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 3 8 ( 2 0 1 3 ) 5 2 1 5 e5 2 2 5

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 17 March 2013 material for reforming processes, which can be used as an alternative CH4 source. The
production of H2 from renewable sources, such as biogas, helps to largely reduce green-
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.
Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction wastewater, landfills, etc.), which is performed by

microorganisms that decompose organic matter in nature or
Biogas is a product composed mainly of methane (CH4) and in equipment/devices known as biodigester tanks [4e6]. H2S
carbon dioxide (CO2), associated with traces of other gases is an undesirable component in biogas, since it is a corrosive
such as hydrogen sulfide (H2S), ammonia (NH3), hydrogen (H2), gas capable of damaging the equipment and accessories
nitrogen (N2), oxygen (O2) and vapor water (H2O). Table 1 used in the process to obtain energy. CO2 and humidity can
shows the typical chemical composition of biogas [1e3]. This also be considered as impurities because they reduce the
mixture of gases is the result of the anaerobic digestion calorific value of biogas in direct combustion for thermal
process of the residual biomass from various sources power generation [7,8]. Of the many variables that can
(animal waste, sewage treatment plants or industrial 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
5216 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 3 8 ( 2 0 1 3 ) 5 2 1 5 e5 2 2 5

In the pursuit to reduce greenhouse gases and to remove

Table 1 e Chemical composition of biogas [1e3].
carbon from the industrial processes, the projected H2
Composite Percentage supply for outside the refineries is a strategic target, which
CH4 55e70 (vol%) will facilitate the entrance of “reforming” technologies from
CO2 30e45 (vol%) renewable resources in the H2 market [17,19].
H2S 500e4000 (ppm) The main techniques used to obtain large-scale H2 promote
NH3 100e800 (ppm) the reforming of light hydrocarbons, especially methane, a
H2 <1 (vol%)
major biogas component [24]. However, several of these
N2 <1 (vol%)
routes produce CO mixed with H2, characterizing the so-
O2 <1 (vol%)
H2 O <1 (vol%) called “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].
and its energy content, the origin and quality of the biomass In many studies that address the reforming processes,
used, the type of biodigester and the management used in there is a research emphasis on catalysts to lower the costs
the anaerobic digestion process should be mentioned [9,10]. and the energy involved.
The use of biogas is quite versatile since: i) its chemical The development and use of catalysts, which have high
energy can be converted into mechanical energy by controlled catalytic activity and stability in the reforming processes, can
combustion processes in stationary engines, which then put ensure reducing the high temperatures normally used,
in motion the generators to promote a direct conversion into accompanied by increased reaction speeds as well as slowing
electrical energy; ii) it can be used to co-generate thermal down the catalyst deactivation process by poisoning (chemi-
energy, generating hot water and steam with the engine’s sorption of sulfur and/or other impurities) or carbon deposi-
high temperatures; iii) it can be burned to generate heat en- tion (coke), which are the main problems usually encountered
ergy in boilers; iv) it can be applied as fuel to automotive and [27e33].
stationary engines [11e16]. The objective of this paper is to present a concise look at
Although there are various types of applications, new the possibilities of using biogas as renewable raw material for
biogas alternatives need to be strategically exploited to the production of H2 to activate fuel cells.
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 2. Processes used for generating hydrogen
herein. from methane and biogas
H2 has high energy capacity, with the largest amount of
energy per mass unit than any other known substance The most common methane reforming processes for
(121.000 kJ/kg). hydrogen production are known as: “steam reforming (SR)”
The best energy use of H2 takes place in fuel cells. Fuel [34e43], “partial oxidation reforming (POR)” [44e51], “auto-
cells achieved remarkable progress in the last decade, which thermal reforming (ATR)” [52e57], “dry reforming (DR)”
were developed for transportation, as well as for power gen- [58e63] and “dry oxidation reforming (DOR)” [1,64e67]. There
eration in stationary or portable installations. The fuel cell are other non-conventional processes reported in the litera-
system can include several applications, such as: large power ture for the production of H2 from methane, such as: “solar
stations; power distribution generators, used in buildings and reforming” [6,24], “thermal plasma reforming” [68e71] and
homes; small portable power supply equipment for micro- “catalytic decomposition” [72,73]. Traditional methods of
electronic devices; and auxiliary power units in vehicles, large scale H2 production used by industries are the first three
among others [19,21,22]. These cells then transform the mentioned, with natural gas as the main source of hydrocar-
chemical energy of the H2 molecules into electrical energy bons (z90% of CH4).
with up to 60% of efficiency [19,21]. Additionally, when H2 is In most studies found in the literature on biogas reforming
used in vehicular fuel cells, it can yield two to three times to produce H2, there are detailed experiments using mixtures
more efficiency than the current devices used in internal of CH4 and CO to simulate laboratory biofuel compositions.
combustion vehicles (20e30%). These qualities make H2 one However, the high purity CH4 (>99%) is commonly used to
of the main alternatives for replacing fossil fuels consumed simulate laboratory scale reforming processes, with few
worldwide [22]. studies found that use biogas from the direct digestion pro-
Currently, H2 is widely used as raw material in the chem- cess of residual biomass (real biogas) in their experiments
ical industry, in food processing, in hydrogenation processes, [5,74,75].
in the production of ammonia and methanol, in the Thus, to choose the reforming process using biogas, its
FischereTropsch synthesis, in the pharmaceutical industry, composition must be taken into account in three different
among others [23]. situations, which may be sequential: i) in natura, with 55e70%
The demand for H2 grows yearly. The available 2008 data of CH4, 30e45% of CO2 and 500e4000 ppm of H2S (Table 1); ii)
indicate that H2 consumption by the oil sector was of 364 partially treated for H2S removal; iii) purified for
billions/m3, while the global H2 consumption was of 409 bil- “biomethane” enrichment (93e96% of CH4, 4e7% of CO2 and
lions/m3. It is also estimated that by 2013 the global H2 de- <20 ppm of H2S). Note that in the latter case, the CH4
mand will increase 18%, with nearly half of this expected content is hardly ever higher than 95% using economically
increase generated outside the refineries by other sectors [7]. viable treatments [1e3,7,8].
 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 3 8 ( 2 0 1 3 ) 5 2 1 5 e5 2 2 5 5217

Before reforming, the methods tipically used for the temperatures ranging from 300 to 450  C and catalysts based
removal of corrosive species in biogas can be divided into two on Fe, Cu, Mo or FeePd alloys (among others), which enables
categories: i) those that involve physico-chemical phenomena the production of an additional amount of H2. Equation 3
(including the processes of absorption in aqueous solutions; shows the reaction of methane SR associated with the shift
chemical adsorption of H2S on solid adsorbents such as acti- reaction [2,3].
vated carbon, modified zeolites and metal surfaces, with Additionally, the harsh conditions required promote par-
consequent formation of metal sulfide, and washing with allel carbon formation reactions (methane decomposition re-
solvents), and ii) those involving biological processes (con- action), Boudouard reaction or disproportionation reduction
sumption of contaminants by living organisms, such as spe- reaction of CO, respectively, Eqs. 4, 5 and 6) favoring catalyst
cies of chemothrophic thiobacteria, which serve as oxidants deactivation by carbon deposition on its surface (coke)
in the sulfur biofilters, biotrickling filter and units of bio- [77e79]. It is usually desired for the carbon to be on the cata-
depuration, and conversion to less harmful forms) [24,76]. lyst surface in the form of nanotubes, which causes lower
In general, H2 can be produced by methane or biogas carbon dispersion over the surface, thus preserving its activity
reforming in a wide temperature range of 600e1000  C for a longer period of time [72].
(endothermic and reversible reactions), involving predomi- The catalysts usually used in SR consist of Ni (transition
nantly catalytic processes that are often combined. Both metal), Pt, Rh or Pd (noble metals), of which the Ni catalysts
reforming processes can be performed under low pressure (in have the advantage of having lower costs. On the other hand,
most cases under atmospheric pressure) in tubular fixed-bed Ni has greater deactivation susceptibility by the coke forma-
or fluidized reactors [7,24,25]. tion due to the high temperatures used, which makes the Pt
The reforming processes in the next items use methane as and Pd catalysts interesting with regards to stability. When
raw material, since it is the main source of hydrocarbons there is limited mass transfer, Rh is used as it has catalytic
used. However, in various reforming processes, biogas can be activity that is much higher than Ni and a lower coke forma-
used as a methane source, which directly depends on its tion tendency [36,42]. Basic supports containing promoter el-
composition. Thus, most of the research involving methane ements such as Ca, Mg and K can also be used to decrease
reforming can also be adapted to biogas reforming. carbon accumulation on the catalyst, since they favor carbon
Table 2 shows the chemical reactions cited and their species gasification by the carbonewater steam reaction
respective thermal reactions at 298 K (25  C), in order to (reverse Eq. 6), due to increased water adsorption [80e83]. The
facilitate the information organization contained throughout metals cited, as well as others, can be used as active species in
the work. the preparation of supported catalysts using various types of
matrices, such as: SiO2, Al2O3, ZrO2, etc. [27,41].
2.1. Conventional reforming processes To obtain high purity H2, the CO2 and CO formed in SR must
be effectively separated, which is not unique to this type of
2.1.1. Steam reforming (SR) reforming, required in all the processes where there is greater
SR is the combination of methane with water vapor in the interest in H2 production rather than synthesis gas. Typically,
presence of a catalyst, producing CO and H2 (Eq. 1). This is a the H2 production applying the conventional SR process uses
highly endothermic process which requires reaction temper- three integrated systems: reformer, conversion reactor (shift
atures ranging between 650 and 850  C, to obtain H2 yields of reaction) and separating unit [84].
60e70% [34e43]. Several studies show good efficiency in the separation
Although it has great energy expenditure SR is the most process using selective membrane reactors with H2, which can
widespread industrial route to obtain H2. The H2/CO ratio be directly fed to the fuel cell. The membrane reactor then
produced in SR is equal to three, the most appropriate one allows all reactions developed in the conventional reactor to
from the H2 generation point of view. In order to eliminate CO, occur on a single device, producing pure H2. Thus, the SR
the WatereGas Shift reaction, commonly known as “Shift methane reaction (Eq. 1) and shift reaction (Eq. 2) occur
reaction” (Eq. 2), is the most widely used, requiring 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 Type of reaction Thermal reaction, DH298 (kJ/mol)

Eq. 1 CH4 þ H2O4 CO þ 3H2 206

Eq. 2 CO þ H2O4CO2 þ H2 41.2
Eq. 3 CH4 þ 2H2O4CO2 þ 4H2 165
Eq. 4 CH44C þ 2H2 74.9
Eq. 5 2CO4C þ CO2 172.4
Eq. 6 CO þ H24C þ H2O 131.3
Eq. 7 CH4 þ 1/2O24CO þ 2H2 35.6
Eq. 8 CH4 þ 2O24CO2 þ 2H2O 801.7
Eq. 9 CH4 þ 1/2xO2 þ yCO2 þ (1xy)H2O4(y þ 1)CO þ (3xy)H2 z0
Eq. 10 CH4 þ CO242CO þ 2H2 247.4
Eq. 11 CH4 þ bCO2 þ (1  b)/2O24(1 þ b)CO þ 2H2 (285b  38) 0  b  1
5218 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 3 8 ( 2 0 1 3 ) 5 2 1 5 e5 2 2 5

catalyst bed. Furthermore, the membrane provides greater reactor, leading to the synthesis of the desired product.
shift ability to the chemical equilibrium of the reaction, Additionally, the combination of these reactions can improves
increasing the productivity of H2, since removing H2 from the the temperature control in the reactor and reduce the for-
reaction medium displaces the dynamic equilibrium for mation of hot-spots, thus avoiding the deactivation of the
forming products. This shift allows the reforming reaction to catalyst [54,90].
be carried out at temperatures below 500  C, without any In this system the partial oxidation reaction of methane
methane conversion loss [38,42,85e87]. occurs simultaneously with SR, which makes the process self-
sustaining, significantly reducing energy costs. Thus, for SR
2.1.2. Partial oxidation reforming (POR) methane to be advantageous over others, it is necessary that it
POR is an alternative method to produce H2 with reduced takes place under autothermal conditions, performed adia-
energy costs, since the reaction is moderately exothermic (Eq. batically together with partial oxidation reaction, in order to
7), contrary to SR which is highly endothermic. In this type of produce synthesis gas with a H2/CO ratio between 2.0 and 3.5,
reaction, methane is partially oxidized to CO and H2 (synthesis using H2O/CH4 ratios between 1.0 and 2.5, O2/CH4 between
gas), at atmospheric pressure, requiring temperatures be- 0.25 and 0.55 [52e54,56].
tween 700 and 900  C to ensure complete conversion (H2/CO It should be noted that the selectivity of products in the
ratio close to 2) and to reduce soot formation. However, a oxidation zone is highly dependent on temperature, that is,
slight decrease in CO selectivity cause the methane to react partial oxidation reactions (Eq. 7) are favored by increased
with oxygen to form CO2 (Eq. 8), leading to complete com- temperature, and total oxidation (Eq. 8) favored by decreased
bustion (strong exothermic reaction), which results in high temperature [91].
reaction temperature increase, which can form hot-spots in
the reactor bed and form coke on the catalyst surface [48e51]. 2.1.4. Dry reforming (DR)
According to ÁVILA-NETO (2009) [88], although the DR occurs when CH4 reacts with CO2 to produce CO and H2 (Eq.
temperature increase favors the CH4 conversion, the O2/CH4 10). This type of reaction is attractive from an environmental
feed ratio applied to the reactor is the variable that most standpoint, since it consumes two gases that contribute to the
influences the conversion. In this case, CH4 is completely greenhouse effect (CH4 and CO2). However, it should be noted
consumed to the O2/CH4 ratio close to 0.5. that the endothermic nature of the reaction minimizes the
Some studies focus on developing high activity and sta- reduction of CO2 emissions, since the CO2 emitted by the
bility catalysts for methane POR. Mixed metal oxides, solid burning of fuel used to generate the heat required for the re-
solutions of NiOeMgO, NieMgeCreLaeO and CaeSreTieNi action should be accounted for. From the industrial point of
are reported as highly active and selective catalysts at view, methane DR also satisfies the requirement of many
elevated temperatures (>800  C), with higher carbon deposi- synthesis processes of oxygenated compounds and liquid
tion resistance [48,89]. hydrocarbons (FischereTropsch synthesis), which is an effi-
cient route for producing synthesis gas, yielding a H2/CO ratio
2.1.3. Autothermal reforming (ATR) close to 1 [59,63,79,80].
Because it is a highly endothermic, SR associated with the According to the literature regarding this topic, the main
Shift reaction (Eq. 3) requires external power supply. A re- reaction (Eq. 10) can be accompanied by competing parallel
actor’s internal heating is generally more efficient than reactions that modify the equilibrium conversion of CO2 in
external heating, and a reaction that releases energy in the CH4, as follows: reverse gasewater shift (Eq. 2 reverse),
catalyst bed can make the manufacturing process of H2 decomposition of carbon monoxide (Boudouard reaction) (Eq.
energetically more economical. However, the partial oxida- 5) and decomposition of methane (Eq. 4) [60]. In general, DR
tion reaction of CH4 has the advantage of being exothermic occurs at temperatures ranging between 700 and 900 C,
(Equation 7), but generates a lower H2/CO ratio in comparison using a CH4/CO2 molar ratio between 1 and 1.5, attaining H2
with SR. yields of around 50% [62,63,92].
Based on these observations, other CH4 reforming types, If the decomposition reaction of the methane (Eq. 4) is
called ATR, can be performed with a combination of the two faster than the carbon removal rate, there will be serious
aforementioned reforming techniques, resulting in the sum of problems for the formation of coke, with the consequent
reactions described by equations 3, 7 and 8 [53e57]. ATR also deactivation of the catalyst and blocking of the reactor by the
occurs in the presence of CO2, represented by Equation 9 coke formed. The decomposition reaction of carbon monoxide
[74,75]. (Eq. 5) is favored at low temperatures and, together with the
There is a thermal zone in the reactor, where the partial decomposition reaction of methane, it can generate carbon
oxidation is conducted to generate the heat required for SR [93e97]. Thus, the main problem of DR is the greater tendency
that takes place in the catalytic zone, fed by a downward to form coke, accumulated on the support as well as on the
steam flow. The heat generated by the zone where the partial active phase of the catalyst, since the carbon-water steam
oxidation takes place does not require external heating, reaction does not occur as it does in SR (reverse Eq. 6). Much
resulting in an efficient energy process. The advantages of effort has been employed in the search for catalysts that avoid
ATR concern the speed with which the reactor can be stopped the deposition of carbon, while being thermally stable,
and restarted, and the capacity to produce higher amounts of maintaining selectivity in the production of H2 [31,63,97,98].
H2 with lower O2 consumption when compared to isolated The most active catalysts for methane DR, reported in
POR, since the H2/CO ratio in the synthesis gas produced can literature, are those that use metals of the groups 8, 9 and 10 of
be easily adapted through the CH4/O2/H2O ratio to feed the the Periodic Table, particularly Rh, Ru and Pt. However, these
 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 3 8 ( 2 0 1 3 ) 5 2 1 5 e5 2 2 5 5219

metals are expensive and of limited availability, and are determines the oxidation process (complete oxidation when
therefore, in practice, not suitable for the process at an in- b ¼ 0 (Eq. 8), or traditional DR when b ¼ 1 (Eq. 10)), and auto-
dustrial level. Therefore, various catalysts have been devel- matically, the amount of heat released or consumed [66,67,79].
oped according to greater availability and lower price, which is Considering that dry reforming in the presence of O2
usually associated with increased coke susceptibility, as in the simultaneously involves the traditional DR (Eq. 10) and POR
case of Ni and Co catalysts [60,61,99e102]. (Eq. 7) processes, characterized as endothermic and
exothermic, respectively, the methane conversion to synthe-
2.1.5. Dry oxidation reforming (DOR) sis gas occurs with high energy efficiency, requiring little
A strategy for the control of carbon deposition on the surface external energy [103e108].
of the catalysts is to combine the methane DR and POR. Co- Research on catalysts for this type of reaction is usually
feeding O2 with CH4 and CO2 provides additional advantages, directed to support development or the insertion of a second
such as: reducing the global energy involved, improving the metal associated with Ni (bimetallic catalyst) to enhance its
conversion of CH4 and increasing the product yield at a lower stability [1,47,64,65]. Regarding DR, the addition of O2 reduces
temperature; enhanced catalyst stability and increased deac- the formation of coke on the catalyst due to greater control of
tivation resistance; control the H2/CO ratio by modulation of the partial oxidation of the novel carbon species, CH4 and CO2,
O2 to meet the flow requirements [1,65]. Methane DOR can be for CO [92].
written as shown in Equation 11, where b is the stoichiometric Table 3 shows a summary of the reaction conditions used
fraction of CO2 fed with traditional DR. It is evident that the in the different H2 production routes using methane or real
theoretical H2/CO ratio, given by 2/(1 þ b), is greater in DOR for biogas as the main raw materials.
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 3. Use of hydrogen in fuel cells
manipulating the process variables, particularly the reaction
temperature and/or relative concentration of O2 in the reactor 3.1. Fuel cell concepts
feeding. In general, the exothermic nature increases for a
given temperature as the O2 concentration in the feed in- Fuel cells are devices that can convert the chemical energy of a
creases. This is due to the fact that the addition of O2 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 Reactor Temperature ( C) Catalyst H2/CO Conversion of CH4 (%) Reference

SR Fixed-bed 600 Ni-Ce0.8Zr0.2O2 3.4 70 [41]

Fixed-bed 650 NiMg17.4Al1.6O20.8 3.7 98 [43]
Fixed-bed 700 Ni/Al2O3 a 85 [39]
Fixed-bed 715 Ru/Al2O3 2.7 90 [105]
Fluidized-bed 850 Ni/Al2O3 2.1 98 [2]
Fixed-bed 750 Ni/CaOeAl2O3 2.5 95 [3]
Fixed-bed 750 Ni/Al2O3 2.0 85 [106]
Fluidized-bed 750 Ni/Al2O3 2.2 96 [106]
POR Fixed-bed 800 Pt/CeO2 2.0 85 [44]
Fixed-bed 850 NiO/MgO 2.0 87 [45]
Fixed-bed 700 Ni/Al2O3 2.0 100 [46]
Fixed-bed 800 NiCoMgCeOx/ZrO2eHfO2 2.0 95 [48]
ATR Fixed-bed 700 Ni/MgAl2O4 3.2 92 [52]
Fixed-bed 800 Pt/ZrO2/Al2O3 2.0 100 [53]
Fixed-bed 700 Rh/Al2O3 3.5 95 [55]
Fixed-bed 750 Ni/Cu5Zr10Ce20Al65O8 3.9 100 [56]
Fixed-bed 750 Ni/cordierite 2.6 90 [74],b
Fixed-bed 850 Ni/insulating (Si,Mg,Al) (monolithic) 2.8 95 [75],b
Fixed-bed 800 Ni/SBA-15 1.4 92 [31]
Fixed-bed 750 Ni/NiOeMgO 1.2 75 [111]
DR Fixed-bed 860 Ni/CeO2eAl2O3 1.3 90 [60]
Fixed-bed 750 Rh-NiLa/g-Al2O3 0.9 70 [92]
Fixed-bed 700 La/hydrotalcite 0.7 67 [62]
Fixed-bed 700 Ni/CeZrO2eMgAl2O4 1.2 85 [63]
DOR Fixed-bed 750 Rh-NiLa/g-Al2O3 1.0 86 [92]
Fluidized-bed 900 Pt-Rh/CeeZrO2eAl2O3 1.0 100 [1]
Fixed-bed 850 NdCoO3 perovskite 1.7 95 [66]
Fluidized-bed 750 5Ni/5ZrO2eSiO2 1.9 77 [47]

a Information not available.

b Real biogas.
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efficiency and with lower polluting emissions than conven- Ru, Sn, Mo and Os, which form alloys or co-deposits
tional equipment/techniques. dispersed on carbon, result in significant tolerance increase
The development of various types of fuel cells partially to CO [118e121].
focuses on optimizing the layer of the catalytic electrodes, and The SOFC fuel cell is currently one of the most studied
specifically on reducing the amount of metal without appre- because of its exceptional application potential as a power
ciable loss of cell performance. It is known, however, that with generation system due to its high-energy conversion efficiency.
the operation there may be significant changes in the struc- Correspondingly, a considerable advantage of SOFC is the
tural properties of the catalyst, and then its stability assumes possibility of using other fuels in addition to H2 such as natural
a significant role in the cell’s useful life [109e111]. gas, biogas, gasoline, methanol and ethanol [19,81,108].
In a fuel cell the power supply is uninterrupted while it is
fed with the fuel and the oxidant, different from a battery in 3.3. Internal reforming of biogas in fuel cells
which the energy storage is limited by the amount of reagent
stored in it. Insofar the theoretical thermodynamic efficiency While the technology to efficiently convert H2 into electrical
of fuel cells are close to 90% in the thermal engines (Carnot), energy and into the required power levels are closer to
this efficiency is of only 40% under typical operating condi- commercialization, parallel attempts have been made for the
tions for both systems. In practice, the efficiency of a fuel cell direct use of biogas in fuel cells, known as “internal reform-
is usually less than 60% [112]. ing” [5,20,109,122e129].
High-temperature fuel cells, such as SOFC and MCFC, are
3.2. Types of fuel cells better suited for the direct use of biogas, because they have a
greater capacity to thermally integrate internal reforming and
Fuel cells have been developed to supply different markets. increase tolerance against contaminants of H2, while main-
Owners of electric stations investigate the use of PAFC cells taining high electrical efficiency (close to 50%). Several studies
(Phosphoric acid fuel cell ), MCFC cells (Molten carbonate fuel cell ) have been reported in the literature on the use of various types
and SOFC cells (Solid oxide fuel cell ). The latter cell promises of biogas internal reforming in high-temperature fuel cells. In
high efficiency (50%e60%) and its market type is not restricted some cases, it was demonstrated that, electricity can be stably
by the size or weight of the cell, hence requiring very durable obtained from biogas without auxiliary fuel, external reformer,
systems. Similarly, residential cells represent a large and humidifier, and precious metal catalyst [124,125,130]. Typi-
attractive market segment. However, for these purposes, as cally, SOFC cells exhibit eletrodic catalysts that comprise: i)
well as for automobile use, there is a size and weight limita- anode and support: Ni-YSZ (yttria-stabilized zirconia) or
tion, requiring to evaluate the ability of intermittent opera- NieScSZ (scandia-stabilized zirconia), ii) cathode: LSM
tion, for the fuel cell PEMFC or PEM (Proton Exchange Membrane (lanthanum strontium doped manganate) or composite and iii)
Fuel Cell ), which has an electrolyte polymeric membrane, the electrolyte: YSZ-TiO2, ZEI-MgO, Y2O3, CeO2, MnOeCeO2 and
most widely studied [19,81,90,108,113]. According to CIPITÍ GdO2eCeO2 [19,127,128].
et al. (2008) [114], PEMFC, stands out as a key option, for A disadvantage of the internal reforming process is the
transportation use (electric vehicles) as well as for small- formation of CO, which acts as a poison to the fuel cell when
scale power generation facilities (homes) due to durability, in the range of 50 ppm [81,126]. Additionally, the variability of
compatibility, low operating temperatures, high conversions biogas composition and the poisoning of the catalysts of the
and low polluting and noise emissions. fuel cell by carbon deposition (coke) by CO disproportionation
The degree of H2 purification required for fuel cells de- (Eq. 5) and the presence of sulfur traces, represent the main
pends on the application. Gas separation by pressure swing problems commonly faced [2].
adsorption (USGAMP) or palladium membranes are used to In the former case, the coke formation reduces the catalyst
produce H2 with purity above 99.999%. For fuel cells PEMFC or activity and simultaneously blocks the pores and can destroy
PAFC (low temperature) CO must be reduced to less than their structure. New approaches to reduce carbon deposition
10 ppm [19]. However, CO drastically affects the performance by adding different promoters (Sn, Mo, Li, Mg, Ca, Sr, Ce, Ru,
of the system, as it usually binds to the metal atoms of the Rh, Pd and Pt) in the anode Ni-YSZ (yttria stabilized zirconia)
catalyst, preventing adsorption and the consequent are reported in the literature. Furthermore, the addition of
oxidation of H2. Thus, the choice of a catalyst electrode water and air for a CO2/CH4 ratio between 0 and 1, is
tolerant to CO and/or the use of tools to minimize the considered a strategy to suppress carbon formation [128].
effects caused by the reaction contaminant (current pulses In the latter case, the sulfur-containing species cause a
in the cell, air insertion with fuel flow, introduction of H2O2 substantial decrease in the conversion to hydrogen. This is
into the cell anode, etc.) are some of the main challenges to due to the strong sulfur chemisorption on the surface and
be overcome regarding the low-temperature fuel cell within particles of the electrodic catalyst. An alternative to
technology [84,115e117]. this problem is to pass a gaseous stream rich in methane and
It is known that at high temperatures the tolerance to CO hydrogen at elevated temperature, which causes the gradual
increases significantly, enabling its use in some fuel cells, increase in conversion as the physically adsorbed sulfur is
such as MCFC and SOFC (high temperatures), H2 with higher removed. Although poisoning appear to be partially reversible,
CO concentrations, expanding the possibilities of using an the initial levels of conversion are not achieved because there
interconnected system for methane or biogas reforming are a slow desorption of such species [131].
processes [19]. In this case the use of bimetallic eletrodic In addition to the problem caused by contaminants, it is
catalysts that contain a second element besides Pt, such as possible indeed that the temperature gradients from the
 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 3 8 ( 2 0 1 3 ) 5 2 1 5 e5 2 2 5 5221

endothermic reforming reactions cause the destruction of the activity. For the partially treated reforming biogas (H2S
electrolyte. In this case, one possible solution is to add air to removed), using a chemical composition with considerable
the biogas, which not only prevents coke formation, but also CO2 content (30e45% vol.), the dry process is interesting, as it
removes the high temperature gradient due to the occurrence enables taking advantage of the CO2 intrinsically present in
of exothermic reactions (complete and partial oxidation of the composition, as an oxidant in this kind of reforming.
methane) [127]. When the biogas has a CO2/CH4 ratio lower than 1 (as it usually
Fig. 1 shows the region with the greatest tendency to occurs), it is necessary to add an alternative oxidant for the
carbon deposition in the diagram of CeHeO ternary phase, production of synthesis gas. Therefore, the addition of O2 by
when biogas internal reforming is used in SOFC fuel cells. In the DOR method could be a possible route for the production
any type of conventional reforming used, the diagram in of H2 from biogas, also promoting a slight increment in the H2/
Fig. 1 is valid, since the C, H and O elements are always CO ratio.
present in the molecules of the reactants (see Table 2). In almost all reforming technologies, one of the main
challenges is developing catalysts capable of preventing car-
bon deposition on the active phase in order to increase its
4. Considerations for H2 production from useful life. In the case of DR, the problem is even worse, often
biogas making this type of process unfeasible due to the rapid
deactivation of the catalyst. In DOR, the periodical passage of
It is acknowledged that biogas has great potential for H2 O2 flow through the catalyst bed helps the gasification of the
generation through several reforming processes. However, carbon deposited on the surface, increasing the availability of
selecting a specific process depends on several factors, some catalytic active sites and temporarily/partially recovering the
of which are: biogas composition, purity required for using H2, activity of the material.
volume production of the desired H2, and investment avail- However, in both reforming cases (DR, DOR) the H2/CO
ability, among others. ratio is usually close to 1, which restricts the H2 production
Some of the reforming technologies mentioned in this potential, requiring a higher CO volume to be separated from
work are already or will soon be commercialized, as for the products by the Shift reaction, making it difficult to obtain
instance e SR, POR and ATR. Other newer technologies, not high purity H2. Furthermore, in the DR biogas, part of the H2
yet consolidated, will take some time to be commercialized, produced reacts with CO2 by the reverse shift reaction (Eq. 2)
currently only used in research, such as internal reforming in producing water and CO, which reduces the production
fuel cells [24]. Among the existing fuel cells, the PAFC type yield of H2.
cells have already been marketed, however they encounter Thus, maximizing the H2 yield from biogas with the SR
problems such as durability and sensitivity to contaminants, process, followed by Shift reactions, seems to be a less elegant
rendering their technological route unviable. Although the but more feasible solution, particularly with respect to mini-
PEMFC, SOFC and MCFC cells are in rapid development, they mizing CO and maximizing H2 production. In this case, the H2/
are not commercial products, but rather advanced prototypes. CO ratio obtained is high (close to 3) and the technology
In natura biogas cannot be used as raw material in con- involved better known and controlled. There are many studies
ventional reforming processes due to the likely poisoning of which adapt biogas in SR, despite the high CO2 content,
the catalyst by H2S, resulting in the rapid loss of catalytic 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
Fig. 1 e Ternary CeHeO diagram CeHeO showing the processes are the most recommended ones.
possibility of coke formation for biogas internal reforming In any conventional reforming process using biogas as raw
in SOFC. Adapted from Shiratori et al. (2010) [122]. material, new catalysts with high catalytic activity at high
5222 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 3 8 ( 2 0 1 3 ) 5 2 1 5 e5 2 2 5

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