i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
Available online at www.sciencedirect.com
journal homepage: www.elsevier.com/locate/he
Review
Overview of hydrogen production technologies from biogas
and the applications in fuel cells
Helton José Alves a,*, Cı́cero Bley Junior c, Rafael Rick Niklevicz c, Elisandro Pires Frigo b,
Michelle Sato Frigo b, Carlos Henrique Coimbra-Araújo a
a
Biofuels Technology Course, Federal University of Paraná (UFPR-Campus Palotina), R. Pioneiro, 2153, Jardim Dallas, 85950-000 Palotina,
PR, Brazil
b
Agronomy Course, Federal University of Paraná (UFPR-Campus Palotina), R. Pioneiro, 2153, Jardim Dallas, 85950-000 Palotina, PR, Brazil
c
International Renewable Energy Center-Emphasis on Biogas (CIER-Biogas), ITAIPU Binacional-Parque Tecnológico Itaipu (PTI),
Av. Tancredo Neves, 6731, 85867-900 Foz do Iguaçu, PR, Brazil
article info
abstract
Article history:
Traditionally, H2 is a large-scale production by the reforming process of light hydrocarbons,
Received 13 December 2012
mainly natural gas, used by the chemical industry. However, the reforming technologies
Received in revised form
currently used encounter numerous technical/scientific challenges, which depend on the
7 February 2013
quality of raw materials, the conversion efficiency and security needs for the integration of
Accepted 13 February 2013
H2 production, purification and use, among others. Biogas is a high-potential versatile raw
Available online xxx
material for reforming processes, which can be used as an alternative CH4 source. The
Keywords:
house gas emissions. Within this context, the integration of biogas reforming processes
Biogas
and the activation of fuel cell using H2 represent an important route for generating clean
Reforming processes
energy, with added high-energy efficiency. This work expounds a literature review of the
Hydrogen
biogas reforming technologies, emphasizing the types of fuel cells available, the advan-
Fuel cells
tages offered by each route and the main problems faced.
production of H2 from renewable sources, such as biogas, helps to largely reduce green-
Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
1.
Introduction
Biogas is a product composed mainly of methane (CH4) and
carbon dioxide (CO2), associated with traces of other gases
such as hydrogen sulfide (H2S), ammonia (NH3), hydrogen (H2),
nitrogen (N2), oxygen (O2) and vapor water (H2O). Table 1
shows the typical chemical composition of biogas [1e3]. This
mixture of gases is the result of the anaerobic digestion
process of the residual biomass from various sources
(animal waste, sewage treatment plants or industrial
wastewater, landfills, etc.), which is performed by
microorganisms that decompose organic matter in nature or
in equipment/devices known as biodigester tanks [4e6]. H2S
is an undesirable component in biogas, since it is a corrosive
gas capable of damaging the equipment and accessories
used in the process to obtain energy. CO2 and humidity can
also be considered as impurities because they reduce the
calorific value of biogas in direct combustion for thermal
power generation [7,8]. Of the many variables that can
automatically change the chemical composition of biogas
* Corresponding author. Tel.: þ55 44 32118595; fax: þ55 44 32118548.
E-mail addresses: [email protected], [email protected] (H.J. Alves).
0360-3199/$ e see front matter Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
2
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
Table 1 e Chemical composition of biogas [1e3].
Composite
CH4
CO2
H2S
NH3
H2
N2
O2
H2O
Percentage
55e70 (vol%)
30e45 (vol%)
500e4000 (ppm)
100e800 (ppm)
<1 (vol%)
<1 (vol%)
<1 (vol%)
<1 (vol%)
and its energy content, the origin and quality of the biomass
used, the type of biodigester and the management used in
the anaerobic digestion process should be mentioned [9,10].
The use of biogas is quite versatile since: i) its chemical
energy can be converted into mechanical energy by controlled
combustion processes in stationary engines, which then put
in motion the generators to promote a direct conversion into
electrical energy; ii) it can be used to co-generate thermal
energy, generating hot water and steam with the engine’s
high temperatures; iii) it can be burned to generate heat energy in boilers; iv) it can be applied as fuel to automotive and
stationary engines [11e16].
Although there are various types of applications, new
biogas alternatives need to be strategically exploited to
consolidate their power generation potential and significance.
A promising possibility is to obtain H2 from biogas for its use in
loading fuel cells [17e20], as proposed in the work presented
herein.
H2 has high energy capacity, with the largest amount of
energy per mass unit than any other known substance
(121.000 kJ/kg).
The best energy use of H2 takes place in fuel cells. Fuel
cells achieved remarkable progress in the last decade, which
were developed for transportation, as well as for power generation in stationary or portable installations. The fuel cell
system can include several applications, such as: large power
stations; power distribution generators, used in buildings and
homes; small portable power supply equipment for microelectronic devices; and auxiliary power units in vehicles,
among others [19,21,22]. These cells then transform the
chemical energy of the H2 molecules into electrical energy
with up to 60% of efficiency [19,21]. Additionally, when H2 is
used in vehicular fuel cells, it can yield two to three times
more efficiency than the current devices used in internal
combustion vehicles (20e30%). These qualities make H2 one
of the main alternatives for replacing fossil fuels consumed
worldwide [22].
Currently, H2 is widely used as raw material in the chemical industry, in food processing, in hydrogenation processes,
in the production of ammonia and methanol, in the
FischereTropsch synthesis, in the pharmaceutical industry,
among others [23].
The demand for H2 grows yearly. The available 2008 data
indicate that H2 consumption by the oil sector was of 364
billions/m3, while the global H2 consumption was of 409 billions/m3. It is also estimated that by 2013 the global H2 demand will increase 18%, with nearly half of this expected
increase generated outside the refineries by other sectors [7].
In the pursuit to reduce greenhouse gases and to remove
carbon from the industrial processes, the projected H2
supply for outside the refineries is a strategic target, which
will facilitate the entrance of “reforming” technologies from
renewable resources in the H2 market [17,19].
The main techniques used to obtain large-scale H2 promote
the reforming of light hydrocarbons, especially methane, a
major biogas component [24]. However, several of these
routes produce CO mixed with H2, characterizing the socalled “synthesis gas”, widely used in industries [25].
Attaining high purity H2 from the synthesis gas is a
relatively expensive process, since CO has to be removed [26].
In many studies that address the reforming processes,
there is a research emphasis on catalysts to lower the costs
and the energy involved.
The development and use of catalysts, which have high
catalytic activity and stability in the reforming processes, can
ensure reducing the high temperatures normally used,
accompanied by increased reaction speeds as well as slowing
down the catalyst deactivation process by poisoning (chemisorption of sulfur and/or other impurities) or carbon deposition (coke), which are the main problems usually encountered
[27e33].
The objective of this paper is to present a concise look at
the possibilities of using biogas as renewable raw material for
the production of H2 to activate fuel cells.
2.
Processes used for generating hydrogen
from methane and biogas
The most common methane reforming processes for
hydrogen production are known as: “steam reforming (SR)”
[34e43], “partial oxidation reforming (POR)” [44e51], “autothermal reforming (ATR)” [52e57], “dry reforming (DR)”
[58e63] and “dry oxidation reforming (DOR)” [1,64e67]. There
are other non-conventional processes reported in the literature for the production of H2 from methane, such as: “solar
reforming” [6,24], “thermal plasma reforming” [68e71] and
“catalytic decomposition” [72,73]. Traditional methods of
large scale H2 production used by industries are the first three
mentioned, with natural gas as the main source of hydrocarbons (z90% of CH4).
In most studies found in the literature on biogas reforming
to produce H2, there are detailed experiments using mixtures
of CH4 and CO to simulate laboratory biofuel compositions.
However, the high purity CH4 (>99%) is commonly used to
simulate laboratory scale reforming processes, with few
studies found that use biogas from the direct digestion process of residual biomass (real biogas) in their experiments
[5,74,75].
Thus, to choose the reforming process using biogas, its
composition must be taken into account in three different
situations, which may be sequential: i) in natura, with 55e70%
of CH4, 30e45% of CO2 and 500e4000 ppm of H2S (Table 1); ii)
partially treated for H2S removal; iii) purified for
“biomethane” enrichment (93e96% of CH4, 4e7% of CO2 and
<20 ppm of H2S). Note that in the latter case, the CH4
content is hardly ever higher than 95% using economically
viable treatments [1e3,7,8].
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
3
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
Before reforming, the methods tipically used for the
removal of corrosive species in biogas can be divided into two
categories: i) those that involve physico-chemical phenomena
(including the processes of absorption in aqueous solutions;
chemical adsorption of H2S on solid adsorbents such as activated carbon, modified zeolites and metal surfaces, with
consequent formation of metal sulfide, and washing with
solvents), and ii) those involving biological processes (consumption of contaminants by living organisms, such as species of chemothrophic thiobacteria, which serve as oxidants
in the sulfur biofilters, biotrickling filter and units of biodepuration, and conversion to less harmful forms) [24,76].
In general, H2 can be produced by methane or biogas
reforming in a wide temperature range of 600e1000 C
(endothermic and reversible reactions), involving predominantly catalytic processes that are often combined. Both
reforming processes can be performed under low pressure (in
most cases under atmospheric pressure) in tubular fixed-bed
or fluidized reactors [7,24,25].
The reforming processes in the next items use methane as
raw material, since it is the main source of hydrocarbons
used. However, in various reforming processes, biogas can be
used as a methane source, which directly depends on its
composition. Thus, most of the research involving methane
reforming can also be adapted to biogas reforming.
Table 2 shows the chemical reactions cited and their
respective thermal reactions at 298 K (25 C), in order to
facilitate the information organization contained throughout
the work.
2.1.
Conventional reforming processes
2.1.1.
Steam reforming (SR)
SR is the combination of methane with water vapor in the
presence of a catalyst, producing CO and H2 (Eq. 1). This is a
highly endothermic process which requires reaction temperatures ranging between 650 and 850 C, to obtain H2 yields of
60e70% [34e43].
Although it has great energy expenditure SR is the most
widespread industrial route to obtain H2. The H2/CO ratio
produced in SR is equal to three, the most appropriate one
from the H2 generation point of view. In order to eliminate CO,
the WatereGas Shift reaction, commonly known as “Shift
reaction” (Eq. 2), is the most widely used, requiring
temperatures ranging from 300 to 450 C and catalysts based
on Fe, Cu, Mo or FeePd alloys (among others), which enables
the production of an additional amount of H2. Equation 3
shows the reaction of methane SR associated with the shift
reaction [2,3].
Additionally, the harsh conditions required promote parallel carbon formation reactions (methane decomposition reaction), Boudouard reaction or disproportionation reduction
reaction of CO, respectively, Eqs. 4, 5 and 6) favoring catalyst
deactivation by carbon deposition on its surface (coke)
[77e79]. It is usually desired for the carbon to be on the catalyst surface in the form of nanotubes, which causes lower
carbon dispersion over the surface, thus preserving its activity
for a longer period of time [72].
The catalysts usually used in SR consist of Ni (transition
metal), Pt, Rh or Pd (noble metals), of which the Ni catalysts
have the advantage of having lower costs. On the other hand,
Ni has greater deactivation susceptibility by the coke formation due to the high temperatures used, which makes the Pt
and Pd catalysts interesting with regards to stability. When
there is limited mass transfer, Rh is used as it has catalytic
activity that is much higher than Ni and a lower coke formation tendency [36,42]. Basic supports containing promoter elements such as Ca, Mg and K can also be used to decrease
carbon accumulation on the catalyst, since they favor carbon
species gasification by the carbonewater steam reaction
(reverse Eq. 6), due to increased water adsorption [80e83]. The
metals cited, as well as others, can be used as active species in
the preparation of supported catalysts using various types of
matrices, such as: SiO2, Al2O3, ZrO2, etc. [27,41].
To obtain high purity H2, the CO2 and CO formed in SR must
be effectively separated, which is not unique to this type of
reforming, required in all the processes where there is greater
interest in H2 production rather than synthesis gas. Typically,
the H2 production applying the conventional SR process uses
three integrated systems: reformer, conversion reactor (shift
reaction) and separating unit [84].
Several studies show good efficiency in the separation
process using selective membrane reactors with H2, which can
be directly fed to the fuel cell. The membrane reactor then
allows all reactions developed in the conventional reactor to
occur on a single device, producing pure H2. Thus, the SR
methane reaction (Eq. 1) and shift reaction (Eq. 2) occur
simultaneously within the reactor that contains a nickel
Table 2 e Chemical reactions involved in the methane reforming processes [7,24,79,81].
Identification of reaction
Eq.
Eq.
Eq.
Eq.
Eq.
Eq.
Eq.
Eq.
Eq.
Eq.
Eq.
1
2
3
4
5
6
7
8
9
10
11
Type of reaction
Thermal reaction, DH298 (kJ/mol)
CH4 þ H2O4 CO þ 3H2
CO þ H2O4CO2 þ H2
CH4 þ 2H2O4CO2 þ 4H2
CH44C þ 2H2
2CO4C þ CO2
CO þ H24C þ H2O
CH4 þ 1/2O24CO þ 2H2
CH4 þ 2O24CO2 þ 2H2O
CH4 þ 1/2xO2 þ yCO2 þ (1xy)H2O4(y þ 1)CO þ (3xy)H2
CH4 þ CO242CO þ 2H2
CH4 þ bCO2 þ (1 b)/2O24(1 þ b)CO þ 2H2
206
41.2
165
74.9
172.4
131.3
35.6
801.7
z0
247.4
(285b 38) 0 b 1
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
4
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
catalyst bed. Furthermore, the membrane provides greater
shift ability to the chemical equilibrium of the reaction,
increasing the productivity of H2, since removing H2 from the
reaction medium displaces the dynamic equilibrium for
forming products. This shift allows the reforming reaction to
be carried out at temperatures below 500 C, without any
methane conversion loss [38,42,85e87].
2.1.2.
Partial oxidation reforming (POR)
POR is an alternative method to produce H2 with reduced
energy costs, since the reaction is moderately exothermic (Eq.
7), contrary to SR which is highly endothermic. In this type of
reaction, methane is partially oxidized to CO and H2 (synthesis
gas), at atmospheric pressure, requiring temperatures between 700 and 900 C to ensure complete conversion (H2/CO
ratio close to 2) and to reduce soot formation. However, a
slight decrease in CO selectivity cause the methane to react
with oxygen to form CO2 (Eq. 8), leading to complete combustion (strong exothermic reaction), which results in high
reaction temperature increase, which can form hot-spots in
the reactor bed and form coke on the catalyst surface [48e51].
According to ÁVILA-NETO (2009) [88], although the
temperature increase favors the CH4 conversion, the O2/CH4
feed ratio applied to the reactor is the variable that most
influences the conversion. In this case, CH4 is completely
consumed to the O2/CH4 ratio close to 0.5.
Some studies focus on developing high activity and stability catalysts for methane POR. Mixed metal oxides, solid
solutions of NiOeMgO, NieMgeCreLaeO and CaeSreTieNi
are reported as highly active and selective catalysts at
elevated temperatures (>800 C), with higher carbon deposition resistance [48,89].
2.1.3.
Autothermal reforming (ATR)
Because it is a highly endothermic, SR associated with the
Shift reaction (Eq. 3) requires external power supply. A reactor’s internal heating is generally more efficient than
external heating, and a reaction that releases energy in the
catalyst bed can make the manufacturing process of H2
energetically more economical. However, the partial oxidation reaction of CH4 has the advantage of being exothermic
(Equation 7), but generates a lower H2/CO ratio in comparison
with SR.
Based on these observations, other CH4 reforming types,
called ATR, can be performed with a combination of the two
aforementioned reforming techniques, resulting in the sum of
reactions described by equations 3, 7 and 8 [53e57]. ATR also
occurs in the presence of CO2, represented by Equation 9
[74,75].
There is a thermal zone in the reactor, where the partial
oxidation is conducted to generate the heat required for SR
that takes place in the catalytic zone, fed by a downward
steam flow. The heat generated by the zone where the partial
oxidation takes place does not require external heating,
resulting in an efficient energy process. The advantages of
ATR concern the speed with which the reactor can be stopped
and restarted, and the capacity to produce higher amounts of
H2 with lower O2 consumption when compared to isolated
POR, since the H2/CO ratio in the synthesis gas produced can
be easily adapted through the CH4/O2/H2O ratio to feed the
reactor, leading to the synthesis of the desired product.
Additionally, the combination of these reactions can improves
the temperature control in the reactor and reduce the formation of hot-spots, thus avoiding the deactivation of the
catalyst [54,90].
In this system the partial oxidation reaction of methane
occurs simultaneously with SR, which makes the process selfsustaining, significantly reducing energy costs. Thus, for SR
methane to be advantageous over others, it is necessary that it
takes place under autothermal conditions, performed adiabatically together with partial oxidation reaction, in order to
produce synthesis gas with a H2/CO ratio between 2.0 and 3.5,
using H2O/CH4 ratios between 1.0 and 2.5, O2/CH4 between
0.25 and 0.55 [52e54,56].
It should be noted that the selectivity of products in the
oxidation zone is highly dependent on temperature, that is,
partial oxidation reactions (Eq. 7) are favored by increased
temperature, and total oxidation (Eq. 8) favored by decreased
temperature [91].
2.1.4.
Dry reforming (DR)
DR occurs when CH4 reacts with CO2 to produce CO and H2 (Eq.
10). This type of reaction is attractive from an environmental
standpoint, since it consumes two gases that contribute to the
greenhouse effect (CH4 and CO2). However, it should be noted
that the endothermic nature of the reaction minimizes the
reduction of CO2 emissions, since the CO2 emitted by the
burning of fuel used to generate the heat required for the reaction should be accounted for. From the industrial point of
view, methane DR also satisfies the requirement of many
synthesis processes of oxygenated compounds and liquid
hydrocarbons (FischereTropsch synthesis), which is an efficient route for producing synthesis gas, yielding a H2/CO ratio
close to 1 [59,63,79,80].
According to the literature regarding this topic, the main
reaction (Eq. 10) can be accompanied by competing parallel
reactions that modify the equilibrium conversion of CO2 in
CH4, as follows: reverse gasewater shift (Eq. 2 reverse),
decomposition of carbon monoxide (Boudouard reaction) (Eq.
5) and decomposition of methane (Eq. 4) [60]. In general, DR
occurs at temperatures ranging between 700 and 900 C,
using a CH4/CO2 molar ratio between 1 and 1.5, attaining H2
yields of around 50% [62,63,92].
If the decomposition reaction of the methane (Eq. 4) is
faster than the carbon removal rate, there will be serious
problems for the formation of coke, with the consequent
deactivation of the catalyst and blocking of the reactor by the
coke formed. The decomposition reaction of carbon monoxide
(Eq. 5) is favored at low temperatures and, together with the
decomposition reaction of methane, it can generate carbon
[93e97]. Thus, the main problem of DR is the greater tendency
to form coke, accumulated on the support as well as on the
active phase of the catalyst, since the carbon-water steam
reaction does not occur as it does in SR (reverse Eq. 6). Much
effort has been employed in the search for catalysts that avoid
the deposition of carbon, while being thermally stable,
maintaining selectivity in the production of H2 [31,63,97,98].
The most active catalysts for methane DR, reported in
literature, are those that use metals of the groups 8, 9 and 10 of
the Periodic Table, particularly Rh, Ru and Pt. However, these
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
5
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
metals are expensive and of limited availability, and are
therefore, in practice, not suitable for the process at an industrial level. Therefore, various catalysts have been developed according to greater availability and lower price, which is
usually associated with increased coke susceptibility, as in the
case of Ni and Co catalysts [60,61,99e102].
2.1.5.
Dry oxidation reforming (DOR)
A strategy for the control of carbon deposition on the surface
of the catalysts is to combine the methane DR and POR. Cofeeding O2 with CH4 and CO2 provides additional advantages,
such as: reducing the global energy involved, improving the
conversion of CH4 and increasing the product yield at a lower
temperature; enhanced catalyst stability and increased deactivation resistance; control the H2/CO ratio by modulation of
O2 to meet the flow requirements [1,65]. Methane DOR can be
written as shown in Equation 11, where b is the stoichiometric
fraction of CO2 fed with traditional DR. It is evident that the
theoretical H2/CO ratio, given by 2/(1 þ b), is greater in DOR for
b < 1, than non-oxidative DR, where b ¼ 1 [67,79].
In methane DOR the product ratio of H2/CO and the
exothermic or endothermic nature can be controlled by
manipulating the process variables, particularly the reaction
temperature and/or relative concentration of O2 in the reactor
feeding. In general, the exothermic nature increases for a
given temperature as the O2 concentration in the feed increases. This is due to the fact that the addition of O2
determines the oxidation process (complete oxidation when
b ¼ 0 (Eq. 8), or traditional DR when b ¼ 1 (Eq. 10)), and automatically, the amount of heat released or consumed [66,67,79].
Considering that dry reforming in the presence of O2
simultaneously involves the traditional DR (Eq. 10) and POR
(Eq. 7) processes, characterized as endothermic and
exothermic, respectively, the methane conversion to synthesis gas occurs with high energy efficiency, requiring little
external energy [103e108].
Research on catalysts for this type of reaction is usually
directed to support development or the insertion of a second
metal associated with Ni (bimetallic catalyst) to enhance its
stability [1,47,64,65]. Regarding DR, the addition of O2 reduces
the formation of coke on the catalyst due to greater control of
the partial oxidation of the novel carbon species, CH4 and CO2,
for CO [92].
Table 3 shows a summary of the reaction conditions used
in the different H2 production routes using methane or real
biogas as the main raw materials.
3.
Use of hydrogen in fuel cells
3.1.
Fuel cell concepts
Fuel cells are devices that can convert the chemical energy of a
fuel directly into electricity, without combustion, with high
Table 3 e A summary of studies on H2 production using methane or biogas in conventional reforming processes.
Process
SR
POR
ATR
DR
DOR
Reactor
Temperature ( C)
Catalyst
H2/CO
Conversion of CH4 (%)
Reference
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fluidized-bed
Fixed-bed
Fixed-bed
Fluidized-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fixed-bed
Fluidized-bed
Fixed-bed
Fluidized-bed
600
650
700
715
850
750
750
750
800
850
700
800
700
800
700
750
750
850
800
750
860
750
700
700
750
900
850
750
Ni-Ce0.8Zr0.2O2
NiMg17.4Al1.6O20.8
Ni/Al2O3
Ru/Al2O3
Ni/Al2O3
Ni/CaOeAl2O3
Ni/Al2O3
Ni/Al2O3
Pt/CeO2
NiO/MgO
Ni/Al2O3
NiCoMgCeOx/ZrO2eHfO2
Ni/MgAl2O4
Pt/ZrO2/Al2O3
Rh/Al2O3
Ni/Cu5Zr10Ce20Al65O8
Ni/cordierite
Ni/insulating (Si,Mg,Al) (monolithic)
Ni/SBA-15
Ni/NiOeMgO
Ni/CeO2eAl2O3
Rh-NiLa/g-Al2O3
La/hydrotalcite
Ni/CeZrO2eMgAl2O4
Rh-NiLa/g-Al2O3
Pt-Rh/CeeZrO2eAl2O3
NdCoO3 perovskite
5Ni/5ZrO2eSiO2
3.4
3.7
a
2.7
2.1
2.5
2.0
2.2
2.0
2.0
2.0
2.0
3.2
2.0
3.5
3.9
2.6
2.8
1.4
1.2
1.3
0.9
0.7
1.2
1.0
1.0
1.7
1.9
70
98
85
90
98
95
85
96
85
87
100
95
92
100
95
100
90
95
92
75
90
70
67
85
86
100
95
77
[41]
[43]
[39]
[105]
[2]
[3]
[106]
[106]
[44]
[45]
[46]
[48]
[52]
[53]
[55]
[56]
[74],b
[75],b
[31]
[111]
[60]
[92]
[62]
[63]
[92]
[1]
[66]
[47]
a Information not available.
b Real biogas.
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
6
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
efficiency and with lower polluting emissions than conventional equipment/techniques.
The development of various types of fuel cells partially
focuses on optimizing the layer of the catalytic electrodes, and
specifically on reducing the amount of metal without appreciable loss of cell performance. It is known, however, that with
the operation there may be significant changes in the structural properties of the catalyst, and then its stability assumes
a significant role in the cell’s useful life [109e111].
In a fuel cell the power supply is uninterrupted while it is
fed with the fuel and the oxidant, different from a battery in
which the energy storage is limited by the amount of reagent
stored in it. Insofar the theoretical thermodynamic efficiency
of fuel cells are close to 90% in the thermal engines (Carnot),
this efficiency is of only 40% under typical operating conditions for both systems. In practice, the efficiency of a fuel cell
is usually less than 60% [112].
3.2.
Types of fuel cells
Fuel cells have been developed to supply different markets.
Owners of electric stations investigate the use of PAFC cells
(Phosphoric acid fuel cell ), MCFC cells (Molten carbonate fuel cell )
and SOFC cells (Solid oxide fuel cell ). The latter cell promises
high efficiency (50%e60%) and its market type is not restricted
by the size or weight of the cell, hence requiring very durable
systems. Similarly, residential cells represent a large and
attractive market segment. However, for these purposes, as
well as for automobile use, there is a size and weight limitation, requiring to evaluate the ability of intermittent operation, for the fuel cell PEMFC or PEM (Proton Exchange Membrane
Fuel Cell ), which has an electrolyte polymeric membrane, the
most widely studied [19,81,90,108,113]. According to CIPITÍ
et al. (2008) [114], PEMFC, stands out as a key option, for
transportation use (electric vehicles) as well as for smallscale power generation facilities (homes) due to durability,
compatibility, low operating temperatures, high conversions
and low polluting and noise emissions.
The degree of H2 purification required for fuel cells depends on the application. Gas separation by pressure swing
adsorption (USGAMP) or palladium membranes are used to
produce H2 with purity above 99.999%. For fuel cells PEMFC or
PAFC (low temperature) CO must be reduced to less than
10 ppm [19]. However, CO drastically affects the performance
of the system, as it usually binds to the metal atoms of the
catalyst, preventing adsorption and the consequent
oxidation of H2. Thus, the choice of a catalyst electrode
tolerant to CO and/or the use of tools to minimize the
effects caused by the reaction contaminant (current pulses
in the cell, air insertion with fuel flow, introduction of H2O2
into the cell anode, etc.) are some of the main challenges to
be overcome regarding the low-temperature fuel cell
technology [84,115e117].
It is known that at high temperatures the tolerance to CO
increases significantly, enabling its use in some fuel cells,
such as MCFC and SOFC (high temperatures), H2 with higher
CO concentrations, expanding the possibilities of using an
interconnected system for methane or biogas reforming
processes [19]. In this case the use of bimetallic eletrodic
catalysts that contain a second element besides Pt, such as
Ru, Sn, Mo and Os, which form alloys or co-deposits
dispersed on carbon, result in significant tolerance increase
to CO [118e121].
The SOFC fuel cell is currently one of the most studied
because of its exceptional application potential as a power
generation system due to its high-energy conversion efficiency.
Correspondingly, a considerable advantage of SOFC is the
possibility of using other fuels in addition to H2 such as natural
gas, biogas, gasoline, methanol and ethanol [19,81,108].
3.3.
Internal reforming of biogas in fuel cells
While the technology to efficiently convert H2 into electrical
energy and into the required power levels are closer to
commercialization, parallel attempts have been made for the
direct use of biogas in fuel cells, known as “internal reforming” [5,20,109,122e129].
High-temperature fuel cells, such as SOFC and MCFC, are
better suited for the direct use of biogas, because they have a
greater capacity to thermally integrate internal reforming and
increase tolerance against contaminants of H2, while maintaining high electrical efficiency (close to 50%). Several studies
have been reported in the literature on the use of various types
of biogas internal reforming in high-temperature fuel cells. In
some cases, it was demonstrated that, electricity can be stably
obtained from biogas without auxiliary fuel, external reformer,
humidifier, and precious metal catalyst [124,125,130]. Typically, SOFC cells exhibit eletrodic catalysts that comprise: i)
anode and support: Ni-YSZ (yttria-stabilized zirconia) or
NieScSZ (scandia-stabilized zirconia), ii) cathode: LSM
(lanthanum strontium doped manganate) or composite and iii)
electrolyte: YSZ-TiO2, ZEI-MgO, Y2O3, CeO2, MnOeCeO2 and
GdO2eCeO2 [19,127,128].
A disadvantage of the internal reforming process is the
formation of CO, which acts as a poison to the fuel cell when
in the range of 50 ppm [81,126]. Additionally, the variability of
biogas composition and the poisoning of the catalysts of the
fuel cell by carbon deposition (coke) by CO disproportionation
(Eq. 5) and the presence of sulfur traces, represent the main
problems commonly faced [2].
In the former case, the coke formation reduces the catalyst
activity and simultaneously blocks the pores and can destroy
their structure. New approaches to reduce carbon deposition
by adding different promoters (Sn, Mo, Li, Mg, Ca, Sr, Ce, Ru,
Rh, Pd and Pt) in the anode Ni-YSZ (yttria stabilized zirconia)
are reported in the literature. Furthermore, the addition of
water and air for a CO2/CH4 ratio between 0 and 1, is
considered a strategy to suppress carbon formation [128].
In the latter case, the sulfur-containing species cause a
substantial decrease in the conversion to hydrogen. This is
due to the strong sulfur chemisorption on the surface and
within particles of the electrodic catalyst. An alternative to
this problem is to pass a gaseous stream rich in methane and
hydrogen at elevated temperature, which causes the gradual
increase in conversion as the physically adsorbed sulfur is
removed. Although poisoning appear to be partially reversible,
the initial levels of conversion are not achieved because there
are a slow desorption of such species [131].
In addition to the problem caused by contaminants, it is
possible indeed that the temperature gradients from the
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
endothermic reforming reactions cause the destruction of the
electrolyte. In this case, one possible solution is to add air to
the biogas, which not only prevents coke formation, but also
removes the high temperature gradient due to the occurrence
of exothermic reactions (complete and partial oxidation of
methane) [127].
Fig. 1 shows the region with the greatest tendency to
carbon deposition in the diagram of CeHeO ternary phase,
when biogas internal reforming is used in SOFC fuel cells. In
any type of conventional reforming used, the diagram in
Fig. 1 is valid, since the C, H and O elements are always
present in the molecules of the reactants (see Table 2).
4.
Considerations for H2 production from
biogas
It is acknowledged that biogas has great potential for H2
generation through several reforming processes. However,
selecting a specific process depends on several factors, some
of which are: biogas composition, purity required for using H2,
volume production of the desired H2, and investment availability, among others.
Some of the reforming technologies mentioned in this
work are already or will soon be commercialized, as for
instance e SR, POR and ATR. Other newer technologies, not
yet consolidated, will take some time to be commercialized,
currently only used in research, such as internal reforming in
fuel cells [24]. Among the existing fuel cells, the PAFC type
cells have already been marketed, however they encounter
problems such as durability and sensitivity to contaminants,
rendering their technological route unviable. Although the
PEMFC, SOFC and MCFC cells are in rapid development, they
are not commercial products, but rather advanced prototypes.
In natura biogas cannot be used as raw material in conventional reforming processes due to the likely poisoning of
the catalyst by H2S, resulting in the rapid loss of catalytic
Fig. 1 e Ternary CeHeO diagram CeHeO showing the
possibility of coke formation for biogas internal reforming
in SOFC. Adapted from Shiratori et al. (2010) [122].
7
activity. For the partially treated reforming biogas (H2S
removed), using a chemical composition with considerable
CO2 content (30e45% vol.), the dry process is interesting, as it
enables taking advantage of the CO2 intrinsically present in
the composition, as an oxidant in this kind of reforming.
When the biogas has a CO2/CH4 ratio lower than 1 (as it usually
occurs), it is necessary to add an alternative oxidant for the
production of synthesis gas. Therefore, the addition of O2 by
the DOR method could be a possible route for the production
of H2 from biogas, also promoting a slight increment in the H2/
CO ratio.
In almost all reforming technologies, one of the main
challenges is developing catalysts capable of preventing carbon deposition on the active phase in order to increase its
useful life. In the case of DR, the problem is even worse, often
making this type of process unfeasible due to the rapid
deactivation of the catalyst. In DOR, the periodical passage of
O2 flow through the catalyst bed helps the gasification of the
carbon deposited on the surface, increasing the availability of
catalytic active sites and temporarily/partially recovering the
activity of the material.
However, in both reforming cases (DR, DOR) the H2/CO
ratio is usually close to 1, which restricts the H2 production
potential, requiring a higher CO volume to be separated from
the products by the Shift reaction, making it difficult to obtain
high purity H2. Furthermore, in the DR biogas, part of the H2
produced reacts with CO2 by the reverse shift reaction (Eq. 2)
producing water and CO, which reduces the production
yield of H2.
Thus, maximizing the H2 yield from biogas with the SR
process, followed by Shift reactions, seems to be a less elegant
but more feasible solution, particularly with respect to minimizing CO and maximizing H2 production. In this case, the H2/
CO ratio obtained is high (close to 3) and the technology
involved better known and controlled. There are many studies
which adapt biogas in SR, despite the high CO2 content,
maintaining a high H2/CO ratio (between 2 and 3), as seen in
Table 3 [2,3,86]. The same can occur in POR and ATR, where
biogas can be used directly without drastically reducing the
ratio of H2/CO [44e47,52,74,82,89,90].
Thus, ATR appears to be an attractive technique for
generating H2 from biogas, from the standpoint of H2 yield, as
well as for the energy efficiency achieved. Additionally, in ATR
the reactor can be stopped and restarted quickly, which when
the discontinuous supply of biogas and energy intake is
considered, directly result in the lowest cost/benefit ratio
among all the other reforming processes.
When biogas is purified, that is enriched in biomethane, it
has a chemical composition (93e96% of CH4, 4e7% of CO2 and
<20 ppm of H2S) that enables it to be used in almost all
reforming processes. The lower the CO2 content in biomethane,
the more efficient the CH4 conversion in the desired products,
which makes it easier to obtain high purity H2. However, it
should be noted that in this case the DR and DOR processes are
not the most suitable ones as CO2 has to be added to the reactor,
which in turn is already removed in the previous step during
the biogas purification treatment. Thus, the SR, POR and ATR
processes are the most recommended ones.
In any conventional reforming process using biogas as raw
material, new catalysts with high catalytic activity at high
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
8
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
temperatures must be developed. They should be chemically
and thermally stable, preventing carbon deposition on its
surface (coke) which consequently slows down the inactivation process. In view of the frequent treatments required to
reactivate the catalyst (inside or outside the catalyst bed), or
the need for periodic replacement due to its permanent
deactivation, which results in production stops, the costs can
be very high. This is a major obstacle for large-scale H2 production using the reforming processes.
According to the operating temperature of the fuel cells,
the production method of H2 can be designed/engineered.
For high-temperature operating cells, H2 can be produced
by internal reforming of hydrocarbons (methane or biogas).
The low-temperature cells, such as PEMFC, require an
external reformer (pre-reformer) using steam (SR), air (POR)
or the combination of both (ATR). Thus, a combined
H2 production unit with one fuel cell is a promising alternative for mobile and stationary applications in the near
future. Given that storage technology and H2 distribution
networks do not yet meet the expectations, fuel efficient
and compact catalytic converters, such as fuel cells, are
crucial.
5.
Conclusion
The main problems encountered in the biogas reforming
processes, cited by most studies found, are related to coke
formation on the catalyst surface and the poisoning by
substances containing sulfur, which can lead to deactivation of the catalyst and reduction of H2 production.
The Ni-based catalysts are the most used in the reform
processes. Many studies focus on evaluating the effect of the
catalyst support and the addition of promoter elements over
coke formation.
Purification of biogas for the reduction or elimination of
corrosive species such as H2S is a necessary step, regardless
of the process that is used. The physico-chemical methods,
adopting chemical adsorption and absorption processes,
have been used frequently, and initiatives involving biological processes with the use of living organisms to
consume the contaminants are also found.
With respect to fuel cells, both the degree of purification of
H2 as the nature of the electrodic catalysts and the electrolyte used, can interfere with the functioning and efficiency
in generating electricity. Cells with higher temperatures
(e.g. SOFC) besides presenting higher electrical efficiency,
they also have a higher tolerance to CO (50 ppm). To these
cells, there are several studies that show that the bimetallic
catalysts (with addition of a second metallic element
beyond Pt or Ni) reduce the tendency to coke formation.
In the internal biogas reforming within high temperature
fuel cells, such as SOFCs, tolerance to the formed CO decreases much above 50 ppm, which can lead to carbon
deposition on the electrodic catalysts, being necessary a
greater control of the chemical composition of the incoming
biogas. The addition of water and air to biogas and promoter
elements in the electrodic catalysts are initiatives to prevent
the destruction of the electrolyte and reduce the buildup of
coke, respectively.
references
[1] Lau CS, Tsolankis A, Wyszynski ML. Biogas upgrade to syngas (H2-CO) via dry and oxidative reforming. Int J Hydrogen
Energy 2011;36:397e404.
[2] 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;84:869e74.
[3] Kolbitsch P, Pfeifer C, Hofbauer H. Catalytic steam
reforming of model biogas. Fuel 2008;87:701e6.
[4] Shiga H, Shinda K, Hagiwara K, Tsutsumi A, Sakurai M,
Yoshida K, et al. Large-scale hydrogen production from
biogas. Int J Hydrogen Energy 1998;23:631e40.
[5] Okubo T, Hideschima Y, Shudo Y. Estimation of hydrogen
output from a full-scale plant for production of hydrogen
from biogas. Int J Hydrogen Energy 2010;35:13021e7.
[6] Muradov N, Smith F. Thermocatalytic conversion of landfill
gas and biogas to fuels. Energy Fuels 2008;22:2053e60.
[7] Fierro JLG. Hydrogen and syngas from biomass. Catal Today
2012.. http://dx.doi.org/10.1016/j.cattod.2012.04.058.
[8] Horikawa MS, Rossi F, Gimenes ML, Costa CMM, Silva MGC.
Chemical absorption of H2S for biogas purification. Braz J
Chem Eng 2004;21(3):415e22.
[9] Lansing S, Botero RB, Martin JF. Waste treatment and biogas
quality in small-scale agricultural digesters. Bioresour
Technol 2008;99:5881e90.
[10] Ferrer I, Garfı́ M, Uggetti E, Ferre-Martı́ L, Calderon A, Velo E.
Biogas production in low-cost household digesters at the
Peruvian Andes. Biomass Bioenerg 2011;35:1668e74.
[11] Solomon KR, Lora EES. Estimate of the electric energy
generating potential for different sources of biogas in Brazil.
Biomass Bioenerg 2009;33:1101e7.
[12] Damrongsak D, Tippayawong N. Experimental investigation
of an automotive air-conditioning system driven by a small
biogas engine. Appl Therm Eng 2010;30:400e5.
[13] Pöschl M, Ward S, Owende P. Evaluation of energy efficiency
of various biogas production and utilization pathways. Appl
Energy 2010;87:3305e21.
[14] Swami NS, Mallikarjuna JM, Ramesh A. An experimental
study of the biogas-diesel HCCI mode of engine operation.
Energy Conv Manag 2012;51(7):1347e53.
[15] Iordanidis AA, Kechagiopoulos PN, Voutetakis SS,
Lemonidou AA, Vasalos IA. Autothermal sorptionenhanced steam reforming of bio-oil/biogas mixture and
energy generation by fuel cells: concept analysis an process
simulation. Int J Hydrogen Energy 2008;31:1058e65.
[16] Borgward RH. Biomass and natural gas as co-feedstocks for
production of fuel-cell vehicles. Biomass Bioenerg
1997;12:333e45.
[17] Levin DB, Chahine R. Challenges for renewable hydrogen
production from biomass. Int J Hydrogen Energy
2010;35:4962e9.
[18] Papadias DD, Ahmed S, Kumar R. Fuel quality issues with
biogas energy e an economic analysis for a stationary fuel
cell system. Energy 2012;44:257e77.
[19] Hotza D, Da Costa JCD. Fuel cells development and
hydrogen production from renewable resources in Brazil.
Int J Hydrogen Energy 2008;33:4915e35.
[20] Herle JV, Membrez Y, Bucheli O. Biogas as a fuel source for
SOFC co-generators. J Power Sources 2004;127:300e12.
[21] Faghri A, Guo Z. Challenges and opportunities of thermal
management issues related to fuel cell technology and
modeling: review. Int J Heat Mass Transf 2005;48:3891e920.
[22] Chen Z, Grace JR, Lim CJ, Li A. Experimental studies of pure
hydrogen production in a commercialized fluidized-bed
membrane reactor with SMR and ATR catalysts. Int J
Hydrogen Energy 2007;32:2359e66.
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
[23] Armor JN. The multiple roles for catalysis in the production
of H2. Appl Catal A Gen 1999;176:159e76.
[24] Holladay JD, Hu J, King DL, Wang Y. An overview of
hydrogen production technologies. Catal Today
2009;139:244e60.
[25] Göransson K, Söderlind U, He J, Zhang W. Review of syngas
production via biomass DFBGs. Renew Sust Energ Rev
2011;15:482e92.
[26] Li J, Smith KJ. Methane decomposition and catalyst
regeneration in a cyclic mode over supported Co and Ni
catalysts. Appl Catal A Gen 2008;349:116e24.
[27] Amin AM, Croiset E, Constantinou C, Epling W. Methane
cracking using Ni supported on porous and non-porous
alumina catalysts. Int J Hydrogen Energy 2012;37:9038e48.
[28] Parkomenko K, Tyunyaev A, Tejada LMM, Komissarenko D,
Dedov A, Loktev A, et al. Mesoporous amorphous silicate
catalysts for biogas reforming. Catal Today 2012;189:129e35.
[29] Halabi MH, Croon MHJM, Schaaf JVD, Cobden PD,
Schouten JC. A novel catalyst-sorbent system for an
efficient H2 production with in-situ CO2 capture. Int J
Hydrogen Energy 2012;37:4987e96.
[30] Sun D, Li X, Ji S, Cao L. Effect of O2 and H2O on the trireforming of the simulated biogas to syngas over Ni-based
SBA-15 catalysts. J Nat Gas Chem 2010;19:369e74.
[31] Barrai F, Jackson T, Whitmore N, Castaldi MJ. The role of
carbon deposition on precious metal catalyst activity during
dry reforming of biogas. Catal Today 2007;129:391e6.
[32] Caglayan BS, Önsan ZI, Aksoylu AE. Production of hydrogen
over bimetallic Pt-Ni/g-Al2O3: II. Indirect partial oxidation of
LPG. Catal Lett 2005;102:63e7.
[33] Muradov N, Smith F, T-Raissi A. Hydrogen production by
catalytic processing of renewable methane-rich gases. Int J
Hydrogen Energy 2008;33:2023e35.
[34] Zhu X, Wang H, Wei Y, Li K, Cheng X. Hydrogen and syngas
production from two-step steam reforming of methane over
CeO2-Fe2O3 oxygen carrier. J Rare Earths 2010;28(6):907e12.
[35] Boyano A, Blanco-Marigorta AM, Morosuk T, Tsatsaronis G.
Exergoenvironmental analysis of a steam methane reforming
process for hydrogen production. Energy 2011;36:2202e14.
[36] Zhai X, Ding S, Liu Z, Jin Y, Cheng Y. Catalytic performance
of Ni catalysts for steam reforming of methane at high
space velocity. Int J Hydrogen Energy 2011;36:482e9.
[37] Zhai X, Ding S, Cheng Y, Jin Y, Cheng Y. CFD simulation
with detailed chemistry of steam reforming of methane for
hydrogen production in an integrated micro-reactor. Int J
Hydrogen Energy 2010;35:5383e92.
[38] Gallucci F, Paturzo L, Basile A. A simulation study of the
steam reforming of methane in a dense tubular membrane
reactor. Int J Hydrogen Energy 2004;29:611e7.
[39] Maluf SS, Assaf EM. Ni catalysts with Mo promoter for
methane steam reforming. Fuel 2009;88:1547e53.
[40] Zhai X, Cheng Y, Zhang Z, Jin Y, Cheng Y. Steam reforming
of methane over Ni catalyst in micro-channel reactor. Int J
Hydrogen Energy 2011;36:7105e13.
[41] Roh H-S, Eum I-H, Jeong D-W. Low temperature steam
reforming of methane over Ni-Ce(1-x)Zr(x)O2 catalysts under
severe conditions. Renew Energy 2012;42:212e6.
[42] Iulianelli A, Manzolini G, Falco M, Campanari S, Longo T,
Liguori S, et al. H2 production by low pressure methane
steam reforming in a Pd-Ag membrane reactor over a Nibased catalyst: experimental and modeling. Int J Hydrogen
Energy 2010;35:11514e24.
[43] Fonseca A, Assaf EM. Production of the hydrogen by
methane steam reforming over nickel catalysts prepared
from hydrotalcite precursors. J Power Sourc 2005;142:154e9.
[44] Corbo P, Migliardini F. Hydrogen production by catalytic
partial oxidation of methane and propane on Ni and Pt
catalysts. Int J Hydrogen Energy 2007;32:55e66.
9
[45] Ruckenstein E, Hu YH. Methane partial oxidation over NiO/
MgO solid solution catalysts. Appl Catal A Gen
1999;183:85e92.
[46] Rogatis L, Montini T, Cognigni A, Olivi L, Fornasiero P.
Methane partial oxidation on NiCu-based catalysts. Catal
Today 2009;145:176e85.
[47] Zhang X, Lee CS-M, Hayward DO, Mingos DMP. Oscillatory
behaviour observed in the rate of oxidation of methane over
metal catalysts. Catal Today 2005;105:283e94.
[48] Choudhary VR, Mondal KC, Choudhary TV. Partial oxidation
of methane to syngas with or without simultaneous steam
or CO2 reforming over a high-temperature stableNiCoMgCeOx supported on zirconia-hafnia catalyst. Appl
Catal A Gen 2006;306:45e50.
[49] Dantas SC, Resende KA, Rossi RL, Assis AJ, Hori CE.
Hydrogen production from oxidative reforming of methane
on supported nickel catalysts: an experimental and
modeling study. Chem Eng J 2012;197:407e13.
[50] Omata K, Kobayashi S, Horiguchi J, Kobayashi Y,
Yamazaki Y, Yamada M. Kinetic model of K-Ni/a-Al2O3
catalyst for oxidative reforming of methane determined by
genetic algorithm. Appl Catal A Gen 2012;425e426:170e7.
[51] Jing QS, Zheng XM. Combined catalytic partial oxidation and
CO2 reforming of methane over ZrO2-modified Ni/SiO2
catalysts using fluidized-bed reactor. Energy 2006;31:2184e92.
[52] Mosayebi Z, Rezaei M, Ravandi AB, Hadian N. Autothermal
reforming of methane over nickel catalysts supported on
nanocrystalline MgAl2O4 with high surface area. Int J
Hydrogen Energy 2012;37:1236e42.
[53] Souza MMVM, Schmal M. Autothermal reforming of
methane over Pt/ZrO2/Al2O3 catalysts. Appl Catal A Gen
2005;281:19e24.
[54] Halabi MH, Croon MHJM, Schaaf JVD, Cobden PD,
Schouten JC. Modeling and analysis of autothermal
reforming of methane to hydrogen in a fixed bed reformer.
Chem Eng J 2008;137:568e78.
[55] Simeone M, Salemme L, Allouis C. Reactor temperature
profile during autothermal methane reforming on Rh/Al2O3
catalyst by IR imaging. Int J Hydrogen Energy
2008;33:4798e808.
[56] Cai X, Dong X, Lin W. Autothermal reforming of methane
over Ni catalysts supported on CuO-ZrO2-CeO2-Al2O3. J Nat
Gas Chem 2006;15:122e6.
[57] Dantas SC, Escritori JC, Soares RR, Hori CE. Effect of different
promoters on Ni/CeZrO2 catalyst for autothermal reforming
and partial oxidation of methane. Chem Eng J
2010;156:380e7.
[58] Fidalgo B, Domı́nguez A, Pis JJ, Menéndez JA. Microwaveassisted dry reforming of methane. Int J Hydrogen Energy
2008;33:4337e44.
[59] Oyama ST, Hacarlioglu P, Gu Y, Lee D. Dry reforming of
methane has no future for hydrogen production:
comparison with steam reforming at high pressure in
standard and membrane reactors. Int J Hydrogen Energy
2012;37:10444e59.
[60] Bereketidou OA, Goula MA. Biogas reforming for syngas
production over nickel supported on ceria-alumina
catalysts. Catal Today 2012;195(1):93e100.
[61] San-José-Alonso D, Juan-Juan J, Illán-Gómes MJ, RománMartı́nez MC. Ni, Co and bimetallic Ni-Co catalysts for the
dry reforming of methane. Appl Catal A Gen
2009;371:54e9.
[62] Serrano-Lotina A, Martin AJ, Folgado MA, Daza L. Dry
reforming of methane to syngas over La-promoted
hydrotalcite clay-derived catalysts. Int J Hydrogen Energy
2012;37:12342e50.
[63] Eltejaei H, Bozorgzadeh HR, Towfighi J, Omidkhah MR,
Rezaei M, Zanganeh R, et al. Methane dry reforming on Ni/
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
10
[64]
[65]
[66]
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
Ce0.75Zr0.25O2-MgAl2O4 and Ni/Ce0.75Zr0.25O2-g-alumina:
effects of support composition and water addition. Int J
Hydrogen Energy 2012;37:4107e18.
Izquierdo U, Barrio VL, Lago N, Requies J, Cambra JF,
Güemez MB, et al. Biogas steam and oxidative reforming
processes for synthesis gas and hydrogen production in
conventional and microreactor reaction systems. Int J
Hydrogen Energy 2012;37:13829e42.
Chen L, Zhu Q, Hao Z, Zhang T, Xie Z. Development of a
Co-Ni bimetallic aerogel catalyst for hydrogen production
via methane oxidative CO2 reforming in a magnetic
assisted fluidized bed. Int J Hydrogen Energy
2010;35:8494e502.
Choudhary R, Mondal KC. CO2 reforming of methane
combined with steam reforming or partial oxidation of
methane to syngas over NdCoO3 perovskite-type mixed
metal-oxide catalyst. Appl Energy 2006;83:1024e32.
Gao J, Hou Z, Liu X, Zeng Y, Luo M, Zheng X. Methane
autothermal reforming with CO2 and O2 to synthesis gas at
the boundary between Ni and ZrO2. Int J Hydrogen Energy
2009;34:3734e42.
Khalaf P, Souza IG, Carasek E, Debacher NA. Production of
synthesis gás by thermal plasma via pyrolysis of methane
and carbon dioxide. Quim Nova 2011;34(9):1491e5.
Yang Y-C, Lee B-J, Chun Y-N. Characteristics of methane
reforming using gliding arc reactor. Energy 2009;34:172e7.
Chun YN, Yang YC, Yoshikawa K. Hydrogen generation
from biogas reforming using a gliding arc plasma-catalyst
reformer. Catal Today 2009;148:283e9.
Zhu B, Li X-S, Shi C, Liu J-L, Zhao T-L, Zhu A- M.
Pressurization effect on dry reforming of biogas in kilohertz
spark-discharge plasma. Int J Hydrogen Energy
2012;37:4945e54.
Hermes NA. Hydrogen and carbon nanotubes by catalytic
decomposition of methane: performance of catalysts based
on cobalt and aluminum [dissertation]. Porto Alegre (Brazil):
Federal University of Rio Grande do Sul; 2010.
Labanca ARC. Development of the plasma pyrolysis reactor
for the decomposition of the methane in hydrogen and
solid carbon [thesis]. Rio de Janeiro (Brazil): Federal
University of Rio de Janeiro; 2007.
Araki S, Hino N, Mori T, Hikazudani S. Autothermal
reforming of biogas over a monolithic catalyst. J Nat Gas
Chem 2010;19:477e81.
Araki S, Hino N, Mori T, Hikazudani S. Durability of a Ni
based monolithic catalyst in autothermal reforming of
biogas. Int J Hydrogen Energy 2009;34:4727e34.
Abatzoglou N, Boivin S. A review of biogás purification
processes. Biofuels Bioprod Bioref 2009;3:42e71.
Sousa FF, Sousa HAS, Oliveira AC, Junior MCC, Ayala AP,
Barros EB, et al. Nanostructured Ni-containing spinel oxides
for the dry reforming of methane: effect of the presence of
cobalt and nickel on the deactivation behavior of catalysts.
Int J Hydrogen Energy 2012;37:3201e12.
Djinovı́c P, Crnivec IGO, Erjavec B, Pintar A. Influence of
active metal loading and oxygen mobility on coke-free dry
reforming of Ni-Co bimetallic catalysts. Appl Catal B
Environ 2012;125:259e70.
Adesina AA. The role of CO2 in hydrocarbon reforming
catalysis: friend or foe? Curr Opin Chem Eng 2012;1:272e80.
Muradov N, Smith F, Garceau N. Dry reforming of biogas to
syngas and hydrogen for fuel cell applications. In:
Proceedings of the spring meeting & 5th global congress on
process safety/09 AIChE - American Institute of Chemical
Engineering; 2009 May. Tampa, Florida, p. 45a.
Xuan J, Leung MKH, Leung DYC, Ni M. A review of biomassderived fuel processors for fuel cell systems. Renew Sust
Energ Rev 2009;13:1301e13.
[82] Trimm DL. Catalysts for the control of coking during steam
reforming. Catal Today 1999;49:3e10.
[83] Lisboa JS, Santos DCRM, Passos FB, Noronha FB. Influence of
the addition of promoters to steam reforming catalysts.
Catal Today 2005;101:15e21.
[84] Silva LC. Optimization of hydrogen production by steam
reforming of methane in membrane reactor laboratory
[dissertation]. Uberlândia (Brazil): Federal University of
Uberlândia; 2008.
[85] Lin Y, Liu S, Chuanga C, Chub Y. Effect of incipient removal
of hydrogen through palladium membrane on the
conversion of methane steam reforming: experimental and
modeling. Catal Today 2003;82:127e39.
[86] Lu GQ, Diniz-Costa JC, Dukec M, Giessler S, Socolowe R,
Williams RH, et al. Inorganic membranes for hydrogen
production and purification: a critical review and
perspective. J Colloid Interface Sci 2007;314:589e603.
[87] Sato T, Suzuki T, Aketa M, Ishiyama Y, Mimura K, Itoh N.
Steam reforming of biogas mixtures with a palladium
membrane reactor system. Chem Eng Sci 2010;65:451e7.
[88] Ávila-Neto CN. Thermodynamic analysis of the reforms
methane (oxidation and autothermal) of ethanol and
naphtha [dissertation]. Uberlândia (Brazil): Federal
University of Uberlândia; 2009.
[89] Zhu J, Van-Ommen JG, Knoester A, Lefferts L. Effect of
surface composition of yttrium-stabilized zirconia on
partial oxidation of methane to synthesis gas. J Catal
2005;230:291e300.
[90] Escritori JC. Autothermal reforming of methane to Ni/
CeZrO2/Al2O3 catalysts for the production of hydrogen
[dissertation]. Uberlândia (Brazil): Federal University of
Uberlândia; 2007.
[91] Horn R, Williams KA, Degenstein NJ, Bitsch-Larsen A,
Nogare DD, Tupy SA, et al. Methane catalytic partial
oxidation on autothermal Rh and Pt from catalysts:
oxidation and reforming zones, transport effects, and
approach to thermodynamic equilibrium. J Catal
2007;249:380e93.
[92] Lucrédio AF, Assaf JM, Assaf EM. Reforming of a model
biogás on Ni and Rh-Ni catalysts: effect of adding La. Fuel
Process Tech 2012;102:124e31.
[93] Gallucci F, Tosti S, Basile A. Pd-Ag tubular membrane
reactors for methane dry reforming: a reactive method for
CO2 consumption and H2 production. J Membr Sci
2008;317:96e105.
[94] Djaidja A, Libs S, Kiennemann A, Barama A.
Characterization and activity in dry reforming of methane
on NiMg/Al and Ni/MgO catalysts. Catal Today
2006;113:194e200.
[95] Chang JS, Hong DY, Li X, Park S. Thermogravimetric
analyses and catalytic behaviors of zirconia-supported
nickel catalysts for carbon dioxide reforming of methane.
Catal Today 2006;115:186e90.
[96] Ferreira OLS. Conversion of biogas into synthesis gas via
reforming reactions of methane with CO2 and steam on
catalysts Ni-Al-Y [dissertation]. São Carlos (Brazil):
University of São Paulo; 2010.
[97] Lima SM, Assaf JM. Preparation and characterization of
LaNi(1-x)CoxO3 perovskites as catalyst precursors for
synthesis gas generation by CO2 reforming of methane.
Quim Nova 2007;30(2):298e303.
[98] Valentini A, Probst LF, Carreño NLV, Leite ER,
Pontes FM, Longo E, et al. Microstructural study of Ni/gAl2O3 catalyst e addition effects of CeO2 on carbon
dioxide reforming of methane. Quim Nova
2003;26(4):648e54.
[99] Sousa HSA, Silva NA, Castro AJR, Campos A, Filho JM,
Oliveira AC. Mesoporous catalysts for dry reforming of
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 0 ) 1 e1 1
[100]
[101]
[102]
[103]
[104]
[105]
[106]
[107]
[108]
[109]
[110]
[111]
[112]
[113]
[114]
[115]
methane: correlation between structure and deactivation
behaviour of Ni-containing catalysts. Int J Hydrogen Energy
2012;37:12281e91.
Serrano-Lotina A, Rodrı́guez L, Muñoz G, Martin AJ,
Folgado MA, Daza L. Biogas reforming over La-NiMgAl
catalysts derived from hydrotalcite-like structure: influence
of calcinations temperature. Catal Commun 2011;12:961e7.
Xu J, Zhou W, Li Z, Wang J, Ma J. Biogas reforming for
hydrogen production over nickel and cobalt bimetallic
catalysts. Int J Hydrogen Energy 2009;34:6646e54.
Nakamura J, Aikawa K, Sato K, Uchijima T. Role of support
reforming of CH4 over Rh catalysts. Catal Lett
1994;25:265e70.
Choudhary VR, Mamman AS. Simultaneous oxidative
conversion and CO2 or steam reforming of methane to
syngas over a CoO-NiO-MgO catalyst. J Chem Tech
Biotechnol 1998;73:345e50.
Ashcroft AT, Cheetham AK, Green MLH, Vernon PDF. Partial
oxidation of methane to syngas using carbon dioxide.
Nature 1991;352:225e6.
Avraam DG, Halkides TI, Liguras DK, Bereketidou AO,
Goula MA. An experimental and theoretical approach for
the biogas steam reforming reaction. Int J Hydrogen Energy
2010;35:9818e27.
Effendi A, Zhang Z-G, Hellgardt K, Honda K, Yoshida T.
Steam reforming of a clean model biogas over Ni/Al2O3 in
fluidized- and fixed-bed reactors. Catal Today
2002;77:181e9.
Asencios YJO, Bellido JDA, Assaf EM. Synthesis of NiO-MgOZrO2 catalysts and their performance in reforming of model
biogas. Appl Catal A Gen 2011;397:138e44.
Naidja A, Krishna CR, Butcher T, Mahajan D. Cool flame
partial oxidation and its role in combustion and reforming
of fuels for fuel cell systems. Prog Energy Combust Sci
2003;29:155e91.
Goula G, Kiousis V, Nalbandian L, Yentekakis IV. Catalytic
and electrocatalytic behavior of Ni-based cermet anodes
under internal dry reforming of CH4 þ CO2 mixtures in
SOFCs. Solid State Ion 2006;177:2119e23.
Zhang S, Yuan X, Hin JNC, Wang H, Friedrich KA, Schulze M.
A review of platinum-based catalyst layer degradation in
proton exchange membrane fuel cells. J Power Sources
2009;194(2):588e600.
Wu J, Martin JJ, Wang H, Zhang J, Shen J, Wu S, et al. A
review of PEM fuel cell durability: degradation mechanisms
and mitigation strategies. J Power Sources
2008;184(1):104e19.
Vielstich W. Ideal and effective efficiencies of cell
reactions and comparison to Carnot cycles. In:
Vielstich W, editor. Handbook of fuel cells: fundamentals,
technology and applications. New York: John Wiley; 2003.
p. 26e30.
Ahmed S, Krumpelt M. Hydrogen from hydrocarbon fuels
for fuel cells. Int J Hydrogen Energy 2001;26:291e301.
Cipitı́ F, Pino L, Vita A, Lagana M, Recupero V. Performance
of a 5 kW and fuel processor for polymer electrolyte fuel
cells. Int J Hydrogen Energy 2008;33:3197e203.
Uribe FA, Valerio JA, Garzon FH, Zawodzinski TA. PEMFC
reconfigured anodes for enhancing CO tolerance with air
bleed. Electrochem Solid State Lett 2004;7(10):A376e9.
11
[116] Adcock PA, Pacheco SK, Norman KM, Uribe FA. Transition
metal oxides as reconfigured fuel cell anode catalysts for
improved CO tolerance: polarization data. J Electrochem Soc
2005;152(2):A459e66.
[117] Schimidt VM, Oetjen HF, Divisek J. Performance
improvement of a PEMFC using fuels with CO by addition of
oxygen-evolving compounds. J Electrochem Soc
1997;144(9):L237e8.
[118] Ge Q, Desai S, Neurock M, Kourtakis K. CO adsorption on PtRu surface alloys and on the surface of Pt-Ru bulk alloy. J
Phys Chem B 2001;105(39):9533e6.
[119] Lee D, Hwang S, Lee I. A study on composite PtRu(1:1)PtSn(3:1) anode catalyst for PEMFC. J Power Sources
2005;145(2):147e53.
[120] Mukerjee S, Lee SJ, Ticianelli EA, McBreen J, Grgur BN,
Markovic NM, et al. Investigation of enhanced CO tolerance
in proton exchange membrane fuel cells by carbon
supported PtMo alloy catalyst. Electrochem Solid State Lett
1999;2(1):12e5.
[121] Santiago EI, Ticianelli EA. The performance of carbonsupported PtOs electrocatalysts for the hydrogen oxidation
in the presence of CO. Int J Hydrogen Energy
2005;30(2):159e65.
[122] Shiratori Y, Ijichi T, Oshima T, Sasaki K. Internal reforming
SOFC running on biogas. Int J Hydrogen Energy
2010;35:7905e12.
[123] Takahashi Y, Shiratori Y, Furuta S, Sasaki K. Thermomechanical reliability and catalytic activity of Ni-Zirconia
anode supports in internal reforming SOFC running on
biogas. Solid State Ion 2012;225:113e7.
[124] Mogensen D, Grunwaldt J-D, Hendriksen PV, DamJohansen K, Nielsen JU. Internal steam reforming in solid
oxide fuel cells: status and opportunities of kinetic studies
and their impact on modelling. J Power Sources
2011;196:25e8.
[125] Shiratori Y, Oshima T, Sasaki K. Feasibility of direct-biogas
SOFC. Int J Hydrogen Energy 2008;33:6316e21.
[126] Assabumrungrat S, Laosiripojana N, Piroonlerkgul P.
Determination of the boundary of carbon formation for dry
reforming of methane in a solid oxide fuel cell. J Power
Sources 2006;159:1274e82.
[127] Lanzini A, Leone P. Experimental investigation of direct
internal reforming of biogas in solid oxide fuel cells. Int J
Hydrogen Energy 2010;35:2463e76.
[128] Benito M, Garcı́a S, Ferreira-Aparicio P, Serrano LG, Daza L.
Development of biogas reforming Ni-La-Al catalysts for fuel
cells. J Power Sources 2007;169:177e83.
[129] Bonura G, Cannilla C, Frusteri F. Ceria-gadolinia supported
NiCu catalyst: a suitable system for dry reforming of biogas
to feed a solid oxide fuel cell (SOFC). Appl Catal B Environ
2012;121e122:135e47.
[130] Silva AL, Dick LFP, Müller IL. Performance of a PEMFC
system integrated with a biogas chemical looping reforming
processor: a theoretical analysis and comparison with other
fuel processors (steam reforming, partial oxidation and
auto-thermal reforming). Int J Hydrogen Energy
2012;37:6580e600.
[131] Farinha JFB. Methane steam reforming in reformer of the
laboratory scale [dissertation]. Lisbon (Portugal): Technical
University of Lisbon; 2008.
Please cite this article in press as: Alves HJ, et al., Overview of hydrogen production technologies from biogas and the applications in fuel cells, International Journal of Hydrogen Energy (2010), http://dx.doi.org/10.1016/j.ijhydene.2013.02.057