FUPROC-02436; No of Pages 7 ARTICLE IN PRESS

F U E L P RO C ES S I NG T EC H NOL O G Y X X (2 0 0 8) XX X– XXX

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Synthesis gas production using steam hydrogasification and

steam reforming

Arun S.K. Raju, Chan S. Park⁎, Joseph M. Norbeck

Bourns College of Engineering, Center for Environmental Research and Technology (CE-CERT), Department of Chemical and Environmental Engineering,
University of California, Riverside, California 92521-0425, United States

AR TIC LE D ATA ABSTR ACT

Article history: Experimental work has been carried out on the mixed reforming reaction, i.e., simultaneous
Received 4 June 2008 steam and CO2 reforming of methane under a wide range of feed compositions and four
Received in revised form different reaction temperatures from 700 °C to 850 °C using a commercial steam reforming
15 September 2008 catalyst. The experiments were conducted for a CO2/CH4 ratio from 0 to 2 and a steam to
Accepted 27 September 2008 methane ratio from 3 to 5. The effect of CO2/CH4 ratio on the exit H2/CO ratio and the
conversions of the reactants indicate that the dry reforming reaction is dominant under
Keywords: increased carbon dioxide in the feed. Steam reforming of typical steam hydrogasification
Steam reforming product gas consisting of CO, H2 and CO2 in addition to steam and methane has also been
CO2 reforming investigated. The H2/CO ratio of the product synthesis gas varies from 4.3 to 3.7 and from 4.8
Synthesis gas to 4.1 depending on the feed composition and reaction temperature. The CO/CO2 ratios of
H2/CO ratio the synthesis gas varied from 1.9 to 2.9 and 2.0 to 3.3. The results are compared with
Aspen Plus simulation results obtained through the Aspen Plus process simulation tool. The results
Steam hydrogasification demonstrate that a coupled steam hydrogasification and reforming process can generate a
synthesis gas with a flexible H2/CO ratio from carbon-containing feedstocks.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction technologies available for syngas production depending on the

input gas composition; each usually resulting in a specific fixed
The efficient commercial production of synthesis gas (a mixture H2/CO syngas ratio [3]. Steam methane reforming produces a H2/
of hydrogen and carbon monoxide) is gaining significant CO syngas ratio of four or higher whereas partial oxidation
attention as the worldwide interest in synthetic fuels and gasification produces a syngas ratio of 1; and autothermal
chemicals is increasing. Synthesis gas (syngas) is a versatile reforming produces a ratio of 2. The composition of the syngas
feedstock that can be used in the production of a number of from either gasification processes or syngas production tech-
hydrocarbons, including synthetic Fischer–Tropsch (FT) diesel. nologies are generally not suited for direct use in the down-
The required molar ratio of hydrogen to carbon monoxide stream fuel process. In several cases, H2/CO syngas ratio
(referred to as the syngas ratio) varies depending on the desired adjustment techniques such as downstream shift reactors,
product and fuel processing technology [1,2]. For example, the membrane separators or pressure swing adsorption are
production of Fischer–Tropsch diesel fuel may require a H2/CO employed to meet the ratio requirement [3,6]. This adds cost
syngas ratio from less than one to over two depending on the and complexity to the overall process.
catalyst and specific technology used [1]. Oxosynthesis and Steam methane reforming is a well known commercial tech-
other processes such as dimethyl ether synthesis generally nology and is often a preferred choice for hydrogen production
require a H2/CO ratio of 1 [2]. There are several commercial from methane. It has been well established that the presence of

⁎ Corresponding author. Bourns College of Engineering, Center for Environmental Research and Technology, University of California,
Riverside, 1084 Columbia Ave, Riverside, CA — 92507, United States. Tel.: +1 951 781 5771; fax: +1 951 781 5790.
E-mail address: [email protected] (C.S. Park).

0378-3820/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2008.09.011

Please cite this article as: A.S.K. Raju, et al., Synthesis gas production using steam hydrogasification and steam reforming,
Fuel Processing Technology (2008), doi:10.1016/j.fuproc.2008.09.011
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2 F U E L P RO C ES S IN G T EC HN O L O G Y X X (2 0 0 8) XXX – XXX

carbon dioxide in a conventional steam methane reformer feed inhibiting effect on CH4 conversion. Similar results were ob-
reduces the product H2/CO syngas ratio [4–6]. The catalytic tained on a Ni/La–Al2O3 catalyst by Olsbye et al. [23].
reaction of methane and CO2 is known as dry reforming. There In contrast, Tsipouriari and Verykios [9] reported that the
has been considerable interest in the dry reforming of methane rate of the reforming reaction was practically unchanged over
since this allows two major greenhouse gases to be utilized a Ni/La2O3 catalyst in the presence of CO. The same study also
simultaneously for the production of synthesis gas. It has been concludes that H2 essentially has no effect on the methane
proposed that the CO2 is shifted to CO and H2O through the reforming activity of the Ni catalyst, but the rate of conversion
reverse water–gas shift (RWGS) reaction and then H2O is reacted of CO2 to CO due to RWGS was found to increase. Experimental
with CH4 to produce syngas during the dry reforming [18]. A work on the steam methane reforming of typical gasification
major disadvantage of dry reforming is the tendency for carbon product gas streams are necessary in order to be able to con-
deposition leading to catalyst deactivation. It has been shown trol the composition of the product syngas.
that this problem can be mitigated by the addition of steam to The objective of the present work is to evaluate the effects of
the process [7–9]. Hence the simultaneous steam and carbon the CO2/CH4 feed gas ratio and the process temperature on the
dioxide reforming of methane, known as the ‘mixed reforming’ mixed reforming reaction under a wide range of steam to
reaction allows some limited control of the H2/CO syngas ratio methane ratios. The experimental work focuses on the H2/CO
while avoiding carbon deposition. Significant research has been and CO/CO2 ratios of the product gas of the steam methane
done on the mixed reforming reaction [7,10–12]. It has been reformer. The H2/CO ratio is an important parameter for further
shown that the presence of carbon dioxide enhances the fuel synthesis whereas a higher CO/CO2 ratio indicates higher
conversion of methane and can have an influence on the H2/ energetic product gas stream. All ratios used in the present work
CO syngas ratio. Other parameters such as temperature, the are on a mole basis. The feasibility of the combined use of steam
steam to methane ratio and the type of catalyst can also hydrogasification and steam reforming to produce a syngas with
influence this ratio. These studies have been primarily focused a highly flexible H2/CO ratio is evaluated in this paper through
on the use of a small amount of steam to avoid carbon depo- experimental and simulation work. This has been accomplished
sition and also to obtain a final syngas ratio of 1 to 2 [4,5,13]. by reforming typical steam hydrogasification reactor (SHR)
Therefore, these studies have been performed over narrow feed product gas using a commercial steam reforming catalyst and
ratios of methane to carbon dioxide and methane to steam. comparing the experimental results with theoretical calculations.
Our laboratory has shown that the hydrogasification of
carbonaceous matter in the presence of steam significantly
enhances the rate of methane formation [15]. This process, 2. Syngas generation by coupled steam
known as steam hydrogasification, can be used to generate a hydrogasification and reforming
methane rich gas stream from carbon-containing feedstocks.
The steam hydrogasification product gas is ideally suited for Steam hydrogasification is a thermo-chemical process where a
reforming to produce synthesis gas due to the presence of a carbon-containing solid feedstock is converted into a methane
significant amount of methane and unreacted steam. The rich gas stream in the presence of steam and H2. As mentioned
production of synthetic liquid fuels using syngas from a earlier, experimental and simulation work performed earlier
hydrogasification reactor directly coupled to a reforming have demonstrated that the enhanced methane production
process have been successfully demonstrated in our laboratory from steam hydrogasification can be combined with steam
using several carbonaceous feed stocks [14,16]. The gasifier reforming to generate synthesis gas with a flexible H2/CO ratio
products from this process also contain significant amounts of from a number of carbonaceous feed stocks. An important
CO2, H2 and CO in addition to methane and steam. To our advantage of this process is the fact that the final H2/CO ratio of
knowledge experimental and modeling results have not been the synthesis gas can be controlled simply by altering the H2O/C
published on mixed reforming of a steam hydrogasification and H2/C ratio of the SHR feed, as shown in the next section [25].
product gas. The effect of H2 and CO on steam reforming in the The details of this process have been published elsewhere,
absence of CO2 has been reported in the literature. The effect of although a brief description of the technology is presented here
hydrogen on the catalytic activity was found to be complex. The [14,17]. Fig. 1 shows a schematic diagram of the process.
methane reforming reaction was inhibited by hydrogen in the The carbonaceous feed such as biomass, coal or biosolids
relatively lower temperature range of 400–600 °C. At higher and the water are fed into the steam hydrogasification reactor
temperatures around 700 °C, no inhibition was observed. (SHR) as a slurry along with the H2. The slurry feed eliminates
Numaguchi et al. [21] state that the activity of the catalyst was the need for drying the feedstock and allows the feed to be
recovered under most conditions after the stopping of H2 pumped in to the reactor [26]. Contaminants such as sulfur,
addition. Lemonidou et al. [13] conducted experiments over a chlorine and other trace metals present in the SHR product gas
Ni/CaO–Al2O3 catalyst at atmospheric pressure to study the must be removed since the steam methane reformer (SMR) is a
effect of H2 and CO presence in the feed. They have reported that catalytic reactor. This task is accomplished using a warm-gas
at a temperature of 630 °C, the presence of hydrogen inhibits CH4 cleanup unit that operates at a temperature higher than the dew
conversion and at the same time has a positive effect on the CO2 point of water, allowing the unreacted steam to be retained in
conversion. These results are in agreement with the experi- the product gas stream and hence enabling the process to retain
mental work on Ni based catalysts by Bradford and Vannice [22]. most of the sensible heat in the gas stream. The clean gas
Under the same conditions, Lemonidou et al. also note that the stream containing significant amounts of methane and steam is
presence of CO has a negative effect on the conversion of CO2. converted into a clean synthesis gas in the steam methane
This is clearly due to the WGS shift reaction. Overall, CO has an reformer (SMR). The syngas from the SMR can be used in a fuel

Please cite this article as: A.S.K. Raju, et al., Synthesis gas production using steam hydrogasification and steam reforming,
Fuel Processing Technology (2008), doi:10.1016/j.fuproc.2008.09.011
 ARTICLE IN PRESS
F U E L P RO C ES S I NG T EC H NOL O G Y X X (2 0 0 8) XX X– XXX 3

Fig. 1 – Schematic diagram of the coupled steam hydrogasification and reforming process.

synthesis process such as a Fischer–Tropsch Reactor (FTR) to models and physical/chemical property databases. A brief
generate synthetic hydrocarbon fuels. The syngas can also be description of the original process model used to perform the
used for power generation if desired. The syngas generated by simulations is given below.
the SMR has a higher H2/CO ratio than is normally required for The model simulates the steam hydrogasification block
the production of fuels such as the Fischer–Tropsch liquids. The using three units, the decomposition, pyrolysis and gasifica-
excess H2 from the syngas is separated using a polymer tion. A non-conventional feedstock mixed with water in slurry
membrane or a pressure swing adsorption unit and is fed into form was fed into the SHR along with the hydrogen at
the SHR as feed, eliminating the need for a separate source of H2 predetermined H2/C mole ratio and water/feed mass ratios.
for the process. It should be noted that the CO2 can also be The gasification product gas compositions were evaluated
removed after the SMR for potential sequestration purposes. through Gibbs free energy minimization. The SMR was
The product gas streams from typical gasification processes simulated using a built-in equilibrium block. The reactions
contain varying quantities of H2, CO, CO2, CH4, NH3, etc. The considered in the SMR are given below.
steam methane reformer requires a steam/CH4 ratio of 3 or
CH4 þ H2 O↔CO þ 3H2 ΔH ¼ 206kJ=mol ð1Þ
higher in order to operate efficiently. In addition, the effect of H2
and CO on the mixed reforming process has not been clearly CH4 þ 2H2 O↔CO2 þ 4H2 ΔH ¼ 165kJ=mol ð2Þ
established in the literature. In order for a steam reformer to
CH4 þ CO2 ↔2CO þ 2H2 ΔH ¼ 247kJ=mol ð3Þ
produce a synthesis gas of desired composition using the
gasifier product as feed, it is necessary to maximize the amount CO þ H2 O↔CO2 þ H2 ΔH ¼ −40kJ=mol ð4Þ
of methane and also to maintain steam/CH4 ratio of 3 or higher
The Fischer–Tropsch reactor block used an external model,
in the gasifier product gas. Current literature does not have data
which was called by the Aspen Plus through a FORTRAN
on the reforming of typical steam hydrogasification product gas
module. This external model was empirically developed by
streams and hence experimental work is necessary. Two sets of
Hamelinck et al., to predict the selectivity of the Fischer–
reforming experiments were conducted in this study, each with
Tropsch process and has been verified to be in accordance
a feed representing different SHR exit compositions. Table 1
with experimental results performed on cobalt catalysts [24].
shows the SMR inlet gas flow rates for the two cases. These feed
As the H2O/Feed and H2/C ratios of the SHR feed are varied,
gas compositions were determined using simulation results.
the SHR product gas composition changes accordingly. Since
The gasifier was operated at 800 °C and 400 psi pressure for Case
1 and at 700 °C and 400 psi for Case 2.

3. Aspen simulations

A detailed process model using Aspen Plus has been devel-

oped and used to predict process behavior, mass and energy
balances. Aspen Plus has the ability to handle non-conven-
tional feed stocks and process streams using built-in process

Table 1 – Input flow rates for SHR product gas reforming

tests
Input Case 1 Case 2
component 3
Flow rate (cm /min) Flow rate (cm3/min)

CH4 (g) 250 270

H2O (l) 0.6 0.7
CO2 (g) 160 110
Fig. 2 – Effect of SHR feed ratios on the H2/CO ratio of the SMR
H2 (g) 600 360 product gas. ♦ — H2O/Wood of SHR feed = 1, ■ — H2O/Wood of
CO (g) 100 20 SHR feed = 2, ▲ — H2O/Wood of SHR feed = 3, ● — H2O/Wood
of SHR feed = 4.

Please cite this article as: A.S.K. Raju, et al., Synthesis gas production using steam hydrogasification and steam reforming,
Fuel Processing Technology (2008), doi:10.1016/j.fuproc.2008.09.011
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4 F U E L P RO C ES S IN G T EC HN O L O G Y X X (2 0 0 8) XXX – XXX

the SHR product gas stream is fed directly into the SMR after with the product and operating manuals. The catalyst perfor-
gas cleanup, the SHR feed ratio changes affect the SMR mance was found to be satisfactory although the results of these
product gas composition [17]. Hence, the H2/CO ratio of the tests are not presented here. The CO2 feed experiments were
syngas can be controlled directly by varying the SHR feed. conducted for CO2/CH4 input ratios of 0 to 2 with a constant
Fig. 2 shows that varying the feed composition of SHR gen- steam/CH4 ratio of 3. A second set of experiments with a
erates a wide range of syngas ratios. In this case, the car- constant CO2/CH4 ratio of 0.5 was conducted for steam/CH4
bonaceous feedstock was assumed to be wood. ratios of 3 to 5. The flow rate of methane was fixed at 250 cm3/
min (ml/min) for all the experiments. Each specific feed ratio
was tested under four different temperatures between 700 °C
4. Experimental section and 850 °C. The pressure was maintained at 25 psi for all the
tests. The catalyst was purged with steam after each test in
A standalone SMR was constructed for these experiments. The order to avoid potential carbon deposition.
packed bed reactor was 61.5 cm long with an i.d. of 0.9 cm and
was constructed using inconel alloy. The experimental set up is
shown in Fig. 3. A steam generator consisting of a heated coil 5. Results and discussion
and a SSI Series I HPLC pump was connected to the reactor inlet.
The reactor was heated using two tubular electric heaters and 5.1. Effect of CO2/CH4 ratio
the pressure was controlled using a backpressure regulator. A
commercial G-90-0-1 (Sud-Chemie Inc.) steam reforming cata- The syngas produced by the steam reforming reaction has a
lyst was used for all the experiments. The catalyst has a nominal theoretical hydrogen to carbon monoxide ratio of 3 according to
nickel oxide content of 14 wt.% supported on aluminum oxide Eq. (1). The actual ratio is usually higher due to the water–gas
along with a small amount of calcium oxide. The reaction shift reaction (Eq. (4)), which is thermodynamically favored only
product gases were passed through a condenser for water at lower temperatures [18]. The water–gas shift reaction (WGS)
removal before being analyzed in real time using a residual gas proceeds in the reverse direction (RWGS) at higher tempera-
analyzer. The catalyst in the oxidized state must be reduced tures. The mole fractions of hydrogen and carbon monoxide
before the start of the reforming experiments in order for it to be through a steam reformer can be expressed in terms of the rate
active. The catalyst reduction was achieved by flowing hydro- constants of the steam reforming and water–gas shift reactions
gen through the catalyst filled reformer at 800 °C. The catalyst and the mole fractions of the species [6].
needs to be reduced only once and after the reduction, it must
not be exposed to air or oxygen. Background tests of steam ½KSMR KWGS 0:25 ½yCH4 0:25 ½yH2 O 0:5
yH2 = ð5Þ
reforming in the absence of CO2 feed were performed under
atmospheric pressure for a wide range of temperatures before
½P 0:5
d ½yCO2 0:25

the actual set of experiments were initiated. The purpose of the ½KSMR 0:25 ½yCH4 0:25 ½yCO2 0:75
background experiments was to test the activity of the catalyst yCO = ð6Þ
and to ensure that the catalyst performance was in compliance
½KWGS  0:75
½P 0:5
d ½yH2 0:5

Hence, the H2/CO ratio of the product synthesis gas can be

expressed as

½yH2 0:5 ½yH2 O 0:5

yH2 =yCO = ½KWGS  ð7Þ
d ½yCO2 

The syngas ratio of the product stream is expected to

decrease as CO2 increases. The H2/CO and CO/CO2 ratios
obtained from experiment and simulation over a wide range of
CO2/CH4 feed ratios are compared in Fig. 4. The experimental
results are generally in good agreement with the simulation.
The theoretical H2/CO ratio according to Eqs. (1) and (3)
decreases from 3 to 1 as the reaction shifts from pure steam
reforming to pure CO2 reforming. However it can be seen from
Fig. 4 that the actual ratio decreases from above 5 to 1. As
expected, the H2/CO ratio steadily decreases with increasing
amount of CO2 in the feed.
The decrease in the H2/CO ratio is caused by an increase of
CO2 reforming and the reverse WGS reaction. It has been
reported that the conversion of methane is enhanced by the
Fig. 3 – Block diagram of the steam methane reformer. 1—Gas increase in CO2 due to the dry reforming reaction, i.e., the
cylinders and mass flow controllers, 2—water container, methane consumption increases with the increase in the CO2
3—pump, 4—steam generator, 5—reactor and heaters, 6—heat partial pressure [13,20]. The results are in agreement with
exchanger, 7—water condenser, 8—back pressure regulator, reported trends and are comparable to that of similar studies
9—dry gas meter, 10—residual gas analyzer and vent line. [4,5], although literature data are not available for the wide

Please cite this article as: A.S.K. Raju, et al., Synthesis gas production using steam hydrogasification and steam reforming,
Fuel Processing Technology (2008), doi:10.1016/j.fuproc.2008.09.011
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F U E L P RO C ES S I NG T EC H NOL O G Y X X (2 0 0 8) XX X– XXX 5

Fig. 4 – Effect of CO2/CH4 ratio of the feed stream on the H2/CO and CO/CO2 ratios of the product synthesis gas. Steam/CH4 ratio of
○
feed = 3, T = 700 °C, P = 25 psi. ■ — Experimental H2/CO, Δ — simulation H2/CO, + — experimental CO/CO2, — simulation CO/CO2.

range of CO2/CH4 ratios used here. Choudhary and Rajput [5] at a constant CO2/CH4 ratio of 0.5. It is recommended that a
concluded that the relative composition of steam and CO2 in minimum steam to methane ratio of 2 be maintained for
the feed has an influence on the final H2/CO ratio as observed commercial reforming catalysts in order to avoid carbon
here. The exit CO/CO2 ratios from the experiments are deposition on the catalyst. The methane reforming reaction
relatively stable for all the CO2/CH4 feed ratios. There was no is dominant over the dry reforming reaction in the presence of
pressure drop observed across the reactor throughout the excess steam and as such, the selectivity for hydrogen is
course of the experiments, indicating that there was no higher than that of carbon monoxide. Hence, the H2/CO ratio
significant carbon deposition, i.e., coking in the reactor. The increases with the increase in the steam/CH4 feed ratio. The
tendency for carbon formation depends on the H/C ratio of the simulation results are in good agreement with the experi-
feed under given conditions and the results demonstrate that mental data. The higher steam/CH4 ratio also enhances the
even in the high CO2 feed experiments, coke formation water–gas shift reaction, as confirmed by the decrease in the
through methane degradation or the Boudard reaction is CO/CO2 ratio of the product stream (Fig. 5). The present
avoided by the presence of steam. The equilibrium composi- experimental data have been compared with literature data
tions calculated using the simulation tool are in reasonable for experiments conducted under similar conditions. Choudh-
agreement with the experimental results as shown in Figs. 4 ary and Rajput [5] conducted experiments over a NiO–CaO
and 5. catalyst, primarily focused on the catalytic activity and the
coking tendencies. Effendi et al. [4] have conducted experi-
5.2. Effect of steam to methane input ratio mental studies of the reforming of a model biogas with a CH4/
CO2 ratio of 1.5 using a Ni/Al2O3 catalyst. The experimental
The effect of steam to methane ratio on the H2/CO ratio of the results of these studies have been compared with the present
syngas is shown in Fig. 5. All the experiments were conducted data in Fig. 6. The results of Choudhary and Rajput are in good
agreement with the current data, whereas the Effendi et al.

Fig. 5 – Effect of steam/CH4 ratio of the feed stream on the

H2/CO and CO/CO2 ratios of the product synthesis gas. CO2/
CH4 ratio of feed = 0.5, T = 700 °C, P = 25 psi. ■ — Experimental Fig. 6 – Comparison with literature data. ■ — Experimental
H2/CO, Δ — simulation H2/CO, + — experimental H2/CO, Δ — simulation H2/CO, + — H2/CO data from Choudhary
CO/CO2, ○ — simulation CO/CO2. and Rajput [5], ◊ — H2/CO data from Effendi et al. [4].

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Fuel Processing Technology (2008), doi:10.1016/j.fuproc.2008.09.011
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6 F U E L P RO C ES S IN G T EC HN O L O G Y X X (2 0 0 8) XXX – XXX

data have a lower H2/CO syngas ratio. This lower H2/CO syngas
ratio is due to the higher CO2/CH4 feed ratio and also due to
varying feed gas/steam volume ratios.

5.3. Effect of temperature

The changes in the product gas H2/CO and CO/CO2 ratios for
different temperatures are presented in Fig. 7. It can be seen
that the selectivity towards CO increases with increasing
temperatures due to the occurrence of the reverse water–gas
shift reaction. This results in a reduction of the H2/CO ratios
with increasing temperatures. These trends are in agreement
with literature data [4,5]. As expected, the conversion of the
reactants also increased with temperature, with methane
conversion reaching 100% as the temperature reaches 800 °C
Fig. 8 – Effect of temperature on the reforming of steam
and the dry reforming reaction becomes dominant at higher
hydrogasification product gas — Case 1. Feed steam/CH4 = 3,
temperatures. Unlike partial oxidation, the H2/CO ratio of the
CO2/CH4 = 0.64, H2/CH4 = 2.4, CO/CH4 = 0.34. ■ — Experimental
syngas generated by the mixed reforming reaction changes H2/CO, Δ — simulation H2/CO, ○— experimental
with changing temperature [19]. Hence, the temperature is an CO/CO2, + — simulation CO/CO2.
important parameter in determining the H2/CO ratio of the
product gas.
feed gas compositions for the reformer. The experimental
5.4. Steam reforming of steam hydrogasification product results along with the experimental conditions are shown in
gas Figs. 8 and 9 and the feed gas compositions are given in
Table 1. The reformer feed rates for Case 1 were based on a
As mentioned earlier, experimental data on the reforming of gasifier simulation performed under 800 °C and 400 psi pres-
SHR product gas is currently not available in the literature. sure. The reformer feed rates were based on gasifier operating
Although experimental work has been performed on the conditions of 700 °C and 400 psi for Case 2.
effects of H2 and CO on the methane reforming reaction, It can be seen from Fig. 8 that for Case 1, the H2/CO ratio of
conclusive data on the effect of the presence of H2 and CO on the product synthesis gas varied from 4.3 to 3.7, while the CO/
the mixed reforming reaction is not available. Hence, it is very CO2 ratio from 1.9 to 2.9. Fig. 9 shows that the H2/CO and CO/
important to conduct experimental studies of the reforming of CO2 ratios varied from 4.8 to 4.1 and 2.0 to 3.3 respectively for
typical gasification product gas streams in order to be able to Case 2 depending on the reaction temperature. These results
determine the conditions that will allow the production of a show that the H2/CO and CO/CO2 ratios of the syngas varied
syngas of the desired composition. Two sets of reforming considerably depending on the feed composition. The experi-
experiments were conducted as part of this study, each with a mental results reasonably agree with that of the simulation
feed representing different gasifier exit compositions as results for most of the cases, although there is a difference,
described earlier. The SHR gasifier simulations were per- especially with respect to the CO/CO2 ratios, as can be seen in
formed using the Aspen Plus software as detailed in Section 3. Figs. 5 and 9. These differences may be attributed to the
The results of these simulations were used to determine the

Fig. 9 – Effect of temperature on the reforming of steam

Fig. 7 – Effect of temperature on the H2/CO and CO/CO2 ratios hydrogasification product gas — Case 2. Feed steam/
of the product synthesis gas. Steam/CH4 = 3, CO2/CH4 ratio of CH4 = 3.2, CO2/CH4 = 0.4, H2/CH4 = 1.3, CO/CH4 = 0.07.
feed = 0.5, P = 25 psi. ■ — Experimental H2/CO, Δ — simulation ■ — Experimental H2/CO, Δ — simulation
H2/CO, + — experimental CO/CO2, ○ — simulation CO/CO2. ○
H2/CO, — experimental CO/CO2, + — simulation CO/CO2.

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Fuel Processing Technology (2008), doi:10.1016/j.fuproc.2008.09.011
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F U E L P RO C ES S I NG T EC H NOL O G Y X X (2 0 0 8) XX X– XXX 7

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Please cite this article as: A.S.K. Raju, et al., Synthesis gas production using steam hydrogasification and steam reforming,
Fuel Processing Technology (2008), doi:10.1016/j.fuproc.2008.09.011