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4182 Energy & Fuels 2008, 22, 4182–4189

Experimental Study of Model Biogas Catalytic Steam Reforming:

1. Thermodynamic Optimization
Mojdeh Ashrafi,* Tobias Pröll, Christoph Pfeifer, and Hermann Hofbauer
Institute of Chemical Engineering, Vienna UniVersity of Technology, Getreidemarkt 9/166,
1060 Vienna, Austria

ReceiVed February 5, 2008. ReVised Manuscript ReceiVed June 13, 2008

The general objective of this investigation is the development of a biogas steam reforming concept and to
bring it to a state of readiness for industrial demonstration. Through biogas steam reforming, H2-rich synthesis
gas will be produced from which gas engines benefit in terms of higher efficiency and lower NOx emissions
compared to direct combustion of raw biogas. Furthermore, pure hydrogen can be produced out of a renewable
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source using this route. The aim of this experimental study is to determine the operational envelope of biogas
steam reforming by optimizing the performance of an externally heated reformer in terms of CH4 conversion,
H2 yield, and catalyst efficiency. Therefore, a clean model biogas, using a constant molar ratio of CH4/CO2 )
1.5, is contacted to different supported nickel catalysts in a fixed bed reactor. The influence of temperature,
water vapor portion, and contact time is analyzed. The resulted reformate composition is plausible with respect
to thermodynamic equilibrium calculations. On the basis of the results, the steam/carbon molar ratio in the
range of 3-4 and operating temperature of 700 °C are found as the optimal operating conditions. In addition,
the catalyst activity, thermal stability, and resistance to carbon formation have been observed as critical
parameters on the application of different kinds of catalysts.

1. Introduction high-quality fuels as an important intermediate in the industrial

syntheses of a wide range of chemicals.7–10
Limited sources of fossil fuels and also global climate changes This work contributes to the current discussion about H2 as
caused by CO2 emissions are currently discussed around the a future energy carrier, where the available sustainable sources
world. Renewable and also green sources of energy are being for the hydrogen required are still raising questions.11,12 Cur-
sought as alternatives to replace fossil fuels. Hence, research rently, hydrogen is, because of economics, produced from fossil
activities on this topic are gaining more and more importance.1,2 fuels through steam reforming.13–16 In analogy, steam reforming
of biogas can also be considered as a possible process for the
Biomass is an attractive renewable energy source. Sustainable
production of H2-rich synthesis gas.7,8 Further steps can either
use of biomass for energy production does not contribute to
be shift conversion to obtain a H2/CO2 gas mixture and, after
CO2 emissions production but has a high CO2 abatement selective CO2 removal, pure H2 from renewable sources or, on
potential.3 Biogas, with a typical composition of 50-75 mol % the other hand, the combustion in gas engines obtaining higher
CH4, 25-45 mol % CO2, 2-7 mol % H2O, 0-2 mol % N2, engine efficiencies and lower NOx emissions. The latter is the
0-1 mol % H2, 0-2 mol % O2, and 0-2 mol % H2S, produced
from anaerobic digestion of biomass has, up to now, been used (7) Effendi, A.; Zhang, Z. G.; Hellgardt, K.; Honda, K.; Yoshida, T.
mainly for combined heat and power production.4–6 Today, Steam reforming of a clean model biogas over Ni/Al2O3 in fluidized- and
fixed-bed reactors. Catal. Today 2002, 77, 181–189.
biogas has also received increased attention for upgrading to (8) Effendi, A.; Hellgardt, K.; Zhang, Z. G.; Yoshida, T. Optimising
H2 production from model biogas via combined steam reforming and CO
shift reactions. Fuel 2005, 84, 869–874.
* To whom correspondence should be addressed. Telephone: (43) 1-58- (9) Zhang, Z. G.; Xu, G.; Chen, X.; Honda, K.; Yoshida, T. Process
801-159-74. Fax: (43) 1-58-801-159-99. E-mail: mashrafi@ development of hydrogenous gas production for PEFC from biogas. Fuel Process. Technol. 2004, 85, 1213–1229.
(1) International Energy Agency. Renewables in global energy supply. (10) Xu, G.; Chen, X.; Honda, K.; Zhang, Z. G. Producing H2-rich gas
An IEA fact sheet: from simulated biogas and applying the gas to a 50 W PEFC stack. AIChE
factsheet.pdf, 2007. J. 2004, 50 (10), 2467–2480.
(2) Maney, J. N. Y. U. Carbon dioxide emissions, climate change, and (11) Rostrup-Nielsen, J. R.; Rostrup-Nielsen, T. Large-scale hydrogen
the clean air act: An analysis of whether carbon dioxide should be listed as production. CATTECH 2002, 6 (4), 150–159.
a criteria pollutant. EnViron. Law J. 2005, 13, 298–378. (12) Zittel, W.; Wurster, R. Hydrogen in the energy sector. Ludwig-
(3) Möllersten, K.; Yan, J.; Moreira, J. R. Potential market niches for Boelkow-Systemtechnik GmbH,
biomass energy with CO2 capture and storage opportunities for energy energiew-eng.html, 1996.
supply with negative CO2 emissions. Biomass Bioenergy 2005, 25, 273– (13) Twigg, M. V. Catalyst Handbook, 2nd ed.; Manson Publishing:
285. London, U.K., 1996.
(4) Biogas Handbook BaVaria; Bavarian State Ministry of the Environ- (14) Rostrup-Nielsen, J. R.; Sehested, J. Hydrogen and synthesis gas
ment: Rosenkavalierplatz 2, 8 1925 München, 2004; Chapters 1-3. by steam and CO2 reforming. AdV. Catal. 2002, 47, 65–139.
(5) Kaltwasser, B. RegeneratiVe Energieerzeugung durch anaerobe (15) Cromarty, B. Effective steam reforming of mixed and heavy
Fermentation organischer Abfaelle in Biogasanlagen, 1st ed.; Bauverlag: hydrocarbon feedstocks for production of hydrogen. Presented at NPRA
Wiesbaden and Berlin, Germany, 1980. Annual Meeting, San Francisco, CA, 1995.
(6) Kaltschmitt, M.; Hartmann, H. Energie aus Biomasse; Springer (16) Rostrup-Nielsen, J. R. Catalytic Steam Reforming; Springer Pub-
Publishing: Berlin, Germany, 2001. lishing: New York, 1984.

10.1021/ef800081j CCC: $40.75  2008 American Chemical Society

Published on Web 09/10/2008
Biogas Steam Reforming Energy & Fuels, Vol. 22, No. 6, 2008 4183

short-term objective of the present investigative work; the results The carbon, which is considered in this definition, is the
will be applied to optimize reformer operation at the anaerobic fraction of organic carbon that takes part in carbon-forming
biomass fermentation plant in Strem, Austria, where a test reactions. Here, a general definition of organic carbon is
facility for autothermal biogas steam reforming with subsequent considered. In biogas, organic carbons are presented in CH4
combustion of the reformate in a 500 kWel gas engine is and CO2. Because this parameter is considered for coking
currently investigated. The efficiency benefits of H2- and CO- tendency and CO2 does not have any influence on carbon
rich fuels for gas engines is discussed in detail by Herdin et al. formation, CO2 is not considered as a carbon carrier. Therefore,
and Gruber et al.17,18 On the basis of these investigations, also, CH4 is the only compound that is relevant for the S/C ratio.
CO contributes to performance improvements of gas engines, Space velocity (SV):
however, in a smaller extent compared to H2.
In a previous study, the high efficiency of nickel was observed V̇in
SV ) (m3 h-1 kg-1) (6)
also for biogas steam reforming.19 Therefore, different nickel- mcat
based catalysts are tested in this work. Among them, two
commercially available catalysts are selected according to The conversions of substance x:
several criteria (e.g., particle size, reactivity, and carbon
Ṅx,BG - Ṅx,SG
formation) for further thermodynamic investigations. Through conversion (x) ) (%) (7)
the experiments, the steam/carbon ratio in the reformer, operat- Ṅx,BG
ing temperature, and space velocity are optimized in terms of H2 yield:
parameters, such as CH4 conversion, H2 yield, and H2/CO ratio.
The CH4/CO2 molar ratio in the raw biogas is normally ṄH2,SG 1
determined by the biomass feedstock and operating parameters H2 yield ) (8)
of the fermenter. If a substantial increase in efficiency for higher ṄCH ,BG 4
CH4/CO2 ratios (i.e., lower CO2 contents) were obtained for a
The H2 yield is defined as a factor showing the molar ratio
plant concept, bulk CO2 removal prior to steam reforming can
of the produced H2 to CH4 in the raw biogas provided to the
be considered.20
system. The factor 1/4 is determined by the fact that maximal 4
mol of H2 can be produced from 1 mol of CH4.
2. Theory
CO selectivity:
2.1. Main Reactions. The global steam reforming mecha-
nism of biogas consists of four reversible reactions. The steam CO selectivity ) (9)
methane reforming reactions 1 and 3 are linked by the YCO,SG + YCO2,SG
water-gas shift reaction 2 and the methane carbon dioxide
During the calculations, it is assumed that the reaction of
reforming reaction 4:
inlet gases produces CO, CO2, H2, and solid C and unreacted

CH4 + H2O T CO + 3H2 ∆rH298 K ) +206 kJ/mol
( ) (1) CH4 and H2O remain in the gas. The calculations of all outlet

fluxes are based on the carbon, oxygen, and hydrogen mass
CO + H2O T CO2 + H2 ∆rH298 K ) -41 kJ/mol
( ) (2) balance. The deposited solid carbon amount can be calculated
◦ using the mass balance equations. Because no carbon deposition
CH4 + 2H2O T CO2 + 4H2 ∆rH298 K ) +165 kJ/mol
( ) (3)
and catalyst deactivation is observed during these experiments,

CH4 + CO2 T 2CO2 + 2H2 ∆rH298 K ) +247 kJ/mol
( ) (4) solid carbon formed is assumed to be zero throughout the
Because of the high CO2 portion in the biogas during CH4 calculations.
reforming with water vapor, dry reforming of methane (reaction It is important to estimate the amount of outlet effluent flux
4) will also proceed. Dependent upon the steam/methane ratio of H2O. In this experimental system, it is impossible to measure
and CO2 content in the feed gas, CH4 is more or less reformed the unreacted H2O amount at the same time with other outlet
with H2O or CO2. Thereby, the equilibrium of the water-gas gases, because H2O gas liquefies easily below 100 °C. Therefore,
shift reaction and portion of H2 and CO in the synthesis gas it should be calculated using the oxygen and hydrogen mass
are effected. balances or measured gravimetrically. The unreacted H2O
2.2. Definitions and Calculation Method. The parameters, amount is also separated in water traps and weighted during
concerning the description of reactions, reaction conditions, and the experiments. Because it can be dried only to a saturation
also evaluation of the results, are defined as follows: temperature of approximately 15 °C, a small amount of
Steam/carbon molar ratio in the reformer (S/C): unreacted water remains in the synthesis gas. After the deter-
mination of synthesis gas composition, this small amount of
YH2O,in water can be determined through iterative calculations.
S/C ) (mol/mol) (5)
ṁH2O,water traps
ṁH2O,out ) + ṁH2O,dried synthesis gas (kg/h) (10)
(17) Herdin, G. R.; Gruber, F.; Klausner, J.; Robitschko, R.; Plohberger, tE - tS
D. Use of hydrogen and hydrogen mixture in gas engines and potentials of
NOx emissions. Presented in ARES-ARICE Symposium on Gas Fired ṁH2O,dried synthesis gas ) ṁSGxs (kg/h) (11)
Reciprocating Engines, Canada, 2005.
(18) Gruber, F.; Herdin, G. R. The use of H2-content process gas in gas where xs is the mass-based saturation degree in (kgH2O /kgSG).
engines. Presented in ASME International Combustion Engine Division,
Spring Technical Conference, Chicago, IL, 1997.
To check the plausibility of the experimental results, the
(19) Kolbitsch, P.; Pfeifer, C.; Hofbauer, H. Catalytic steam reforming thermodynamic equilibrium of reactions 1 and 2 (reactions 3
of model biogas. Fuel 2008, 87, 701–706. and 4 are dependent) is calculated for each experiment based
(20) Ashrafi, M.; Pröll, T.; Hofbauer, H. Biogas upgrading to hydrogen on the given input stream and the prevailing temperature in the
rich gas by steam reforming: Comparison and optimization of plant
configurations. Proceeding of the World Bioenergy Conference, Sweden, reformer. The equilibrium concentrations are calculated by the
2006. IPSEpro steady-state simulation program using the minimization
4184 Energy & Fuels, Vol. 22, No. 6, 2008 Ashrafi et al.

Scheme 1. Flow Chart of the Experimental Setup Table 1. Parameters Used for the Empty Pipe Experiment
parameter unit value
inlet CH4 mol % 23.15
inlet CO2 mol % 15.50
inlet H2O mol % 61.35
inlet CH4 (wf) mol % 60
inlet CO2 (wf) mol % 40
CH4/CO2 ratio mol/mol 1.5
S/C ratio mol/mol 2.72
reactor temperature °C 700
test duration min 180

After condensation of the steam and drying of the gas mixture, the
effluent is sent to the analysis section.
3.2. Model Biogas and the Used Catalysts. Because no natural
biogas is available at the equipment location, model biogas
(synthetic biogas), containing 60% CH4 and 40% CO2, is used
throughout this investigation. H2S is usually present in biogas, and
even very small concentrations of it can lead to significant catalyst
of Gibbs free-energy method. The thermodynamic property data deactivation.13,14,16 A smaller effect on catalytic activity has been
has been taken from Burcat and McBride.21 reported for NH3.8 The experiments in the present work are executed
in the absence of sulfur and ammonia. Thus, different catalyst
activity, stability, and resistance against coking are studied. Further
3. Experimental Section investigations on catalyst poisoning will be presented in the
subsequent part of this paper. However, in traditional commercial
3.1. Experimental Setup. A schematic diagram of the experi-
applications, sulfur is removed prior to the steam reforming step.
mental equipment used is given in Scheme 1. It consists of three
The most commonly encountered catalysts for methane steam
main sections: feed section, reaction section, and analysis section.
reforming are nickel-based.13,14,16,22 In this work, two commercially
The feed section supplies the components of interest, such as
available catalysts, both with the description “G-90” from the
CH4, CO2, H2O, and N2. Nitrogen is used as the carrier gas, needed
company Sued-Chemie, are used in the thermodynamic investiga-
for heating and cooling the reactor. After pressure reduction from
tions. The catalysts are in spherical form and termed in the
the gas cylinders, the flow rate of each gas is controlled by a mass
flow controller at the desired value. After mixing, the model biogas following: catalyst A (diameter ) 5-7 mm) and catalyst B
flows into the preheater. The necessary water is deionized before (diameter ) 2-4 mm).
being added to the biogas and delivered by a peristaltic pump to 3.3. Execution of the Experiments. In each experiment, the
the evaporator, where it is vaporized and simultaneously mixed catalyst bed is initially heated to the desired temperature at a heating
with other gases. The model biogas/water mixture reaches the rate of approximately 6-7 °C/min with the help of a nitrogen flow
desired temperature in the preheater/evaporator section. of 300 L/h. In the second step, steam is introduced into the reactor
Subsequently, the gas mixture flows into the reactor and over for about 15 min and then both reactants, CH4 and CO2, are supplied
the catalyst bed. A straight section serves as the reactor, while the and nitrogen is terminated. If methane alone is supplied into the
upper section is used as the combined preheater/evaporator. The reactor, there will be serious coke formation on the metallic Ni
fixed bed reactor and preheater/evaporator section used in the sites. The start-up process for each experiment lasts up to 3 h until
present work are made from a stainless-steel (1.4841, X15CrNiSi25- the reactor reaches a steady-state condition and the measuring is
20) tube enclosed by three electric resistance heating coils. The started.
catalytic bed, supported on a metallic mesh, is 47 mm in diameter The amount of water in the beaker is gravimetrically determined
and can reach a maximum length of 700 mm. Because of the short at the beginning and end of each test run to calculate the actual
length of the catalyst bed in the present experiments (less than 100 steam/carbon ratio. The water content of the water traps is also
mm), the reactor is operated at nearly atmospheric pressure and measured approximately once per hour, and they are emptied
any pressure profile inside the reactor can be neglected. thereby.
Because of simplicity, a fixed-bed reactor is used here. In The experiments are terminated by introducing a nitrogen flow
traditional steam reforming configurations, a low-temperature shift of 300 L/h and switching off the gas valves and water pump. The
reactor follows the high-temperature steam reformer, to convert heating coils are then switched off, and the reactor is cooled below
more CO to CO2 through the exothermic shift reaction (reaction 2) 300 °C under N2 flow. The N2 flow is then switched off, and the
and improve H2 production.13,15 However, because CO is a fuel reactor is cooled to room temperature automatically. The shut down
for gas engines, therefore and for means of process simplicity, the process lasts for about 2 h.
shift reactor following the reforming step is avoided here.
The reactor is also electrically heated to apply the necessary heat 4. Results and Discussion
of the endothermic reforming process. A thermocouple is placed
near the heating coil, surrounding the evaporator, and two other 4.1. Empty Pipe Experiment. Because the entire reactor is
thermocouples are located along the axis of the reactor, one before made of stainless steel and this material can exhibit a catalytic
and one after the reactor section. The three thermocouples are effect, the reactor is operated in the first test without a catalyst
connected to the temperature indicator and controller. The heaters to quantify the auto-catalytic effect of the reactor itself. The
are regulated in such a way that all temperature measuring points parameters are shown in Table 1, and the experimental results
(TMP1, TMP2, and TMP3) have the same constant temperature. are shown in Table 2.
In the consequent section of the catalyst bed, the synthesis gas As it can be seen, methane conversion in the absence of
is cooled to ambient temperature. A cold trap at the outlet of the catalyst is low at the experimental conditions used in this work.
reactor is used to condense any water from the product gas stream. Thus, it can be concluded that the auto-catalytic effect of the
reactor material can be neglected.
(21) Burcat, A.; McBride, B. Ideal gas thermodynamic data for
combustion and air pollution use. Technion Israel Institute of Technology,
Aerospace Engineering Report, TAE 804, (22) Beurden, P. V. On the catalytic aspect of steam reforming. ECN,
burcat.html, 1997., 2004.
Biogas Steam Reforming Energy & Fuels, Vol. 22, No. 6, 2008 4185

Table 2. Results of the Empty Pipe Experiment Table 5. Results of the Experiments for Catalyst Activity,
Catalyst B
parameter unit value
outlet CH4 (wf) mol % 56.51 equilibrium
outlet H2 (wf) mol % 3.24 parameter unit value at S/C ) 3.50
outlet CO2 (wf) mol % 39.81 outlet CH4 (wf) mol % 3.88 0.35
outlet CO (wf) mol % 0.45 outlet H2 (wf) mol % 62.05 65.55
CH4 conversion % 2.50 outlet CO2 (wf) mol % 18.69 18.36
H2 yield 0.09 outlet CO (wf) mol % 15.38 15.74
CO2 conversion % -2.57 CH4 conversion % 82.87 98.30
CO selectivity 0.01 H2 yield 2.63 3.17
H2/CO ratio mol/mol 7.23 CO2 conversion % -23.34 -33.23
CO selectivity 0.45 0.46
Table 3. Parameters of the Experiments for Catalyst Activity H2/CO ratio mol/mol 4.04 4.16
parameter unit catalyst A catalyst B
Table 6. Parameters of the Experiments for Optimizing Reactor
CH4/CO2 ratio mol/mol 1.5 1.5 Temperature
S/C ratio mol/mol 3.19 3.50
space velocity m3 kg-1 h-1 18.77 30.07 parameter unit value
reactor temperature °C 700 700 CH4/CO2 ratio mol/mol 1.5
catalyst amount g 110 70 S/C ratio mol/mol 2.71 ( 0.20
catalyst bed height mm 62 45 space velocity m3 kg-1 h-1 16.94 ( 0.74
residence time s 0.20 0.13 reactor temperature °C 600-900
test duration h 8 8×5 catalyst type A
catalyst amount g 110
Table 4. Results of the Experiments for Catalyst Activity, catalyst bed high mm 62
Catalyst A residence time s 0.20
equilibrium test duration min 180
parameter unit value at S/C ) 3.19
The experiment is repeated for catalyst B for totally more
outlet CH4 (wf) mol % 1.74 0.44
outlet H2 (wf) mol % 64.02 65.14
than 40 h. During these experiments, the catalyst remained stable
outlet CO2 (wf) mol % 16.15 17.65 in activity and the product distribution was close to equilibrium.
outlet CO (wf) mol % 18.09 16.77 In this condition, there was no deactivation over more than 40 h.
CH4 conversion % 91.93 97.91 As it can be seen in the results, despite a lower active surface
H2 yield 2.84 3.11 of catalyst A and also the influence of channeling (because of
CO2 conversion % -11.90 -26.57
CO selectivity 0.53 0.49 the larger dimensions), the result obtained with this catalyst is
H2/CO ratio mol/mol 3.54 3.88 better than that of catalyst B. This can be related to the lower
space velocity selected in the experiment with catalyst A.
4.2. Catalyst Activity and Resistance toward Carbon However, in the following experiments to test the influence of
Formation. To obtain acceptable reaction rates, a catalyst is the S/C ratio (presented in section 4.4), the higher activity of
required to accelerate the process. Even more, the catalyst should catalyst B in comparison to catalyst A in the same operating
be stable under the rather extreme conditions under which high conditions and also space velocity is proven.
CH4 conversion can be reached (i.e., high temperatures and high 4.3. Variation of Reaction Temperature. According to the
probabilities of unwanted side reactions involving carbon acceptable results for both catalysts A and B, catalyst A is
deposition).22 Because nickel is economically and highly active selected for further investigations because of its availability. In
in steam methane reforming, it has proven to be very efficient this part, the effect of different operating temperatures is studied
in commercial scale for more than 40 years.13,14 The correct under steam reforming conditions. The experimental parameters
choice of a catalyst can overcome the problems raised by carbon are listed in Table 6. The reaction conditions are employed
formation. considering the commercial steam methane reforming process;
Therefore, six commercially available catalysts are tested to thus, excess steam is used (S/C ) 2.5-3).
determine their activity, stability, and resistance to carbon For the experiment for catalyst A at similar conditions and
formation. Two of them (catalysts A and B, as mentioned again in the absence of H2S, no carbon formation and therefore
before), which have shown the best results, are selected for no catalyst deactivation is observed for about 8 h. The product
further thermodynamics investigations, and the results of the gas composition remained also constant when all experimental
primary experiments are also presented here. According to the parameters were in the steady-state condition. Therefore, 3 h
laboratory scale of the reformer, the proper size and shape of of experiment in the steady-state condition seems to be enough
these two catalysts were also important factors. A reference for each test in this part. The experiments at 600, 650, and 750
temperature of 700 °C is selected to test their activity and °C are performed consequently, while the temperature is
resistance toward carbon formation. According to the lower changed stepwise during the test, and at each temperature,
active surface of catalyst A, a lower space velocity is selected the steady-state condition is reached for at least 180 min. The
for the experiment with this catalyst. Other experimental experiments for 800, 850, and 900 °C are also executed in the
parameters are listed in Table 3. Tables 4 and 5 summarize the same way.
results. The space velocity depends upon the catalyst quantity, the
Both catalysts maintain constant conversion and product adjusted S/C value, and biogas volume flow rate, which are
distribution after about half an hour after the feed inlet dependent upon the temperature. Therefore, to have a constant
throughout the duration of the experiments. SV value, the volume flow rate of the biogas is adapted for
The H2/CO ratio in the run with catalysts A is lower compared each experiment to obtain respective reactor parameters.
to catalyst B, while the methane conversion is higher. This During each experiment, it is observed that the used peristaltic
indicates that the water-gas shift reaction is more favorable pump promotes a constant flow rate. However, the flow rate
when CH4 conversion is relatively low. varied for each experiment. Thus, S/C values and therefore also
4186 Energy & Fuels, Vol. 22, No. 6, 2008 Ashrafi et al.

Table 7. Actual S/C and SV Values for the Experiments to

Optimize Reactor Temperature
reactor temperature (°C) S/C (mol/mol) SV (m3 kg-1 h-1)
600 2.58 16.41
650 2.67 16.75
700 2.91 17.68
750 2.72 17.00
800 2.81 17.33
850 2.77 17.19
900 2.51 16.20

Figure 4. CO selectivity versus equilibrium temperature.

Figure 1. CH4 conversion versus equilibrium temperature.

Figure 5. H2/CO ratio in synthesis gas versus equilibrium temperature.

high value. Therefore, the reactor temperature should be within

the range of 700-750 °C but not below 700 °C because the
CH4 conversion decreases significantly below 700 °C.
It can be seen that high exit temperatures enhance H2
production through higher conversion of methane up to a certain
point, where the H2 yield reaches a maximum value in the
temperature range of 650-700 °C. At higher exit temperatures,
Figure 2. H2 yield versus equilibrium temperature. there is a slight decrease in H2 yield, because the prevented
exothermic water-gas shift reaction at high temperatures results
in a decrease of the hydrogen production.
The increase of CO2 conversion with temperature shows that
the methane dry reforming reaction (reaction 4) takes place. At
higher temperatures, this endothermic reaction is favored and
therefore CO2 is consumed.
It is recognized from the diagrams that the theoretical
characteristic of the calculations are well-observed in the
experimental results. Anyway, the difference between the
experimental and theoretical results can be related to the high
space velocity, which results in a short contact time between
the active catalyst surface and particles. On the other hand, as
a result of irregular flow, the individual feed gas molecules can
Figure 3. CO2 conversion versus equilibrium temperature. pass the reactor without sufficient catalyst contact and not be
the SV values are not exactly the same in all experiments. Table reformed. The distinction between them is anyway not easily
7 shows the actual S/C and SV values for each experiment. possible. At lower SV values, equilibrium condition can be
The results are presented in Figures 1–5. In addition to the reached, which make the comparison of experimental results
experimental measured values, the diagrams contain equilibrium especially at higher temperatures impossible; therefore, inten-
values for S/C ) 2-5 (mol/mol) and also S/C ) 2.71 (mol/ tionally an approximate high SV value is selected and seems
mol) as the actual mean S/C value of the experiments. to be appropriate for such investigation.
From the diagrams, it can be observed that high temperatures 4.4. Variation of Steam/Carbon Ratio. From reactions 1
would favor the steam reforming reactions, reactions 1 and 3 and 2, it can be seen that the overall stoichiometric requirement
according to their strong endothermic nature, lead to higher for steam per carbon atom is 2. However, carbon forming
conversion of methane in the reactor. reactions are promoted in the presence of active catalysts. This
According to the equilibrium calculations, at higher reformer results in rapid deactivation of catalysts.7,8,13–16,23–25 Therefore,
temperature, an increasing steam concentration in the feed results
in a slight increase of the CH4 conversion. At outlet temperatures (23) Xu, J.; Froment, G. F. Methane steam reforming, methanation and
water-gas shift: 1. Intrinsic kinetics. AIChE J. 1989, 35 (1), 88–96.
higher that 750 °C, CH4 conversion is observed to remain (24) Rostrup-Nielsen, J. R.; Bak Hansen, J. H. CO2 reforming of methane
practically constant and independent of S/C and also shows a over transition metals. J. Catal. 1993, 144, 38–49.
Biogas Steam Reforming Energy & Fuels, Vol. 22, No. 6, 2008 4187

Figure 6. CH4 conversion versus S/C ratio. Figure 10. H2/CO ratio in synthesis gas versus S/C ratio.

Table 8. Parameters of the Experiments for Optimizing S/C

parameter unit value
CH4/CO2 ratio mol/mol 1.5
S/C ratio mol/mol 1.52-4.69
space velocity m3 kg-1 h-1 12.52 ( 0.73
reactor temperature °C 700
catalyst amount g 158
catalyst bed high mm 89
residence time s 0.28
test duration min 120

Table 9. Parameters of the Experiments for Different S/C

Figure 7. H2 yield versus S/C ratio. Values
parameter unit value
CH4/CO2 ratio mol/mol 1.5
S/C ratio mol/mol 1-5
space velocity m3 kg-1 h-1 7-18
reactor temperature °C 700
test duration min 120

and carbon removal reactions. Overall, the steam reformer must

be operated in a carbon-removing regime. While a very low
value of S/C may cause significant carbon formation, a high
S/C ratio enhances CH4 conversion but requires an additional
amount of energy to produce the steam and also increase the
mass flow through the plant and thus the size and cost of the
Figure 8. CO2 conversion versus S/C ratio. equipment. Moreover, it involves the heating of the excess steam
up to the reforming outlet temperature and subsequent conden-
sation of the water downstream. Hence, an optimum S/C ratio
should be optimized according to these considerations.
For an experimental determination of the S/C effect on
catalyst A and also reactor performance, a further series of tests
are carried out at a reactor temperature of 700 °C and variable
S/C values. The parameters are listed in Table 8.
The results are shown in Figures 6–10. In addition to the
experimentally measured values, the diagrams also contain
equilibrium values for temperatures from 650 to 850 °C.
An increase in the steam concentration of the feed results in
a very strong increase of the CH4 conversion and a steep
Figure 9. CO selectivity versus S/C ratio. decrease of the CO2 conversion. A maximum CH4 conversion
of about 99%, corresponding to an S/C ratio of about 4 is
excess steam is practically provided (S/C > 2). There are several reached. However, a slighter effect of the S/C ratio is observed
reaction mechanisms that can cause carbon to be formed at higher temperatures. More steam in the feed also results in
depending upon the conditions in the steam reformer (i.e., gas reaction 3 dominating over reaction 1, producing more CO2 and
composition, operating temperature, total pressure, catalyst less CO. Consistently, a higher CO2 consumption is observed
loading and selectivity, and also reformer design), and deposited for lower steam/carbon ratios, indicating a higher rate of dry
carbon can be gasified again by steam or oxygen.15,23,25 Thus, reforming. The CO2 conversion equal to zero shows the balance
there is a dynamic equilibrium between the carbon formation of the CO2 consuming reaction (reaction 4) with CO2 producing
reactions (reactions 2 and 3). The increased S/C value leads to
a smaller CO concentration and a higher selectivity toward H2
(25) Groote, A. M. D.; Froment, G. F. Simulation of the catalytic partial
oxidation of methane to synthesis gas. Appl. Catal., A 1996, 138, 245– in the product stream. The H2 yield was observed to increase
264. for increasing steam/methane ratios.
4188 Energy & Fuels, Vol. 22, No. 6, 2008 Ashrafi et al.

Figure 11. CH4 conversion versus S/C ratio (mol/mol) and space Figure 13. CO2 conversion versus S/C ratio (mol/mol) and space
velocity (m3 kg-1 h-1). velocity (m3 kg-1 h-1).

Figure 12. H2 yield versus S/C ratio (mol/mol) and space velocity (m3 Figure 14. CO selectivity versus S/C ratio (mol/mol) and space velocity
kg-1 h-1). (m3 kg-1 h-1).

The experimental results follow closely those predicted by

equilibrium calculations, and the difference as mentioned before
can be related to the high space velocity or irregular gas flow.
It can be finally recognized that, for S/C ratios in the range
of 3-4 (mol/mol), an acceptable CH4 conversion and H2 yield
can be obtained. Anyway, the available waste heat has an
important effect on the optimization of this parameter in a plant,
which is investigated for two plant concepts in Ashrafi et al.20
4.5. Variation of Space Velocity. The space velocity (or
feed gas contact time with active sites of the catalyst) has a
high impact on the investment costs of the installation. High
space velocities induce small reactor dimensions and little Figure 15. H2/CO ratio in synthesis gas versus S/C ratio (mol/mol)
catalyst content. At the same time, reactor performance is and space velocity (m3 kg-1 h-1).
reduced.19 Therefore, the space velocity has a high potential water-gas shift reaction is controlled by thermodynamic
for optimization. parameters rather than kinetic limitations.
The following diagrams show steam reforming dependency It should be noted that catalyst A showed lower conversion
on contact time over catalysts A and B under atmospheric than catalyst B at the same space velocity equal to about 17.85
pressure condition. In these experiments, the S/C ratio was m3 kg-1 h-1, according to its higher active contact surface.
changed stepwise from higher to lower values at a constant space
velocity. Other parameters are listed in Table 9. 5. Conclusion
The results are shown in Figures 11–15. Six different Ni-based commercial catalysts have been
As observed clearly at low space velocities, methane conver- investigated in terms of their activity, stability, resistance to
sion increases. In the case of catalyst A, a space velocity of carbon formation, size, and shape. Among these catalysts, two
7.78 m3 kg-1 h-1 led almost to equilibrium methane conversion. catalysts of Süd Chemie are employed for further investigations
However, at higher SV values, methane conversion decreased on the purpose of testing model biogas steam reforming
drastically. The steep decrease of methane conversion with a thermodynamics, which are presented in this paper. On the basis
decreasing space velocity can be reflected in the reforming of the above results, the following conclusions are drawn.
ability of the catalysts. It is confirmed that both employed catalysts are very active
On the other hand, the H2/CO profiles remained unchanged and stable under the typical steam methane reforming conditions.
for both catalysts for different space velocities, indicating much No catalyst deactivation and carbon formation is observed during
higher reaction rates of the water-gas shift reaction (reaction the above experiments. Anyway deactivation and coking are of
2) in comparison to other reactions. The relative yields of CO great importance in long-term experiments, which will be
and CO2 are in good agreement with a fully equilibrated performed at the pilot plant in Strem, Austria. The investigation
thermodynamic model of the system even at high SV values. of other Ni-based catalysts with different compositions and
This suggests that, under the present operating conditions, the supports and also iron-based catalysts could be suggested.
Biogas Steam Reforming Energy & Fuels, Vol. 22, No. 6, 2008 4189

Steam reforming of biogas (60% CH4 and 40% CO2) must Acknowledgment. The authors gratefully acknowledge the
therefore ideally be carried out at a high temperature and high financial support by the Renewable Energy Network Austria (ReNet
steam/carbon ratio to achieve maximum conversion. A high S/C Austria), Energy from Biogas (Austrian funds program KNET/KIND),
ratio always improves the reformer performance, which should as well as the company Süd-Chemie for providing the catalysts.
be optimized according to economics and entire plant heat
integration. However, at S/C ratios lower than 3, the impact of Nomenclature
the dry reforming reaction of methane with CO2 is significant. BG ) biogas
A high temperature always improves methane conversion in cat ) catalyst
the reformer, while it remains approximately constant at E ) end
temperatures higher than 750 °C. On the other hand, operating in ) inlet stream of the reformer
at temperatures lower than 700 °C is not suggested because of m ) mass, kg
Ṅx ) molar flow rate of component x, mol/h
the significant decrease of methane conversion, higher danger
ṁx ) mass flow rate of component x, kg/h
of carbon formation, and high required catalyst load. In contrast, out ) outlet stream of the reformer
as a result of the exothermic nature of the water-gas shift S ) start
reaction, H2 yield shows a maximum value within the range of SG ) synthesis gas
650-700 °C, which can be different depending upon the entire S/C ) steam/carbon molar ratio, mol/mol
plant configuration. According to the above results, 700 °C is SV ) space velocity, m3 kg-1 h-1
found to be the optimal choice. t ) time, h
Finally, it should be examined how these parameters affect V̇x ) operating volume flow rate of component x, m3/h
the entire plant and how the efficiency will be changed wf ) water free
consequently; thus, the optimum operating area will be limited. xs ) mass-based saturation degree, kgH2O/kgSG
Basic investigations regarding this topic have been performed YA ) concentration of component A in a mixture, mol %
∆rH ) enthalpy change of a reaction, kJ/mol
for two different plant configurations and presented by Ashrafi
et al.20 EF800081J