high temperatures favor the
formation of hydrogen while simultaneously reducing
tars, carbon dioxide and hydrocarbons.
2. CHEMISTRY AND THERMODYNAMICS OF
GASIFICATION
The main reactions that occur during the gasification
process involve steam, oxygen, hydrogen, carbon dioxide,
carbon monoxide, and methane are provided in the
following [8]. The pyrolysis and gasification can make

Corresponding author: A. K. Gupta, akgupta@umd.edu

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 Proceedings of International Symposium on EcoTopia Science 2007, ISETS07 (2007)
significant contributions to the waste fuel conversion to
result in significant variations in the product gas
composition [9-16].
Combustion reactions:
C + O2 => CO2 - 394 MJ/kmol (2.1)
C + ½ O2 => CO - 111 MJ/kmol (2.2)
CO + 2 O2 => CO2 - 283 MJ/kmol (2.3)
H2 + 2 O2 => H2O - 242 MJ/kmol (2.4)
Boudouard reaction:
C + CO2 <=> 2 CO + 172 MJ/kmol (2.5)
Carbon shift reaction:
C + H2O <=> CO + H2 + 131 MJ/kmol (2.6)
Hydrogenation reaction:
C + 2 H2 <=> CH4 - 75 MJ/kmol (2.7)
The combustion reactions proceed as long as there is
free oxygen in the reactor. Once free oxygen is depleted
and the combustion reactions are complete, only the last
three reactions (Boudouard, Carbon shift and
Hydrogenation) can be considered to determine the
equilibrium composition of the syngas. As soon as carbon
conversion is complete, only two homogenous reactions
are needed to describe the process:
Water gas shift reaction:
CO + H2O <=> CO2 + H2 - 41 MJ/kmol (2.8)
Steam methane reforming reaction:
CH4 + H2O <=> CO2 +3 H2 + 206 MJ/kmol (2.9)
All these reactions proceed in both the directions until
thermodynamic equilibrium is reached, as long as the
residence time in the reactor is satisfied. It can be seen
from the above reactions that decreasing the amount of
oxygen in the reactor and using pure, high temperature
steam will favor endothermic reactions (Boudouard,
carbon shift and steam methane reforming reactions, no.
2.5, 2.6 and 2.9 respectively), which are responsible for
production of hydrogen and minimize hydrocarbon
formation. Therefore, it is favorable to use pure high
temperature steam as a gasifying agent in order to obtain
hydrogen-rich syngas.
3. EXPERIMENTAL
The experiments were carried out in a specially
designed gasification facility that allowed the gasification
of different types of wastes in a batch form using
different gasifying agents at desired temperatures. The
key components in the gasification facility (Fig. 1)
consist of a combustion chamber and an electrically
heated furnace. High temperature steam is produced from
the combustion of hydrogen and oxygen in the chamber.
The steam then flows into the electrically heated furnace,
which maintains a constant temperature at the desired
gasification temperature. The sample is placed into a
stainless steel basket and then inserted into a 2 ¼”
diameter stainless steel tube, located inside the furnace.
A gas sampling probe is placed at the outlet of the furnace
to collect representative sample of the syngas produced.
A peristaltic pump is used to withdraw the syngas. The
618
moisture and particulates from the syngas are condensed
out by passing the sample through a moisture condenser
and a set of particulate filters. The sample composition
is then analyzed by a Micro Gas Chromatograph. A set of
thermocouples are also used to monitor the temperature at
various locations in the process.
Furnace
Steam bypass
Steam inlet
To micro GC
Feedstock
Combustion Chamber
H2
O2
Fig. 1. A schematic diagram of the continuous flow
gasification reactor.
The samples used in the present study consist of: white
paper, yellow pine woodchips and Pittsburgh coal.
Table 1 provides the chemical composition of each
sample feedstock examined in this study. Nominal sample
weight for each material examined was about 30 grams.
The steam flow rate was varied between 3.3 g/min and
6.3 g/min to analyze the effect of steam/feedstock ratio
on the composition of the syngas. This allowed for more
than 2 fold increase in the steam/feedstock ratio during
the gasification. The temperature of the steam as
gasifying agent was varied between 700°C and 1200°C.
Table 1. Ultimate analysis of the sample materials [8].
Materials Ultimate Analysis [ wt% dry ]
C H O N S
Paper 49.0 6.9 35.0 0.5 0.1
Woodchips 52.6 7.0 40.1 0.0 0.0
Coal 83.3 5.4 8.1 1.6 1.6
4. RESULTS AND DISCUSSION
To estimate the global behavior under various
gasification conditions and also to reduce the large test
experimental matrix under which the gasification process
occurs, a commercial code, Fluent, was used. The method
allowed one to determine the extent of thermal filed
uniformity in the reactor. These results in conjunction
with a set of experiments were used to determine the
thermal field associated with the steam in test section of
the reactor. Fig. 2 shows a sample of the simulated
temperature profile associated with the steam flow in test
region of the reactor, which reacts with the feedstock.
The assumptions made in the simulation were: constant
reactor pipe wall temperature of 900°C inside the furnace,
initial steam temperature of 380°C (determined
 Proceedings of International Symposium on EcoTopia Science 2007, ISETS07 (2007)

experimentally) and a steam flow rate of 6.3 g/min
(determined from the metered amounts of hydrogen and
oxygen fed to the combustion chamber to produce steam.
The tail end of the test section pipe, outside the furnace
section, was cooled down by the surrounding air to near
room temperature to about 25°C. It can be seen from the
simulation results that a uniform steam temperature of
900°C is maintained in the entire test section where the
sample is located and reacts with the high temperature
steam. To validate this simulation, an experiment was
conducted, in which the wall temperature was kept
constant by the resistance heating coils of the electrical
furnace and a steam flow rate of 6.3 g/min was used.
The results compared favorably well for the sample
gasification case of 900°C. The temperature profiles were
found to be similar at other locations and gasification
temperatures. A sample of the comparison between
simulation and experiments at different locations in the
reactor is given in Table 2.
hydrogen as well as carbon monoxide production
increases with increase in gasification temperature, while
production of methane and carbon dioxide decreases.
Almost no methane or any higher series of hydrocarbons
are present at the high gasification temperatures
examined. Hydrogen and carbon monoxide concentration
is expected to be the high at high gasification
temperatures due to the endothermic nature of the
water-gas shift and Boudouard reactions. Also, the
endothermic steam-methane reforming reaction
contributes to three moles of hydrogen from each mole of
methane. At 1200°C the hydrogen concentration at steam
flow rate of 6.3 g/min was 51.1 % for paper, 50.5 % for
woodchips and 55.1 % for coal. However, as seen from
the reactions, the steam provides important contributions
on the amounts of hydrogen produced. Indeed the above
amounts of hydrogen concentrations were later found to
be higher at a lower steam flow rate.

7 0.0
H ydro gen

6 0.0 Me tha ne
C a rbon m on oxid e

5 0.0 C a rbon dioxide

Mol % [ dry gas ]

4 0.0

3 0.0

2 0.0

1 0.0

0.0
6 00 70 0 80 0 9 00 10 00 1 10 0 12 00 13 00

Fig. 2. Simulated temperature profile in the gasification Te m pe ra ture [ C ]

furnace.
Fig.3. Syngas composition from the gasification of paper
at different temperatures at a steam flow rate of 6.3
Table 2. Comparison of temperature profiles between g/min.
simulation and experiment.

Simulation Experiment
Location
[ ºC ] [ ºC ] 70.0
Hydrogen
T1 380 380 60.0 M ethane
Carbon m onox ide
T2 920 900 50.0 Carbon dioxide
Mol % [ dry gas ]

T3 900 850 40.0

30.0

Once the experimental conditions had been 20.0

determined, experiments were conducted using three 10.0

different feedstocks at several different steam gasification
temperatures to determine the influence of these variables 0.0
600 700 800 900 1000 1100 1200 1300
on the subsequently evolved syngas composition. A steam Tem perature [ C ]
flow rate of 6.3 g/min was used at a nominal feedstock
sample weight of 30 g. The sample gas composition was
acquired after 1, 2 and 3 minutes from the start of the
gasification. For all cases examined, highest hydrogen Fig. 4. Syngas composition from the gasification of
yield was obtained at high retention time of sample in the woodchips at different temperatures at a steam flow rate
gasification chamber (three minutes). Figs. 3 to 5 show of 6.3 g/min.
the syngas composition from the gasification of paper,
woodchips, and coal, respectively. It can be seen that

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 Proceedings of International Symposium on EcoTopia Science 2007, ISETS07 (2007)

70.0 60
Hydrogen
Methane
paper
60.0

Hydrogen [ mol % of dry gas ]

50 woodchips
carbon monoxide
Carbon dioxide coal
50.0
40
Mol % [ dry gas ]

40.0
30
30.0
20
20.0

10
10.0

0
0.0
0 50 100 150 200
800 900 1000 1100 1200 1300
Temperature [ C ] Re action tim e [ sec. ]

Fig. 5. Syngas composition from the gasification of coal Fig. 7. Influence of steam/feedstock molar ratio (increase
different temperatures at a steam flow rate of 6.3 g/min. with acquisition time) on hydrogen yield at 900 °C and
steam flow rate of 6.3 g/min.

Fig. 6 shows the lower heating value of the syngas

produced from the syngas containing hydrogen, CO and 60.0
paper
methane (since the amounts of other gases produced were
Hydrogen [ mol % of dry gas ]
50.0 woodchips
in trace amounts and hence considered negligible to the coal
heating value) from the gasification of paper, woodchips 40.0
and coal. The heating value in the case of paper increases
somewhat with increase in the gasification temperature. 30.0
However, for the case of woodchips and coal, the change
in heating value observed was negligible. 20.0

10.0

300.0
0.0
0 50 100 150 200
250.0
Rea ction time [ sec. ]
LHV of dry gas [ kJ/mol ]

200.0
150.0
100.0
50.0
0.0
800
Fig. 6. Lower heating value of the syngas produced from
gasification at a steam flow rate of 6.3 g/min.
Since a fixed weight of feedstock was used, while
keeping the steam flow rate constant, the steam to
feedstock molar ratio varied as a function of residence
time in the reactor. Syngas samples were taken at 1, 2 and
3 minutes after inserting the feedstock into the reaction
chamber to determine the influence of molar ratio on
hydrogen yield. Equilibrium calculations showed an
increase in hydrogen production (on a dry basis) with
increase in molar ratio. The results in Figs. 7 and 8 show
the same trend as that predicted from the equilibrium
calculations. Over the range of temperatures examined,
the highest hydrogen yield was consistently seen at 3
minutes after the start of the gasification.
Fig. 8. Influence of steam/feedstock molar ratio (increase
with acquisition time) on hydrogen yield at 1100 °C and
steam flow rate of 6.3 g/min.
paper
woodchips
The trend observed in figures 7 and 8 on hydrogen
coal
yield is also complemented by CFD simulations using
commercial Fluent code for the gasification process.
900 1000 1100 1200 1300 Figs. 9 and 10 show hydrogen concentration in the
Temperature [ C ] reactor after one and three minutes from the start of
gasification process, respectively, using paper. The
process is simulated by pyrolysis products with fixed
carbon reacting with steam at 900°C and 6.3 g/min flow
rate. Fluid flow is simulated by k-ε turbulent model.
Endothermic reactions are simulated by the EDC reaction
model. The feedstock is simulated as a porous volume.
The results show increased concentration of hydrogen at
longer residence time in the reactor, similar to that
observed experimentally.
Fig. 9. Simulated hydrogen concentration in the reactor
60 seconds after beginning of the gasification process
with steam temperature of 900 °C and flow rate of 6.3
g/min.

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 Proceedings of International Symposium on EcoTopia Science 2007, ISETS07 (2007)
Fig. 10. Simulated hydrogen concentration in the reactor
180 seconds after beginning of the gasification process
with steam temperature of 900 °C and flow rate of 6.3
g/min.
Two different steam flow rates were used to analyze
its effect on the syngas composition produced. While
higher steam/feedstock ratio usually produce higher
hydrogen yield in a batch reactor, as shown by
equilibrium calculations, this is not necessarily the case in
a continuous flow reactor. In this type of reactor kinetics
also provide a role. Furthermore, with increase in the
steam/feedstock ratio, a higher steam flow rate also
reduces residence time in the gasification volume due to
higher linear velocity of steam since the amount of
feedstock gasified is held constant. Mixing also plays a
role here, as the pyrolyzed sample and steam may not
have enough time to completely mix and react with each
other in the shorter residence time available. These two
aspects of the continuous flow reactor are expected to
contribute to lower hydrogen yields in the case of the
higher steam flow rate. As seen in figure 11, the highest
hydrogen yield results from 3.3 g/min steam flow rate at
1200 °C and at three minutes after the start of the
gasification for all three feedstocks (paper, woodchips
and coal) examined. At higher steam flow rate of 6.3
g/min, carbon dioxide emissions are higher for all the
three feedstocks but methane yield decreased slightly in
the case of coal.
70
60
50
40
Mol %
30
20
10
0
3.3 g/min 6.3 g/min 3.3 g/min 6.3 g/min 3.3 g/min 6.3 g/min
Paper Woodchips
Fig. 11. Comparison of the syngas composition from
three different feedstock at 1200 °C using two different
steam flow rates at 3 minutes after beginning of
experiment.
The amount of tar generation from gasification of
paper, woodchips and coal was also measured to examine
the effect of steam temperature on the total tar yield.
Tar is an undesired product from any gasification or
pyrolysis process. However, in the pyrolysis process the
yield of tars can be quite high so that measures must be
taken to control its amount in the gasification process. It
is formed during pyrolysis of solid fuel (at fuel
temperature of 300 °C to 620 °C) and it consists of heavy
hydrocarbons, which condense upon cooling to ambient
conditions. Tar is responsible for corrosion of gasifiers
and its deposits can clog channels which can be quite
difficult to remove. High gasification temperatures can
significantly reduce the amounts of tar yield. Experiments
were conducted to determine the amounts of tar yield
from the gasification of paper, woodchips and coal at
increased gasification temperatures. The results are
shown in figure 12. A nearly ten-fold reduction in tar
yield was observed by increasing the steam temperature
from 600 °C to 1200 °C in the case of woodchips and
paper. The observed tar generation from coal was
significantly smaller for low gasification temperatures
and the effect of high temperature was not as significant
as in the case of paper and woodchips. However, the mass
of tar generated was reduced by a factor of two when the
temperature was increased to 1200 °C. The lower tar
yield can be attributed to the heavy hydrocarbon chains
being cracked at high temperatures which react with
steam to eventually form hydrogen and carbon dioxide.
5
4.5
4
mtar /mfeedstock *100%
3.5
3
Paper
2.5
Woodchips
2 Coal
1.5
1
0.5
0
500 600 700 800 900 1000 1100 1200 1300
Temperature [C]
Fig. 12. Percent tar yield as a function of temperature.
H2
5. CONCLUSIONS
CO
CO2
The experimental and simulation results from this
CH4 study have shown that high temperature steam
gasification process can produce hydrogen-rich syngas
containing up to 60% hydrogen with minimal CO2 and
hydrocarbons. At sufficiently high gasification
temperatures, tar production can be almost eliminated
Coal
from the gasification products, thus making the process
attractive for the clean conversion of wastes and other
solid hydrocarbon materials to syngas with high
hydrogen content. The process is particularly attractive
for solid wastes since the amount of tars produced is
negligible at high gasification temperatures. The kinetics
provides an important role in the amounts of hydrogen
and heating value of the syngas produced as well as in the
reduction of tars from the process. The amounts tar
produced is affected by the gasifying agent type and its
temperature. A nearly ten-fold reduction in tar yield was
observed by increasing the steam temperature from
600 °C to 1200 °C in the case of woodchips and paper.
The observed tar generation from coal was significantly
smaller at low gasification temperatures and the effect of
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 Proceedings of International Symposium on EcoTopia Science 2007, ISETS07 (2007)
high temperature was not as significant as in the case of
paper and woodchips. The kinetics, which has provided
an important role in the flow reactor used here, should be
further examined. Reaction rates and mixing cause
deviations from the thermodynamic equilibrium and need
to be studied in detail in order to determine the optimum
conditions for the different kinds of wastes encountered
as well as some of the mixing strategies.
ACKNOWLEDGMENTS
This research was supported by the Office of Naval
Research, Program Director, Dr. Steve McElvany. This
support is gratefully acknowledged.
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