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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5

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Review Article

Overview of hydrogen production from biogas

reforming: Technological advancement

Ravindra Kumar a, Anil Kumar a,b,*, Amit Pal a

a
Department of Mechanical Engineering, Delhi Technological University, Delhi 110042, India
b
Centre for Energy and Environment, Delhi Technological University, Delhi 110042, India

highlights graphical abstract

Biogas reforming is done in order

to production of H2.

Methane requires high tempera-
ture for reaction in steam reform-
ing process with catalyst.

H2/CO ratio is 3 and 2 means H2
yield above 70% and almost 67%,
respectively.

H2 yield around 74%, with H2/CO
ratio close to 2.8 in auto thermal
reforming.

Dry reforming process leads to
molar ratio H2/CO nearly 1 and H2
yield approx 50%.

article info abstract

Article history: In this article, possibilities of biogas reforming techniques for hydrogen production are
Received 30 April 2022 discussed. The consideration of biogas reforming to produce H2 and fuel cell application
Received in revised form from membrane technology is presented. In steam reforming process, methane requires a
31 July 2022 high temperature for reaction, but a suitable catalyst can manage a higher temperature.
Accepted 5 August 2022 The ratio of H2/CO is close to 3, which means higher H2 yield (above 70%). The ratio of H2/
Available online 10 September 2022 CO to nearly 2 and H2 yield almost 67% and also reduces the soot formation for partial
oxidation process. In Auto thermal reforming, higher yield of H2 is around 74% with the
Keywords: ratio of H2/CO close to 2.8. The dry reforming process leads to a molar ratio H2/CO of nearly
Biogas one and H2 yield of approximately 50%. The ratio of H2/CO correspondingly improves and
Hydrogen generates H2 yield of approximately 60% for dry oxidation reforming process. For sus-
Reforming tainable decentralized power generation in remote and rural areas, large-scale develop-
Catalyst ment of H2 energy technology is required. Biogas reforming is an auspicious process for the
Membrane reactor production of green hydrogen gas as well as for reducing overburden on natural gas. The
main benefit of using biogas for H2 production as a renewable energy source is reducing

* Corresponding author.
E-mail address: anilkumar76@dtu.ac.in (A. Kumar).
https://doi.org/10.1016/j.ijhydene.2022.08.059
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
34832 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5

excessive burden on natural gas and greenhouse gas emissions. Nowadays, the importance
of renewable H2 production has increased due to many reasons such as depletion of fossil
fuel reserves, global environmental issues, energy issues, and demand for pure H2.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34832
Biogas potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34833
Biogas reforming techniques for H2 production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34834
Steam reforming process (SR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34834
Partial oxidation reforming (POR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34834
Auto thermal reforming (ATR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34835
Dry reforming process (DR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34835
Dry oxidation reforming (DOR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34835
Current research on conventional processes from biogas reforming based on catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . 34836
Steam reforming of biogas (SRB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34836
Partial oxidation of biogas (POB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34837
Auto thermal reforming of biogas (ATRB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34837
Dry reforming of biogas (DRB) and dry oxidation reforming of biogas (DORB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34838
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34839
Membrane reactor (MR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34841
Concept of MR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34841
Arrangement of membrane reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34842
Packed bed membrane reactor (PBMR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34842
Fluidized bed membrane reactor (FBMR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34844
Modeling outcomes from PBMR and FBMR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34845
Recommendations for the production of H2 from biogas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34846
Hydrogen utility in fuel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34847
Recent status of biogas reforming for H2 production from conventional reactors and membrane reactors . . . . . . . . . 34848
Future prospect of biogas reforming in research direction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34849
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34850
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34850
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34850
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34850

contribution to sustainable progress and energy systems in

Introduction
The current energy sector focuses on producing energy via
traditional resources like fossil fuels. Growing worldwide de-
mand for energy and environmental alarms related to green-
house gas emissions has fueled the introduction of alternative
power generation possibilities. Biogas reforming is an auspi-
cious process for the production of green hydrogen gas as well
as for reducing overburden on natural gas. Currently, Hydrogen
production has become the most important research area,
especially renewable energies due to globally growing energy
demand, depletion of fossil fuels, environmental issues, and
progressive fuel cell technology [1,2]. As a renewable energy
source created through biological material derived from living
organisms and plant-based material used as a fuel termed
biomass. Biomass energy systems make an important
developing and developed countries in the coming decades [1].
Biomass could be the highest appropriate renewable en-
ergy option compared to other renewable energy sources
because of its several benefits and abundantly available
worldwide. The waste biomass can be used for generating CH4
from decomposition of organic materials; otherwise, it may
contribute to greenhouse effect. Gaseous fuels such as biogas
and producer gas could be generated through biomass and
agricultural residues like rice straw or wheat straw can be
transformed into biogas from anaerobic digestion. In contrast,
biogas contains primarily mixture of CH4 and CO2, including
other gas traces like H2S, H2, N2, NH3, H2O and O2 [2].
Biogas can also be attained through landfills known as
landfill gas. Biogas composition can vary from site to site,
feedstock, and anaerobic digesters used. The most important
technology for large-scale production of H2 is to facilitate 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
reforming of light hydrocarbons (HCs), predominantly
methane (CH4) which is the main component of biogas [3].
However, some of these routes produce a combination of CO
and H2, also called synthesis gas, widely used in industry [4].
The production of purity H2 via synthesis gas is quite expen-
sive due to the need to remove CO [5].
According to literature on reforming, the research has
highlighted cost and energy-saving catalysts. The use of cat-
alysts with higher catalytic activity and stability in reforming
route can lead to a decrease in the high temperatures
commonly used, which can be accompanied by improvement
in the reaction rate and a slowdown in the catalyst deactiva-
tion process. Poisoning effect, additional impurities, and car-
bon deposition (coke) are often severe problems [2].
Generally, hydrogen is generated from various hydrocar-
bons like methane, methanol or ethanol, and naphtha oil
through the traditional steam reforming method. However,
according to industrial scale, mostly H2 (above 80%) is produced
from SR of natural gas (CH4) using fixed bed reactors (multi-
tubular). In order to small scale, other two alternate options
considered with SR such as partial oxidation and auto-thermal
reforming, whereas POx occurs less efficiently compared to SR
and ATR occurs both exothermic reaction (via POx) and endo-
thermic reaction (via SR) conduct in same reactor [6].
The limitation of equilibrium reactions is the main draw-
backs of conventional reforming processes such as SR, POx
and ATR. In order to complete conversion of fuel, generates
hydrogen with rich gas mixture involving CO2 and other by-
products. Thus, to produce pure hydrogen, this chemical
process takes place in several reaction units such as high
temperature reformers, high temperature (HT) and low tem-
perature (LT) shift reactors, followed by separation units
mainly such as pressure swing adsorption (PSA). The number
of different process steps reduces system efficiency and
makes scale-down uneconomical. A typical illustration of the
reaction process of SR is shown in Fig. 1.
Although this method provides high hydrogen yields,
obtaining the desired high purity hydrogen requires complex
energy integration, expensive heat exchangers (High temper-
ature), and various process units. Among the various tech-
nologies associated with hydrogen generation, purification
and separation, membrane technology appear to be more
auspicious, and membrane separation is progressively gaining
attention as a good candidate for replacing existing systems.
The specific constraints of thermodynamics and limitations of
conventional reactors can be avoided with innovative inte-
grated systems, also known as membrane reactors (MRs).
Membrane reactors are technical systems where reaction and
separation take place in single unit [7], and compared to con-
ventional configurations wherein the reactor is coupled to a
unit of downstream separation, the utility of membrane
reactor can offer many potential benefits, such as lower capital
costs (caused by reduced size unit), increased yield and selec-
tivity (caused by equilibration shift effect) and decreased
downstream cost of separation (integrated separation unit).
The achievement of membrane reactors in order to H2
production depends on few factors such as advancement in
thin membrane production with high H2 perm-selectivity and
high H2 fluxes, an innovative reactor concept that integrates
energy exchange and separation unit, reduces resistance to
34833
the transfer of heat and mass, and simplifies shells and seals
of membranes.
The main goal of this manuscript is to highlight the
numerous possibilities of biogas reforming for hydrogen pro-
duction based on various conventional and membrane re-
actors. Catalysts play a key role in hydrogen production
methods. Different catalyst compositions in various biogas
reforming methods have also been extensively studied. In
addition, membrane reactors, their types, and simulation
models for the production and purification of hydrogen were
investigated. This review presents biogas as renewable energy
in hydrogen production and fuel cell applications.
Biogas potential
Biogas is viable, sustainable, and efficient energy resource
because of plentiful supply of low cost feedstocks. The
countless applications such as in power sector, heating, fuel,
and hydrogen production by chemical processing and biofuels
through raw materials. Worldwide, biogas-based power gen-
eration capacity has been increasing from 65 GW (year 2010) to
120 GW (year 2019) [145].
The global capacity of biogas plants was approximate
19.5 GW at the end of the year 2019 with growth driven by
factor as high prices of fossil fuels, easy access to low cost
biomass feedstock and more concerns over global warming
and emissions [146,147]. The development of biogas accoun-
ted 0.25% energy market and 27% biofuel market worldwide in
2011 [148]. In 2005, biogas digesters (small households) were
available to nearly 16 million worldwide, but most were in
India and China. In India, the firewood was switched by biogas
as an equivalent of 16 million tons (MT) up to 1996, while in
China, about 4% of total energy demand is fulfilled by 7 million
biogas digesters [148].
Production of biogas and its utilization have numerous
benefits. It offers greenhouse reduction, alternative fuel, heat
and electricity, fertilizer as by-product, waste recycling, and
safety of environment from pollutants. Biogas arrangements
could be renovated manure or organic domestic waste mate-
rials into gas to light and cook. The waste products like rice,
fruits, and vegetables can be transformed into energy rather
than disposed of. The waste materials storage and disposal
invite insects and pests. Biogas supports waste management
and donates to enriched hygiene in rural zones [8].
Biogas can also help dipping deforestation by using less
firewood and promoting fertilizers that carry a carbon foot-
print and affect the soil quality. Biogas consumption drops
GHG emissions compared to known fuels (fossil fuels). The
combustion of Bio-CNG produces nearly 8e22 g CO2 eq./MJ,
which is 80% lower with compare to fossil fuels. Biogas com-
bustion generally does not generate polyaromatic hydrocar-
bons (HCs) and hazardous aromatics. Lacking these HCs
avoids tenet soot emissions and particulate matters via
combustion process. Formation of soot from combustion of
biogas/natural gas depends upon combustion conditions,
whereas net soot emission is reduced from gas combustion
control that is tough to attain along with liquid fuel. Filling
stations of biogas (liquefied) are well known in the US, China
and Europe [9].
34834 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
Fig. 1 e Steam reforming process via conventional method using various reactors [6].
Biogas is primarily used as fuel for cooking purposes and
stationary engines. Biogas potential has not yet been fully
explored and used. To promote domestic biogas, the Indian
government established the National Biogas Development
Project (NPBD) in 1981. The number of biogas plants in India
has increased from 1.23 million in 1990 to 4.54 million in 2012,
despite the enormous potential of 12.34 million digesters [10].
The installation of biogas plants has increased related to its
potential by approximately 26%e37% from 2002 to 2012. As
domestic scale (biogas plants) leads to an expected saving of
4.0 million tons of fuel (wood type) every year, as well as
producing one Mt of enhanced organic manure [11]. In Europe,
the production of biogas has been growing nearly from
9.29  109 L (2009) to 1.65  1010 L (2016) through the using
biogas technology [147].
Biogas is currently used in integrated heat and power (CHP)
plants for heat and power generation. In Sweden and Ger-
many, biogas has been used as a transport fuel. It can be
turned not only into fuel but also into a valuable commodity
as synthesis gas or syngas (H2þCO).
Syngas is used to produce alcohol, alternative fuels, syn-
thetic ammonia-based fertilizers and petroleum-based re-
finery feedstock [8].
Biogas reforming techniques for H2 production
The reforming method can be carried out both in tubular type
fixed bed reactors and in fluidized bed reactors and contin-
uous type fixed-bed reactors have become widespread due to
their relatively low cost and simple design. Generally, all these
methods can be performed at low pressures, but in practice,
intermediate pressures are used from 10 to 20 bars to increase
the efficiency [12].
Steam reforming process (SR)
On an industrial scale, H2 has been produced mainly by steam
methane reforming (SMR) over the past 100 years and mainly
used in refineries and fertilizer production. The general
equation for SMR from biogas or methane is mentioned below
[13,143,144].
CH4 þ H2 OðSteamÞ /CO þ 3H2 DH298K ¼ þ206:2ðkJ = molÞ
In this process, methane molecule reacts with steam
molecule in the presence of suitable catalyst to generate
syngas and reaction takes place at high temperature. This
process includes steam reforming (SR), water gas shift (WGS)
and combined steam reforming reactions [7]. First, methane is
reacted with water vapor in SR to form syngas containing
carbon monoxide (CO) and hydrogen (H2) in the presence of an
appropriate catalyst (Equation (1)). Syngas gas (mixture of
CO þ H2) is then cooled to a temperature between 300  C
500  C and fed into the WGS reactor, where carbon monoxide
(CO) reacts with water (H2O) to reduce the CO content and
produce carbon dioxide(CO2) and hydrogen(H2) (Equation (2))
[7]. Additionally, combined or direct steam reforming reaction
is sum of SR and WGS reaction (Equation (3)).
Water gas shift reaction:
CO þ H2 OðSteamÞ /CO2 þ H2 DH298K ¼ 41:2ðkJ=molÞ (2)
Combined reaction:
CH4 þ 2H2 OðSteamÞ /CO2 þ 4H2 DH298K ¼ þ165ðkJ = molÞ (3)
The ratio of H2/CO is close to 3, which means higher yield of
H2 (above 70%). Methane requires a high temperature
(840e950  C) for reaction, but a higher temperature can be
managed by a suitable catalyst [14]. Most industrial steam
reforming units use ceramic-based nickel catalysts operating
at temperatures of 700e1000  C and a pressure between 15 and
30 atm [15].
The main detriment of this process is that enormous heat
is required to shift equilibrium reaction rightward with the
formation of H2 and CO. The reason is that the reaction is
endothermic and requires an external heat source [16].
Partial oxidation reforming (POR)
POR is another reforming process with methane reforming to
produce H2 with minimum energy costs, and it is done by
exothermic process with the utility of air or oxygen.
1
CH4 þ O2 /CO þ 2H2 DH298K ¼ 35:6ðkJ = molÞ (4)
2
In this process, methane molecule is partially oxidized to
generate a mixture of CO and H2, requires temperature be-
(1) tween 700 and 900  C at atmospheric pressure, ratio of H2/CO
 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
to nearly 2 and H2 yield almost 67% and reduces the soot
formation [17].
One important characteristic to consider during processing
is the molar ratio (O2/CH4). A higher molar ratio (O2/CH4) re-
sults in complete combustion by fuel, as seen in Equation (5),
which is an exothermic reaction type that increases the
temperature of reaction, which can initiate the development
of hot spots and coke on the catalyst surface in the reactor and
decrease the yield of H2 compared with SR process [2].
CH4 þ 2O2 /CO2 þ 2H2 O DH298K ¼ 801:7ðkJ = molÞ
Nickel-based catalysts are regularly used for POR reactions.
Several selective and highly active catalysts for POR methane
have been described, such as mixed crystals of NiOeMgO,
CaeSreTieNi and NieMgeCreLaeO. Among the most suit-
able catalysts for POR reaction, the Ru-based catalyst has
excessive coke resistance at very high temperatures. Since
ruthenium oxide has good thermal and chemical stability and
more resistance to chemical corrosion, it increases the selec-
tivity of H2 production and conversion of methane [19].
Auto thermal reforming (ATR)
To mitigate the disadvantages of the endothermic nature of
SR process and low H2 recovery from POR process, auto ther-
mal reforming (Equation (6)) was developed as combined
group of the two processes [8].
1 1 5
CH4 þ H2 OðSteamÞ þ O2 /CO þ H2 DH298K ¼ 0ðkJ = molÞ
2 4 2
The term ‘Autothermal’ denotes no need for heat required
through the external source for the reaction. It manages the
demand of heat of endothermic reaction by releasing heat
through the exothermic reactions and can be reflected as an
effective process for H2 production [8]. Partial oxidation and
methane reforming reactions are injected by steam and oxy-
gen simultaneously. The higher H2 yield is around 74%, with
the ratio of H2/CO close to 2.8 [18].
In an ATR reformer, partial oxidation reaction consists in
the thermal zone and producing heat to steam reforming oc-
curs in the catalytic zone [12]. The major drawbacks associated
with the ATR process are soot formations in combustion zone
that feed steam to cause upturns capital and operating cost of
reformer [8]. Higher plant efficiencies achieved by biogas
reforming via ATR process are 75%, operating temperature
range varies from 500 to 700  C and molar ratio of O/C from 0.80
to 0.90. Generally, maximum temperate is applied for the
process since low temperature rises molar ratio H2/CO due to
the enlarged content of the non-reacted CH4. Additionally, a
low temperature is suitable for further removal of CO [12].
Dry reforming process (DR)
In the DR process, methane reacts with CO2 to generate CO and
H2 and reaction temperature increases above 640  C. The gen-
eral Equation (7) for dry reforming process is as follows [19].
CH4 þ CO2 /2CO þ 2H2 DH298K ¼ 247ðkJ = molÞ
The reaction of DR is the conversion of methane and car-
bon dioxide into syngas. In addition to reactions, other
34835
chemical reactions can also take place at the same time dur-
ing the process. A typical side reaction is reverse water gas
shift (RWGS) (Eq. (8)) which can reduce the ratio of H2/CO in
syngas products. Though it may be undesirable in syngas
production, this reaction helps establish the correct H2/CO
ratio for higher hydrocarbon production [149].
CO2 þ H2 4CO þ H2 O DH298K ¼ 41ðkJ = molÞ (8)
Particular side reaction contributes formation of coke
during the process. The methane (CH4) decomposition pre-
(5)
sented by Eq. (9), wherein methane decomposed completely
toward solid carbon over the catalytic surface and emitted H2.
The CO disproportionation is termed as Boudouard reaction,
presented in Eq. (10). The hydrogenation of CO2 and CO in Eqs.
(11) and (12), respectively, wherein CO2 reacts with H2 to
develop solid carbon (C) and water vapor (H2O) [150].
CH4 4C þ 2H2 DH298K ¼ 74:9ðkJ=molÞ (9)
2CO 4 C þ CO2 DH298K ¼ 172:4ðkJ = molÞ (10)
CO2 þ 2H2 4C þ 2H2 O DH298K ¼ 90ðkJ = molÞ (11)
CO þ H2 4C þ H2 O DH298K ¼ 131:3ðkJ = molÞ (12)
There is a need for an external heat source due to endo-
thermic reaction and also this process is attractive for biogas
because of two basic elements involved in raw biogas such as
CH4 and CO2. This process leads to molar ratio H2/CO of
(6) nearly 1 and yield of H2 of approximately 50% [2]. The main
problem with DR is that coke can build up, deactivate the
catalyst and blockage the reactor. From previous processes,
catalytic materials with H2 selectivity and thermal stability
have been used and countless interests to reduce carbon
deposition [2]. Although catalysts based on Ru, Rh, and Pt
improve the production of H2, they have not received indus-
trial development due to limitations of availability and their
high cost, while catalysts based on Ni and Co are widely used
[2,12]. Circulating bed reactors and regenerators are a tech-
nical process often used to deposit coke on catalysts to avoid
catalyst deactivation during continuous operation. The coke
formation accumulated on the catalyst surface is removed by
incineration, and the generated heat can be used for endo-
thermic dry reforming [12].
Dry oxidation reforming (DOR)
DOR process has been developed by combining two processes
as dry and partial oxidation reforming of methane and used
for controlling the carbon deposition on catalyst surface. The
general equation (Eq. (13)) of DOR is represented by Refs. [2,12]:
1 1 3
CH4 þ CO2 þ O2 / CO þ 2H2 DH298K ¼ 123:5ðkJ = molÞ (13)
2 4 2
Combined feed of O2 with CH4 and CO2 offers the following
additional benefits: Minimized overall energy consumption,
increased conversion of CH4 and enlarged yield of product at
(7) low temperatures, increased stability of catalyst and better
resistance of deactivation and manage the ratio of H2/CO by
adjusting the O2 flow condition [20]. This route additionally
34836 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5

diminutions the reaction of energy demand as the exothermic
partial oxidation system releases heat and is more useful for
dry oxidation process (endothermic). The ratio of H2/CO
correspondingly improves and generates H2 yield of approxi-
mately 60% [12].
Current research on conventional processes from
biogas reforming based on catalyst
Steam reforming of biogas (SRB)
Hydrogen production process from steam reforming of biogas
is considered as a promising alternative route to steam
methane reforming with similar efficiency [2] and presented a
detailed assessment of hydrogen production method using
biogas [21]. Table 1 expresses the catalytic performance of
steam reforming biogas (SRB) and their calculations. The
noble metals offer a high conversion rate with low tempera-
tures than Ni metal, which offers a high conversion rate with
high temperatures.
The main challenge in developing catalysts in hydrogen
production via biogas is avoiding deposition of carbon in en-
ergetic phase to raise its life. Furthermore, it involves
improving the catalyst resistance to poising sulphur content
and increasing catalyst of surface area in order to promote
activity [8].
Ahmed et al. evaluated catalyst (4 wt% Rh/LaeAl2O3)
through SBR in hydrogen production. The catalyst perfor-
mance was analysed in order to temperature variation from
(590e685  C), the molar ratio of steam to carbon range
(1.28e3.85), molar ratio of CO2/CH4 (0.54e1.50) and the range of
GHSV (9810-27000 h1). It was observed that highest conver-
sion of CH4 and lowest conversion of CO2 at 650  C (in Table 1)
at GHSV 9810 h1 and 1.32 S/C low CO2 conversion rate due to
low temperature of reaction results in more contribution of
WSR reaction. The increasing S/C positively affected CH4
conversion, resulting in higher H2 yield and the marginal ef-
fect of GHSV on their process performance [26].
Effendi et al. performed the comparison of fluidized and
fixed bed reactors at catalyst (11.5 wt% Ni/Al2O3), molar ratio
of H2O/CH4 (2.2), GHSV (18,000 h1) and along with tempera-
ture 750  C. The fluidized bed reactor was evaluated to offer
(5e15%) better performance than fixed bed reactor. Higher
feeding of ratio (gas to steam) was introduced to strong carbon
formation due to reduced fluidization in reactor and carbon
formation was minimized by increased steam feed. The poor
performance of fixed bed produces cold spot formation in the
bed of catalyst [29].
Izquierdo et al. estimated the result of various composi-
tions on bimetallic RheNi and Ni catalyst performance in
steam biogas reforming at temperature 800  C, ratio of CH4/
CO2 (1.5) and WHSV (131.6 ggas/gcat h1), whereas catalyst
(13 wt% Ni/CeeZreAl2O3) observed at steam methane ratio of
one gives 99.5% of CH4 conversion and 67% of CO2 conversion
[30]. In addition, as per Ahmed et al. [26], increasing ratio of S/
C was a positive advantage in CH4 conversion, but CO2 con-
version was unfavorable, resulting in improvement of WGS
over the catalyst (4 wt% Rh/LaeAl2O3).
Despite higher conversion of CH4 and CO2, catalyst pre-
sented low H2 yield compared with the catalyst of Ni/
CeeAl2O3 and Ni/ZreAl2O3. The catalysts activity and stability
are affected by H2S, which is present in biogas. Sulphur con-
tent from H2S reduced the catalyst activity because it reacts
with active metals, limiting access of reactants to active sites.
Furthermore, the development of stable metal adsorbate
bonds could lead to non-selective side reactions [31]. Addi-
tionally, H2S acts as a toxic gas for metal-based catalysts, but a
certain amount of H2S in the feed increases the reforming
activity of the catalyst [32]. Due to the toxic effect, the content
of H2S in biogas sharply reduces the catalytic activity. There-
fore, several purification methods have been used to remove
H2S, such as membrane technology, adsorption, and biological
methods [7].
In contrast, Appari et al. reported catalyst activity loss of
98% with catalyst (15 wt% Ni/Al2O3) suffered by suphur poising
effect [33]. Ashrafi et al. observed that temperate is indepen-
dent of H2S concentration and depends on sulphur content
over the catalyst's surface in loss of catalyst activity. The
poisoning effect of catalyst at the temperature (700  C) is not
recovered by elimination of H2S content through the feed, but
from temperature (800  C) could be reversed by eliminating
H2S content through the feed. The deactivation of catalyst
activity was recovered at (800  C) and fully deactivated at
(700  C); with increasing temperature H2S removal increases
the catalyst regeneration limit.

Table 1 e Summary of Catalyst performance calculated by Steam reforming of biogas (SRB).

Process Catalyst XCH4 XCO2 Yield Experiment condition Ref.
o
YH2 YCO S/C Temp( C) CH4/CO2 O2/C
SR 10 (wt.%) Ni on CeZrLa 43.0 12 47.20 2.1 3.0 550 1 e [22]
SR 5 wt% NiO/CeO2 52 48 72 12 1 873 1.5 e [23]
SR 15% (Ni) on Al2O3 82 8.0 e e 2.0 1072 1.2 e [24]
SR 0.09 (wt%) [Pd(7)eRh(1)]/(CeZrO2Al2O3] 90 6.4 71.2 0.8 1.50 1072 1.5 e [25]
SR 4 wt%RhO2/3 wt% La2O3eAl2O3 93 10.5 2.62a 0.98a 1.3a 685a 1a e [26]
SR 1.3 wt %PdeRh/CeZrO2eAl2O3 93 5 e e 1.2b 800b 1.5b [25]
SR Ni0.4Ce0.8O2 96 40 72 5 2 700 3 6.2 [27]
SR 7.5 (wt%) Ni/CeO2 98 4.0 55 29 1.0 901 1.5 e [28]
a
Experiment was performed using WHSV of 9810 h1. The yield was evaluated based on mol of H2 produced/mol of CH4. The experiments were
completed for 40 h.
b
The experiment was executed for 200 h using WHSV of 20,000 h1.
 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
Efficient removal of sulphur content could be costly in
biogas applications but it can be economical to operate the
reformer with a higher feed of H2S biogas at higher tempera-
tures. Reformers process at high temperature conduct exten-
sive issues such as hot spot formation, sintering metal
crystallites, and decreased surface area of catalyst etc. These
issues generate loss in activity, stability, and catalyst life [34].
Catalyst such as Ni based is more active in SR of biogas process
from Table 1(numerous catalysts in SRB). In maximum ap-
plications, conversion of CO2 was low compared to conversion
of methane, while some research also described high con-
version of CO2. The high conversion of methane and CO2 has
been expressed in higher hydrogen yield.
Partial oxidation of biogas (POB)
Partial oxidation of biogas has several benefits over SRB,
including compactness, less sensitivity, and better response
time for fuel variants. The reactors of partial oxidation in-
crease interest in energy conversion for high temperatures
utilized in fuel cell. It is a faster chemical reaction than SRB
due to its exothermic reaction [35].
Hydrocarbon (HC) conversion to syngas via partial oxida-
tion process can occur at high temperatures lacking catalysts.
Conversely, the operating temperature will be significantly
decreased using catalyst. Most of the studies via partial
oxidation catalysts are same as catalyst used in steam
reforming process as noble metal and transition metallic el-
ements such as Ni, Fe and Co [36].
Pantaleo et al. described supported catalyst (La2O3, CeO2
and combined CeO2eLa2O3) with Ni catalyst from Partial
oxidation of methane. The support of Ni catalyst is prepared
from wet impregnation and co-precipitation. Carbon is
formed on Ni/La2O3 and Ni/CeO2 and carbon is not formed on
combined support (CeO2eLa2O3) during test [37].
Chen et al. analysed spiral type Swiss roll reactor via Cat-
alytic partial oxidation of methane (CPOM) and Rh-based
catalyst. Three types of biogas are considered for studies:
sewage, landfill, and farm biogas. Syngas yield was found at
2.80 mol/mol of CH4) and 31.12% CO2 conversion. The con-
version of CH4 (99%) (Table 2), yield of H2 more than 1.49 mol/
mol CH4 and ratio of H2/CO were higher than in other studies
[38].
Table 2 e Summary of Catalyst performances via partial oxidation of biogas (POB).
Catalyst Performance CH4
parameters conversion (%)
Rh CO selectivity is 52% H2 90
selectivity is 80%
Rh H2 yield is 1.5 79
Ni/MgO H2/CO is 2.6e1.6 81
NiO/Y2O3/ZrO2 H2/CO is 1.01 76
NaCaCoO4 e 89
Rh H2 selectivity is 80.93% 99
CO selectivity is 74.23%
H2 yield is 1.63
CO yield is 1.24 H2/CO
ratio is 1.56
34837
Tsyganok et al. evaluated catalyst Pt-, Rh- and Ru-based via
joint operation of both dry and partial oxidation of methane
(CH4) and supported on MgeAl mixed oxides. The experiment
was conducted at 850  C and 1 atm, using the ratio of O2/CH4
(0.46) and GHSV (79 NL CH4/(gcat$h)). The authors investigated
Rh-and Ru-based catalysts with high activity performed dur-
ing the experiment and no carbon deposit during 5 h [39].
While Moral et al. studied syngas production from biogas
catalytic partial oxidation and dry reforming used by several
Rh-based catalysts with different support SiO2, CeO2 and g-
Al2O3. It was measured that the molar ratio O2/CH4 (0.45) was
favorable for higher hydrogen yields and maximum CH4
conversion. The results were obtained by feeding various
amounts of O2 and the mixture of biogas in catalytic perfor-
mance using dissimilar Rh-based catalyst and conducting the
experiment with GHSV value of 150 NL CH4/(gcat$h) and tem-
perature at 700  C [40].
Rafiq et al. studied through the experimentally and ther-
modynamic analysis in a plasma assisted gliding arc reactor
using Ni catalyst via partial oxidation model biogas as CH4
(60%) and CO2 (40%) and reported highest CH4 conversion as
90%, while the ratio of CH4/O2 as 3 at temperature 800  C. The
ratio of CH4/O2 as 2, methane conversion was obtained as
97.5% using Ni catalytic filter in tabular reactor without
considering hydrogen. These studies also show that calcium
silicate could be a good base material for catalytic filters from
partial oxidation of biogas mixture [41].
Table 2 represents the various kinds of catalytic perfor-
mance from partial oxidation of biogas model. Rh-based
catalyst is more useful with various conditions and different
parameters.
Auto thermal reforming of biogas (ATRB)
Number of research is limited to auto-thermal reforming of
biogas (ATRB). Araki et al. performed ATRB model biogas with
catalyst (30 wt% Ni/Al2O3) and reported the effect of the ratio
of S/C and O2/C at the same temperature. Optimum results of
S/C (1.5e2.5) and O2/C (0.44e0.56) at 750  C and investigated
90% conversion of CH4 [46].
Vita et al. investigated catalyst (Ni/CeO2) in auto-thermal
reforming of biogas (ATRB). The conversion of CH4 (97.3%)
and CO2 (90.5%) with ratio of S/C (0.3) and ratio of O2/C (0.1) was
Temperature GHSV Feed gas References
( C)
630 318,500/h CH4: CO2: N2 ¼ 50:45:5.0 [42]
O2:CH4 ¼ 0.625
700 150 NL/(gcat h) CH4:CO2:N2 ¼ 54:40:6.0 [40]
O2/CH4 ¼ 0.20 and 0.45
700 18 L/(gcat h) O2/CH4 ¼ 1:2 [43]
750 0.1073a L/min O2:CH4:CO2 ¼ 0.25:1.5:1.0 [44]
785 17 000mL/(gcat$h) O2:CH4 ¼ 1:1.8e1.91 [45]
1923 10,000/h O2:CH4:CO2:N2 ¼ 0.6 [38]
e0.7:1:0.6e0.91:2.25
e2.70
34838 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5

reported (Table 3). The performance of catalyst was tested
150 h with minor sign of deactivation. The catalyst activity was
retained due to NiO distribution over the catalyst surface [47].
Izquierdo et al. reported that the catalyst (13 wt% Ni/
CeeZreAl2O3) also utilized in SRB method and ATRB method
observed with ratio of S/C (1), O2/C ratio (0.25), and WHSV (161
per hours), see in (Table 3). Bimetallic catalyst (RheNi/
CeeAl2O3) exposed the maximum yield of H2 in ATR process
among the catalysts inspected [48].
Bawornruttanaboonya et al. investigated catalyst (ReeNi/
g-Al2O3) in auto thermal reforming of biogas. Micro-reactor
(Channel type) was compared to novel micro-reactor and
noted that novel reactor was optimum condition was O2: H2O:
CO2:CH4 (25:5:28:42) % (v/v) at 730  C and pressure 1 bar [49].
Camacho et al. examined homogeneous (lattice structure)
and convention (random form) for H2 production via ATR re-
action. Structured catalyst (15e0.05 wt%-Ni-Rh/MgAl2O4-
eSiSiC) and monolith (LiFeO2eSiC) were chosen for biogas
conversion to H2 gas. The investigations were executed using
a ratio of S/C (2), ratio of O/C (1.1), and GHSV (10,000 per hour)
through the experimental section and achieved more than
98% methane conversion [50].
Table 3 represents the detail of numerous catalysts in
ATRB. It is apparent that catalysts such as Ni based are more
active in also ATR of biogas process. The high conversion of
methane and CO2 has also been expressed with higher
hydrogen yield in the ATR method.
Dry reforming of biogas (DRB) and dry oxidation reforming
of biogas (DORB)
Several studies containing dry and oxidative reforming of
biogas were investigated apart from reforming SRB and ATRB
methods.
Table 4 briefly details different catalyst performances via
DRB and DORB and offers extensive results from various
catalyst effects under different conditions. This method's
main benefit is using greenhouse gases such as CH4 and CO2
[53]. This process is used CO2 for reaction and provides heat
source from external due to its endothermic reaction in na-
ture. The key problem of DR process is the development of
coke over the catalyst surface during the process due to defi-
cient steam and methane reaction, and this coke formation
can blockage the rector. The research on Hydrogen production
from DR method has been directed toward thermal stability
and growth of carbon tolerant and well-suited noble metallic
elements such as Pt, Ru and Rh for DR process, but these
metals are more costly. Hence it becomes expensive and un-
attractive for industries. On the contrary, Ni-based catalyst
has been invested for availability and cost factors [8]. The need
for high temperature for DR reaction and high carbon content
as in reactant makes those metals disposed to deactivate
through carbon deposit and sintering. Various researchers
investigated bimetallic catalysts in DRB process as Ni-Co [55],
NieK [56] and NieB [57].
Xu et al. communicated the comparison of high-
performance catalyst (NieCo/La2O3eAl2O3) and (Ni/
CeeZreAl2O3) in DRB process and arranged loading of catalyst
in wt% (6, 3 and 7) for La, Co and Ni respectively [58]. The
higher CH4 conversion and CO2 conversion (94% and 97%) and
H2 selectivity 92.7% (Table 4) were detected at a temperature
800  C along with ratio of CH4/CO2 approx.1 through the period
of 500 h, with low 1.9 (wt%) carbon deposition over the catalyst
surface.
The authors described the advantages of catalyst Ni/La2-
O3eAl2O3 with adding Co in DRB process [58]. Arbag et al. also
express that Co content plays a significant role in the catalyst
operation. Large amount of Co (5 wt%) forms CoAl2O4, which is
challenging to reduce and interferes with catalytic activity.
For comparison, bimetal (2.5 wt% Ni) -(2.5 wt% Co) from Al2O3
performed better. Despite the better characteristics, the
bimetallic catalyst with a concentration of 2.5 wt% has a
higher load. CH4 conversion is increased due to 5 wt% NieCo/
Al2O3, NieCo metal loading. This indicates a limited contri-
bution of the DR response to CH4 conversion [59].
Several researchers have recently tried increasing the
conversion rate in response to biogas reforming. The low
steam carbon ratio was maintained to contribute to CO2 in SRB
by Appari et al. [33]. Lai et al. performed biogas (CH4-50%: CO2-
50%) as equimolar in ODRB. Experiment results from ODR
showed that adding a significant amount of oxidant could
increase the methane conversion rate, but unnecessary
oxidation can reduce the CO2 conversion efficiency [53].
Lau et al. simulated biogas model via oxidative reforming
was obtained higher efficiency. In addition, the catalytic ac-
tivity level of (0.5% Ce)/Ni/SiO2 measures the equilibrium
condition and is comparatively stable throughout 24 h of
ODRB [54].

Table 3 e Summary of Catalyst performance calculated by auto-thermal reforming of biogas (ATRB).

Process Name Catalyst composition XCH4 XCO2 Yield Experiment condition Ref.
YH2 YCO S/C TRemperature(oC) CH4/CO2 O2/C
ATR 25%(Ni) on MgAlCe 52 48 72.5 12 1 873 1.5 e [51]
ATR 1.5 wt% NiO/CeO2 97.3 90.5 96.2 1.3d 0.3d 800d 1.5d 0.1 [47]
ATR 5 wt% Ni on Mg 0.4Al2O3 99 15 e e 3 1073 1.5 0.5 [52]
ATR 13 (wt%)-NiO/CeeZre Al2O3 99 34 67e 1.5f 1f 800f 1.5f 0.5f [48]
ATR 1 wt%RhO2-13(wt%)- NiO/Cee Al2O3 99 39 75e 1.7f 1f 800f 1.5f 0.5f [48]
d
The catalyst performance was evaluated with 100 ppm S in the feed for 9 h. The selectivity of H2 was obtained by dividing molar flow rate of H2
divided by molar flow rate of 2 CH4 reacted.
e
The H2 selectivity was attained by dividing H2 molar flow rate divided by molar flow rate of 2 CH4 reacted. The performance of catalyst was
estimated without presence of S.
f
The catalyst performance was performed for 300 min at WHSV of 1200 per hour over 8 (wt %) Ni supported catalyst.
 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5 34839

Table 4 e Catalyst activity examined via DRB and ODRB.

Process Catalyst XCH4 XCO2 YH2 YCO Temp(oC) CH4/CO2 O2/C Ref.
a
[DRB] 75(Ni-25) Co/(Al2O3) 25.0 e e 0.6 600 1 e [61]
[DRB] (13 wt%) NiO/(CeeZreAl2O3) 60 94 63 1b 800d 1.5d e [48]
[DRB] 1 (wt%) RhO2-13 wt % NiO/(Cee Al2O3) 64.0 85 57 0.9b 800d 1.5d e [48]
[ODRB] 20 (wt %) NiO/Al2O3) 70.0 85 e e e 1.5 1 [60]
[DRB] 8 (wt%) NiO/20 wt% CeO2e Al2O3) 70.0 97 76 60 860f 1.5f e [62]
[DRB] 20 (wt%) NiO/MgO 80.0 85 1.14 750 150 0.1 [63]
[DRB] 7NiO-3(wt%) CoO2/6 wt% La2O3e Al2O3) 93 94 95 98 800j 1j e [64]
[DRB] 9 (wt%) NiO/Ce0.82Sm0.18 O1.91 98.0 97 0.8 e 800 1 e [65]
a
The catalyst arranged15 wt% metal loading.
b
The CO yield was calculated on the basis of H2/CO ratio.
d
The catalyst performance was evaluated at 100 ppm S in the feed for 9 h. The H2 selectivity is obtained by dividing the H2 molar flow rate and
divided by 2 M flow rates of CH4 reacted.
f
The performance evaluation of the catalyst was at WHSV of 1200 per hour for 300 min over 8(wt)% Ni supported catalyst.
j
The performance of the catalyst was estimated using GHSV of 6000 cm3 gcat1 h1 for 300 h.

Asencios et al. tested the experiment on Ni catalyst support
via ODRB and represented the various pH conditions with
Al2O3. Commercially available NieAl2O3 showed the highest
activity at 750  C reaction temperature, but it was deactivated
after 3 h. The synthesized NieAl2O3catalyst showed good sta-
bility during the 6-h test at more pH conditions close to 7, but
obtained only 70% methane conversion rate while the CO2
conversion maintained the equilibrium [60] (Table 4). The
catalyst activity is based on the low acidity of the carrier, so less
coke is deposited on the catalyst. The low acidity of the sub-
strate reduces the CO2 reaction in the main Al2O3 core, which
leads to an acid-base interaction that promotes this reaction.
Summary
Hydrogen production through biogas claims to be a sustain-
able system from environment point of view. However, sig-
nificant efforts are still required for its generation process to
be estimated from a comprehensive environment viable sys-
tem. Biogas H2 production can be attained through various
methods such as SRB, POB, ATRB, DRB and DORB. Table 5
compares the merits and demerits of various reforming pro-
cesses. Table 6 shows the maturity of hydrogen production
with various parameters and conventional reactors. The main
key to H2 production via biogas is the development of resistant
carbon and sulphur tolerant catalysts. H2 production from
SRM is broadly studied and commercially activated. However,
the main issue with SRB is the occurrence of CO2 affecting the
catalyst performance.
The production of hydrogen from biogas is significantly
increasing due to the increasing demand for energy and little
literature has been examined. Converting biogas to H2 gas
requires the development of small reformers. Wide area
synthesis gas applications are used in power generation,
chemical industry and energy conversion. Syngas could be
directly used in internal combustion engines for energy gen-
eration. On the other hand, the direct use of biogas for com-
bustion is disadvantageous due to its high content of CO2 and
decreased heating value related to synthesis gas.
The main important aspect of the production of H2 from
biogas is the advance of catalysts unaffected by carbon and
sulphur content. H2 production with SMR is broadly studied
and used commercially. However, the main problem with SRB
is the existence of CO2, which affects the catalyst perfor-
mance. Water gas shift reaction occurs during the SR process
and negatively affects CO2 conversion [26].
Low conversion rate of CO2 due to the high activity of the
water gas shift changes the composition of the reformation,
changes the H2/CO ratio and decreases the quality. In addi-
tion, CO2 in feeding as biogas can accelerate the carbon for-
mation reaction and reduce the activity and performance of
catalyst. Most issues can be solved by removing present CO2 in
biogas, but this removal method is more expensive on a small
scale. The existence of CO2 will also be beneficial in decreasing
the hot spots produced in the reactor caused by higher tem-
perature operation. Additionally, broadly studied literature
via DR method has been reported as deactivation of catalyst
and low yield of H2 due to carbon formation. DR and SR pro-
cesses are endothermic, while dry reforming is more intense
and needs an external source of energy supply. Another
experiment examined the effect of increasing process effi-
ciency by adding O2 in oxidative dry reforming biogas (ODRB)
and removing carbon by oxidation along with O2.
Partial oxidation of biogas appears to have several advan-
tages over SRB, including lower sensitivity and better reaction
time to fuel conversion. Partial oxidation reactors are
increasingly interested in fuel cells' high-temperature energy
conversion. Most research on catalysts for partial oxidation is
similar to that used in steam reforming processes such as
transition metals and noble metallic elements such as Fe, Ni
and Co.
Research on hydrogen production using ATRB is sparse,
suggesting more research is needed. The effect of H2S on the
catalytic action of ATR catalysts should be evaluated. Like-
wise, the impact of the ATR method on CO2 conversion rate
was not examined in the study and must be assessed.
Composition of molar gas and conversion of CH4 from ATRB
process is measured, which does not fully take into account
the characteristics of the process. The yield of H2 and CO must
be assessed through ATRB process and efficiency should be
measured contrary to corresponding chemical stability con-
ditions. Main disadvantage of ATR reformer is the associated
decrease in the yield of H2 and low H2/CO ratio.
34840 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5

Table 5 e Merits and demerits of H2 Production from biogas reforming via literature.
Technology Merits
SR ✓ Carbon formation is low.
✓ Purity of H2 is high.
✓ Yield of H2 is high.
✓ No need O2 for operation.
Partial ✓ Operating temperature is relatively
oxidation low.
✓ Energy efficiency is high.
✓ Lower methane slip.
✓ No need feedstock desulfurization.
ATR ✓ No requires external heat.
✓ Low cost.
✓ Energy efficiency is high.
✓ Main content can be used as CH4
and CO2 from biogas.
✓ Reformer size is compact.
DR ✓ Conversion efficiency is high.
✓ Both greenhouse gases can be used
from biogas as CH4 and CO2.
✓ Environment friendly using biogas.
ODR ✓ Formation of carbon is low.
✓ Conversion efficiency is high.
✓ Improved deactivation resistance
and catalyst stability.
✓ Decreased total energy involved.
Demerits Remarks
✓ Costly catalyst ✓ Mostly used in industry applications.
✓ Need higher temperature ✓ Requires removing CO2 from biogas.
✓ Need to add H2O (vapor)
✓ Highest CO2 emissions are high.
✓ Air emissions are also high.
✓ Need huge size reformer.
✓Hot spot seems during increasing ✓ very few industrial applications
temperature on catalyst surface. ✓ Unite with other methods.
✓ Low Co selectivity can oxidize CH4 ✓ Need air or O2.
completely. ✓ Catalyst deactivates due to exothermic
✓ Low H2 yield compares to SR. reaction.
✓ H2/CO ratio is low.v
✓ Highly exothermic reaction leading
to catalyst deactivation by vforma-
tion of hot spots.
✓ Need various types of catalysts. ✓ Combination of SR and POR process.
✓ Hydrogen yield is low compared to ✓ ATR improves temperature control and
SR. decreases hot spot formation and in-
✓ Need control of complex processes. creases temperature control.
✓ Need air or O2.
✓ Separate unit is required for using ✓Self-sustaining method.
oxygen.
✓ High formation of carbon. ✓ Biogas is much more suitable for this
✓ Operating temperature is high. process as both content (CH4 and CO2)
✓ Expensive catalyst. are available.
✓ Reformer size is large.
✓ Commercial experience is low.
✓ Production of CO2 is more. ✓ Industrial application is low.
✓ Expansive catalyst. ✓ Combination of DR and POR process.
✓ Limited availability of catalyst. ✓ Exothermic or endothermic reactions
✓ Another metal is needed for catalyst depend on O2 feeding.
stability.
✓ Complicated control process.

Table 6 e Conventional process for H2 production from biogas or methane reforming.

Process Reactor type CH4 conversion (%) H2/CO Catalyst Temperature (oC) Reference
(SR) Fixed bed (FB) 70 3.4 NieCe0.8Zr0.2O2 600 [66]
Fixed bed (FB) 98 3.7 NieMg17.4Al1.6O20.8 650 [72]
Fixed bed (FB) 90 2.7 Ru/Al2O3 715 [67]
Fixed bed (FB) 85 2 Ni/Al2O3 750 [29]
Fixed bed (FB) 95 2.5 Ni/CaOeAl2O3 750 [68]
Fluidized-bed 96 2.2 Ni/Al2O3 750 [29]
Fluidized-bed 98 2.1 Ni/Al2O3 850 [69]
(POR) Fixed bed (FB) 100 2 Ni/Al2O3 700 [70]
Fixed bed (FB) 95 2 Ni-CoMgCeOx/ZrO2-HfO2 800 [71]
Fixed bed (FB) 85 2 Pt/CeO2 800 [73]
Fixed bed (FB) 87 2 NiO/MgO 850 [112]
(ATR) Fixed bed (FB) 92 3.2 Ni/MgAl2O4 700 [113]
Fixed bed (FB) 95 3.5 Rh/Al2O3 700 [114]
Fixed bed (FB) 75 1.2 Ni/NiOeMgO 750 [115]
Fixed bed (FB) 92 1.4 Ni/SBA-15 800 [116]
Fixed bed (FB) 100 2 Pt/ZrO2/Al2O3 800 [117]
(DR) Fixed bed (FB) 85 1.2 Ni/CeZrO2eMg Al2O4 700 [118]
Fixed bed (FB) 67 0.7 La/hydrotalcite 700 [119]
Fixed bed (FB) 70 0.9 RheNiLa/Y-Al2O3 750 [120]
Fixed bed (FB) 90 1.3 Ni/CeO2eAl2O3 860 [62]
(DOR) Fixed bed (FB) 86 1 RheNiLa/Y-Al2O3 750 [120]
Fluidized-bed 77 1.9 5Ni/5ZrO2eSiO2 750 [121]
Fixed bed (FB) 95 1.7 NdCoO3 perovskite 850 [122]
Fluidized-bed 100 1 PteRh/CeeZrO2eAl2O3 900 [54]
 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
H2 production technology via biogas can be efficiently
achieved from several processes like steam reforming (SR)
method, partial oxidation (POx) method, auto thermal
reforming (ATR) method, Dry reforming (DR) and oxidative dry
reforming (ODR) method. Table 5 compares the advantages
and disadvantages of many reforming technologies.
Membrane reactor (MR)
Due to various factors, the membrane technology is not
competitive with SR of methane for hydrogen production. In
addition, membrane stability cannot yet be fully secure,
implying constant maintenance cost. In contrast, membrane
technology has not yet been developed for high temperature
applications, as degradation occurs when operating at tem-
peratures above 500  C [151]. However, most pieces of litera-
ture have been focused on membrane fabrication for low
temperature applications and development progress in high
temperature applications has been seen in last few years. The
improved membrane stability for high temperature attained
by advances in preparation methods, preparation multilayer
and Pd based alloy with other materials [152].
A reactor as a fuel processor has numerous major parts
such as reforming, combustion, permeating, separation, and
purification. The reactor consists of a vessel with a typical
closed tubular design or shell type, as shown in Fig. 2. Hy-
drocarbons are fed into the reactor through another inlet
connected to the coil, where the feed is vaporized. The
reforming catalyst responds via the vaporized feed tributaries
to create a mixed gas flow around the separation section
containing an end cap hydrogen sampling membrane sup-
ported by tension springs. The hydrogen-rich stream is
generated from a portion of the mixed gas stream passing
through the membrane, and the remaining mixed gas stream
forms a by-product stream. The hydrogen-rich stream passes
in the area, penetrating through the tubular membrane. The
purification portion is at least partially included in the
permeate portion containing the additional catalytic reform-
ing bed. The side stream can be used or stored for other
Fig. 2 e Illustration of fixed bed type membrane reactor [142].
34841
Fig. 3 e A cross-sectional view of fixed bed (FB) membrane
reactor [142].
purposes, including fuel for combustion, to meet some or all of
the heating needs of the reactor [142].
Several other implementations use this concept. Fig. 3
schematically shows an alternative reactor design with an
enlarged outer metal shell to provide a relatively large com-
bustion portion and one or more membrane tubes [142].
Concept of MR
Conventional steam reformers are widely used industrially for
hydrogen production but suffer from several drawbacks such
as the formation of carbon, limitation of thermodynamic
chemical equilibrium and deactivation catalyst. In addition,
the materials used for the reactor walls must be very strong.
The reactors operate at high temperatures (650e850  C) [7].
Membrane reactors have a compact design, in which the
chemical reaction and the purification process occur in the
same reactor. Membrane reactors also offer low requirement of
energy and higher production of hydrogen. Membrane reactors
reduce the disadvantages involved with conventional reactors
by using selective membrane and the operation of chemical
reactions can take place at low temperature (550e600  C)
compared with conventional reactors. In addition, this reactor
permits materials to be used at lower temperatures and higher
hydrogen yields [7,142]. The assessment of conventional and
membrane reactor producing H2 from steam reforming method
through the biogas in fuel cell as shown in Fig. 4.
34842 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
Fig. 4 e Flow process by conventional and membrane reactors [7,74].
The membrane is the key role play in membrane reactor for
higher hydrogen yield, having more H2 permeation and
permitting more hydrogen flow rate. Membrane is a barrier
that prevents the passage of non-hydrogen components in the
feed gas mixture. The membrane reactors contain a reaction
side (region of H2 production) and permeation side (region of
H2 separation), as shown in Fig. 5. The membrane must have
more selectivity, chemical, low cost and mechanical stability
for separating hydrogen from mixture of gases [6].
Membranes can be classified into biological and synthetic
membranes, but having several drawbacks involving a pH
value range, less operating temperature (<100  C) and being
challenging to clean [75].
Synthetic membranes are mainly divided into organic type
(polymer) and inorganic type (matallic and ceramic). The
operating temperature is used from 100 to 300  C in organic
membranes, and an operating temperature of more than
200  C is used in inorganic membranes [7,76]. Fig. 6 shows the
mechanism of hydrogen transport through solid Pd-based
membranes.
The dense material membranes are classified into sup-
ported type and unsupported type membranes. Unsupported
type membranes involve drawbacks with brittleness, lower H2
permeability and poising surface. In addition, the membrane
area must be improved to ensure high H2 flow rate. Increasing
membrane area, as well as increasing membrane thickness,
increases material cost [77].
These aspects indicate the need to use composite mem-
branes with porous support and thin selective membranes to
improve mechanical steadiness and reduce cost. Pd-based
membranes (composite type) selectivity and stability depend
on support material quality. Porous material such as stainless
Fig. 5 e Working principle of the membrane system [7].
steel is regularly used as carrier material due to its properties
like good weldability, uniform coefficient of thermal expan-
sion, ease of manufacture, and low cost [78].
Besides the membrane category, various membrane re-
actors such as micro-reactor, fixed bed and fluidized bed are
essential in H2 production. The utility of a fluidized bed reactor
has several advantages over a fixed bed as increased heat and
mass transfer and eradication of external resistance to mass
transfer. The main reasons why this type of reactor is not
preferred as rapid decomposition of the catalyst and the
complexity of the reactor fabrication [79]. Thus, the fixed bed
membrane reactor is the most common.
Arrangement of membrane reactors
Technology of membrane reactors is emerging with a variety
of H2 purifiers to offer high-purity H2 and recuperate hydrogen
via miscellaneous gas tributaries. The literature has presented
various categories of membrane reactors in order for
hydrogen production. Most of the study has been done in
Packed Bed type membrane reactors. However, there is
growing interest in new type configurations like fluidized bed
membrane reactors, mainly due to better temperature control
where mass transfer restrictions can be reduced [6]. Addi-
tionally, the membrane geometry can be planner, tubular,
spiral wound and plate and frame type. Currently, flat and
tubular shapes are most commonly used to separate gas. The
planar membranes have been widely used in previous
research laboratory, while the tubular membranes are often
used on industrial scale. As a result, the ratio of surface area to
volume is higher compared to planar membranes [6].
Packed bed membrane reactor (PBMR)
The concept of PBMR is the well-known membrane reactor in
the literature that has several advantages over the other
reactor arrangements, especially in terms of membrane inte-
gration and ease of use. The PBMR arrangement generally
indicates a system in which the catalyst is introduced into the
reactor with a fixed bed configuration with the membrane. In
this system, catalyst can be located either in shell or inside
membrane, whereas selective gas permeation occurs via re-
action side from permeate side (gas separation) or through
 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
Fig. 6 e H2 transport mechanism through the dense Pd-based membrane [6].
membrane side into the catalyst bed. A more thorough
description of PBMR design can be seen in Fig. 7.
In this concept, the sweep gas on permeate side makes the
most of the driving force in gas separation. The sweep gas via
membrane increases the difference of partial pressure, which
results in nearly partial pressure being zero with permeate side
and is related to increased H2 production. Using a sweep gas
also reduces the surface area required for gas separation and is
generally attractive if the resulting gas mixture can be used for
other processes. Regarding the practice of membrane reactors
for applications at high temperatures, reforming steam
methane and auto-thermal methane are the two most
considered methods. High temperature reactions are preferred
over other high temperature reactions and lower tempera-
tures, such as alcohol reforming or water gas shift [140].
Saric et al. investigated SMR with small scale membrane
reactor from Pd-based ceramic membrane operating at tem-
perature 580  C and pressure 28 bars. The membrane thick-
ness was used as 3.8 mm and carried out the steam methane
reaction over a nickel catalyst. Methane conversions were
nearly (80e95%) and the factor of hydrogen recovery of around
(60e80%) during 1100 h of operation, but membrane was
presented 12% CO2 concentration on permeate side while
content of CO around (55e154 ppm) and also gas leakage at
last stage of experiment [80].
Dittmar et al. also studied the reaction of SMR using Pd-
based membrane using thickness 12 mm, length 1.9 cm and
6 mm diameter. The performance evaluations of experiment
Fig. 7 e Schematic of fixed bed membrane reactor (FBMR) configuration along with the catalyst confined in shell [140].
34843
were done in FBR using inner dia. 27.7 mm and 820 mm length
with pallets of Ni catalyst. The operation was performed at
600  C with S/C ¼ 3 and maintained pressure 16 bar on
retentate side and 1.3 bar on permeate side, at last, 60% CH4
conversion and H2 recovery around 70% at 650  C [81].
Marcoberardino et al. performed 1D reactor model for SMR,
compared with experimental data using FBMR (fixed bed
membrane reactor) and used catalyst NieAl2O3.1% during
5 bar and 600  C. Modeling approach archived low CH4 con-
version as 47.4% and hydrogen recovery factor 28. Dry
methane reforming is another method for producing H2 that
has been extensively researched in the literature, including
membrane technique. In this technique, no required steam
(H2O) is fed into the reactor, so no steam is generated at high
temperatures, resulting in significant energy savings. How-
ever, this process is subject to higher carbon and lower H2
production [82].
Silva et al. used a commercial PdeAg alloy using thickness
50 mm to convert methane (CH4) to CO2 in a membrane reactor
(packed bed) to produce hydrogen. This study evaluated with
conventional packed reactor and used catalyst (Pt/CeZrO2/
Al2O3) for both cases. The main reaction has done the ratio of
gas mixture (CH4/CO2 ¼ 1/1) and rate of feed flow 100 mL/min
at 550  C. The gas separation driving force was formed by
feeding Ar (sweep gas) into the membrane, whereas overall
pressure (atmospheric) was retained on both sides. The main
outcome of this study H2 recovery factor achieved 75% and
60% methane conversion at equilibrium conditions from
34844 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
conventional reactor and measured countless hydrogen
selectivity via membrane deprived of any deterioration for all
experiments [83].
Garcia-Garcia et al. similarly performed in a membrane
reactor (packed bed) through methane dry reforming method
with membrane (Pd-based) and its 5-mm thickness, supported
catalyst Al2O3 with hollow fibre and provided overall surface
area 4.4 cm2. The process has been done to compare mem-
brane reactor with Pd-based membrane via stainless steel
support, 17 mm thickness and overall surface area 22 cm2 over
conventional reactor (Fixed bed reactor). All experiments
conducted catalyst (4% Ru/ZrO2eLaO3) and tested activity at
various temperature up to 550  C using a feeding ratio of He:
CH4: CO2 ¼ 8:1:1 [84].
The experimental investigation is relatively easy in a
packed bed membrane reactor, but it suffers from limitations.
The main limitations to this type of configuration reactors
such as concentration polarization (limitation of mass trans-
fer bed to wall) [85], huge pressure drop related to catalytic bed
(that can be eliminated by using larger particles with a suit-
ably increased internal mass transfer restrictions) and lack of
membrane/thermal control freedom. All these disadvantages
can limit the further development of membrane reactor
technology ( [6].
Fluidized bed membrane reactor (FBMR)
FBMR configurations have attracted attention in recent years
due to limitations encountered in configurations of mem-
brane reactors (packed bed). This system consists of perm-
selective membranes immersed in a fluidized catalyst bed in
a bubbling regime. The main advantage of this reactor is
decreasing the limitation of bed to wall mass transfer and
permitting the operating reactor at a virtually isothermal form
(due to catalyst movement). This opportunity can be used to
carry out auto thermal reforming of hydrocarbons in mem-
brane reactors. ATR of methane in PBMR is relatively chal-
lenging due to hot spot at inlet of reactor. This can melt
Fig. 8 e Left side: Fluidized bed membrane reactor configuration with U-shaped membrane to sustain auto-thermal
operation [141]; Right side: Two-zone fluidized bed membrane reactor for continuous catalyst reactivation [90].
membrane. Membrane fluidized bed reactors can completely
solve this problem. Both auto thermal reforming and H2 re-
covery can be carried out in the same reactor [86]. The several
advantages of membrane supported fluidized bed reactor as
listed [87].
✓ Pressure drop is negligible, which permits using sizes of
tiny particles, resulting in no internal limitation of heat and
mass transfer.
✓ (Virtual) isothermal process.
✓ Membrane flexibility, arrangement of membrane bundles
and heat transfer surface area.
✓ Advanced fluidization behavior on account of:

Decreased axial gas back mixing.

Concentrated average bubble size as a result of enriched
bubble breakage.
Adris et al. reported the first design of FBMR and proposed
Pd-based membranes for selective H2 separation [88]. Over the
past period, this design has increased attention, especially
after it was shown that Pd-based membranes could sustain
perm-selectivities for long periods, even under intense fluid-
ization regimes [89].
Despite the advantages of this arrangement, this concept
has been less studied in the literature than fixed bed, and it is
suitable for intermediate temperatures. Fuel reforming and
alkenes dehydrogenation have been utilized last few years
from FBMR with high temperatures. Gallucci et al. described
Pd membrane immersed in catalyst bed with air supply and
combusted permeated H2 as an exothermic reaction, which
offers the necessary heat to reform the process [141].
Medrano et al. also proposed a “Two-Zone” membrane
reactor (fluidized bed) reactor. This conception has been
proposed and applied to processes in which catalyst deacti-
vation occurs rapidly because of carbon deposition, such as
the alkenes dehydrogenation. In this system, the fuel is fed
center of bed and the deactivated catalyst is redeveloped over
 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5 34845

combustion; carbon deposits in catalyst particles with an

Ref.

[80]
[92]
[93]
[94]
[83]
[84]

[95]

[96]

[89]
[91]
[91]
[91]
[97]
insignificant quantity of oxygen supplied through the bottom.
This reaction develops a large quantity of heat and that heat

HRF (%)
is released into the catalyst bed to withstand auto thermal

60e80

>75
process [90]. A representation of the two new concepts is

35

23
20
35
35
e

e
shown in Fig. 8.
Roses et al. informed the stability of FBMR to steam

XFUEL (%)

80e95
methane reforming process. The experiment was performed

>60

>60
>40

>80
at a temperature of 500e630  C and the pressure in the re-

90
96

65

99

55
89
92
96
actors was from 2 to 5.3 bar used 3.2 mm dia. of membrane
and thickness 3.2 mm of PdeAg layer. The test has demon-

1(Ar sweep gas)

1(Ar sweep gas)

1(N2sweep gas)
strated the membranes mechanical strength under the

1.3(Vacuum)
1.3(Vacuum)
1.3(Vacuum)
Table 7 e Summary of key achievements in configuration of packed and fluidized bed membrane reactors worked at high temperatures.
P (bar)
bubbling fluidization situation and the permeated H2 purity
remains high throughout entirely parametric studies per-

3.5
formed during long period testing by measured CO impurity

28

10
10
9

4
<10.0 ppm. Tests were run with two different kinds of con-

T ( C)
figurations. Firstly, in a conventional reactor (fluidized bed),

580
550
525
550
550
525

550

650

600
600
600
600
600
then in an FBMR configuration. In all cases, the H2 output was
increased [89].

Thickness (mm)
Fernandez et al. also informed the performance of mem-
branes (ceramic supported) for ATR and SMR processes

6e10
3.80

15.4
4e5

5e6

3.2
through fluidization conditions at temperatures from 500 to

50
5

4
4
4
5
600  C. The membranes used in reactor as diameter (1 cm) and
length (14.5 cm), respectively. 4 mm thick, PdeAg membranes
supported on alumina tubes along with an external zirconia

Ru/(Ce0.75Zr0.25O2)
Ru/(Ce0.75Zr0.25O2)
Ru/(Ce0.75Zr0.25O2)
layer were arranged with an electroless plating process. The

Pt/CeZrO2/Al2O3
Ru/ZrO2eLaO3
NiePt/CeZnLa
Catalyst

membrane reactor performance was compared via conven-

CPO catalyst
Pt(Ni)/CeO2

Ni/CaAl2O4
tional reactor (Fluidized bed) and membrane reactor
Ni-based
Ni-based

Ni-based

Ni/Al2O3
mounting commercial REB membranes [91]. Outcomes from
this study achieved higher hydrogen recovery factors (HRF)
with the ceramic supported membranes compared to the
Process

commercial membranes (self-supported).

SMR
SMR
SMR
SMR

SMR
SMR
ATR

ATR
ATR
ATR
DR
DR

DR
Thus, the fluidized bed membrane reactor represents less
studied configuration for high temperature methods, and few
studies have been published in recent years. This involves the Pd membrane prepared by ELP on ceramic tube support of Al

PdeAg membrane prepared by ELP on metallic Hastelloy X

complex hydrodynamics presence of internals and the diffi-
Pd76Ag19Cu5 alloy membrane on a porous stainless-steel
Pd based membrane supported on an Al2O3 hollow fiber
Pd membrane prepared by porous ceramic (NiO-8YSZ)

culty of obtaining reliable models for predicting the fluidized

PdeRu membrane (ceramic porous alumina support)

10 PdeAg commercial membranes prepared by ELP

bed membrane reactor behavior. However, the demand for 5 PdeAg membranes supported by ELP on ZrO2

5 PdeAg membranes supported by ELP on ZrO2

this concept is expected to increase in the next few years as it
overcomes many of the drawbacks associated with the design
of a packed bed membrane reactor, and it will improve with
PdeAg alloy provided by REB Research
Configuration

development of novel ultra-thin membranes. All literature

Pd membrane (Ceramic supported)

Pd membrane (Ceramic supported)

presenting configurations for packed membrane reactor and

5 commercial REB membranes

fluidized bed membrane are given in Table 7.

Modeling outcomes from PBMR and FBMR

It is well recognized that modeling is a tool to optimize,

describe, and solve complex problems. The models are cate-
support

support
and Zr

gorized based on various configuration reactors, and their

disk

complexity depends on the considering number of conserva-

tion equations and assumptions. In general, need few basic
Membrane reactor

membrane reactor

membrane reactor

equations to solve the problems by mass and energy equation,

continuity equation and momentum equation. Predicting the
behavior of temperature and changes in concentration by first
Fluidized bed
Packed bed

two equations and assessing the pressure change and change

Type of

in mass due to membrane permeation [98].

All reactor models can be categorized according to the
degree of complexity. In particular, the PBMR model can be
34846 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
divided into 1D (one-dimensional), 2D (two-dimensional) and
3D (one-dimensional) models depending on the number of
dimensions. Meanwhile, for FBMR, two types of models based
on two-phase or pseudo-homogeneous approaches have been
proposed [98].
In general, 1D model is only considered in axial gradient
direction and this model is widely used and easy to solve [99].
For example, Simakov and Sheintuch optimized membrane
reactor for auto thermal process to H2 production using steam
methane reforming reaction in terms of membrane area and
heat loss from a pseudo homogeneous one-dimensional
model [100].
2D models, such as mass and heat transfer over mem-
branes, are used when radial gradients cannot be neglected
[101]. Although this model is more accurate, it is more
computationally intensive and takes longer time. Two
dimensional (2D) CFD model and highlighted the negative
impact of polarization effects on membrane performance are
studied by Tiemersma et al. [86]. Oyama and Hakarlioglu
studied the packed bed membrane reactor performance,
simulated work compared with 1-D and 2-D models and pro-
posed criteria for selecting a model for use in given operating
conditions. The 2D model provided better results than the 1D
model, which predicts higher conversions at high pressures
than those observed experimentally [102].
Roses et al. developed a 2D CFD model, simulating the fuel
processor work to hydrogen production via biogas or natural
gas based on realistic architecture and its analysis of the
possibility of thermally integrated PBMR endothermic with
hot steam gas. The significant fuel processor arrangement
made favorable to attain very high efficiency, mainly appro-
priate for incorporation with fuel cells [103].
The 3-D models are intricate and implemented, while no-
symmetrical reactors require to be modeled [104].
However, several researchers have studied PBMR and
FBMR modeling over the years. Table 8 provides an overview
of the mathematical model and the most important results
obtained from modeling the methane steam reforming
response in two types of reactors.
In summary, it should be noted that no single working
model has been developed for performing MSR processes in
PBMR and FBMR, and further research is needed to expand the
knowledge of modeling these reactors.
Recommendations for the production of H2 from
biogas
It is recognized that biogas has prodigious potential to produce
H2 through several reforming methods. However, the choice of
a particular process will depend on many factors such as
composition of the biogas, the purity required to use the H2, the
desired H2 yield, investment availability and others. Reforming
technologies exposed in this paper, such as SR, POR and ATR,
are already commercialized or will soon be commercialized.
New technologies that have not been integrated but are only
presently used in research, for example, internal reforming of
fuel cells, will take some time to commercialize [3].
Biogas as feedstock cannot be used directly in the tradi-
tional reforming technique for producing hydrogen gas due to
the involvement of H2S content in biogas, resulting in catalyst
poisoning and diminution in catalyst activity. It means need to
remove H2S for partially treated reforming of biogas. Dry
reforming method is interesting for biogas due to need for CO2
content. If the CO2/CH4 ratio in the biogas is less than 1 (typical
case), an additional oxidizer must be added to generate
hydrogen or synthesis gas. Thus, adding oxygen according to
the DOR process may be a possible method of slightly
increasing H2/CO ratio while recovering H2 from biogas [2].
Fig. 9 shows composition and simulating biogas with the ratio
of Air-Biogas close to 1, representation of simulation of biogas
from dry reforming, plotted CeHeO ternary diagram and
located region of carbon inside and outside.
One of the key challenges in practically entire reforming
technologies is the development of catalysts that can increase
their life by preventing carbon build-up in the active phase.
Particularly in the DR process, the problem is even more
serious because this process is often impossible due to rapid
catalyst deactivation. Now from DOR, a periodic flow of O2
from the catalyst bed promotes the gasification of carbon
deposited top of the surface, raising availability of catalytically
active sites and temporarily or partially restoring material
activity. Though, in reforming cases (DR and DOR), the ratio of
H2/CO is nearly one, limiting the possibility of H2 formation,
which requires the separation of more CO from the product
through the conversion reaction. This makes it challenging to
acquire pure H2. In addition, some of the H2 generated in the
DR biogas responses with CO2 through a reverse shift reaction
to form water (H2O) and carbon monoxide (CO), which di-
minishes H2 production yields.
Therefore, increasing H2 yield from biogas through the
steam reforming process, hereafter shift reactions, appears
less elegant but higher practical solution, mainly in terms of
diminishing CO and increasing production of H2. In this situ-
ation, high obtained ratio of H2/CO is related to 3 and this
technique is better controlled and well-known. There are
several studies to adapt biogas to SR, despite the higher con-
tent of CO2, while maintaining a higher H2/CO ratio close to
2e3. A similar can occur using POR and ATR, where biogas can
be used directly without significantly reducing the ratio of H2/
CO [124e126].
Thus, ATR seems to be an attractive method for H2 pro-
duction through biogas regarding H2 yield and energy effi-
ciency. In addition, ATR reactors can be quickly shut down and
restarted, leading to the lowest price of any other reforming
process in biogas interruption and energy consumption.
Biogas is enhanced bio-methane after biogas purification,
which involves composition such as CH4 (93e96%), CO2 (4e7%)
and H2S (below 20 ppm) that permits use in all types of
reforming approaches. If low content of CO2 in bio-methane,
the higher conversion efficiency of methane for the desired
product results in higher H2 yield. However, DR and DOR
methods are not suitable as CO2 content has to be added to
reactor, which is already CO2 removed in the previous step
during biogas purification. Thus, SR, POR and ATR processes
are the best-suggested ones [2].
Conventional feedstock biogas reforming processes re-
quires the development of innovative catalysts with their high
temperatures and catalytic activity. It must be chemically and
thermally stable to prevent carbon (coke) deposition on 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5 34847

Table 8 e Summary of mathematical models for modeling MSR response via PBMR and FBMR.
Configuration Classification Assumptions Outcomes Ref.
of reactor
PBMR 1-D Isothermal conditions pseudo-homogeneous Enhanced MSR reaction regards heat losses [100]
membrane hydrogen perm-selective and membrane area.
PBMR 1-D Plug flow membrane hydrogen perm- The distribution of reactive/permeating phase [99]
selective no-isothermal conditions Ergun's can be disused.
equation
PBMR 1-D Plug flow membrane hydrogen perm- The performance of the membrane is affected [105]
selective no-isothermal conditions Ergun's by hydrogen diffusion as the thickness
equation decreases in a certain area.
PBMR 1-D Plug flow membrane hydrogen perm- Complete conversion of methane and high H2 [106]
selective Pseudo-homogeneous Ergun's recovery factor is lower for PBMRs than CRs.
equation
PBMR 1-D Isothermal conditions pseudo-homogeneous Better prediction for permeate flow and [107]
membrane hydrogen perm-selective composition of PBMR performance.
PBMR 2-D Isothermal conditions pseudo-homogeneous PBMR performance affected by parameters [101]
membrane hydrogen perm-selective such as space velocity and temperature
reaction.
PBMR 2-D Plug flow membrane hydrogen perm- Showed the membrane thermal stability and [108]
selective no-isothermal conditions Ergun's its permeability for PBMR.
equation
PBMR 2-D Pseudo-homogeneous membrane hydrogen The high permeability of H2 emphasizes the [86]
perm-selective concentration polarization effect. The
porosity profile should be considered so as not
to overestimate hydrogen penetration.
PBMR 2-D 2-D CFD simulation models a system based on CFD modeling confirms the potential for [103]
a realistic architecture, ideal gas mixing law thermal interaction of membrane hydrogen
membrane hydrogen perm-selective reformers with hot flue gases in architectures
designed for use in PEMFC-based micro-CHP
systems.
FBMR 1-D Membrane H2 perm-selective dense catalytic The capacity of membrane and its position [109]
bed composed of two phases as dense and between catalyst and free board area have
bubble phase, reaction takes place at dense been considered as an important design
phase parameter in this configuration.
FBMR 1-D Membrane hydrogen perm-selective constant The modeling and simulation that have been [110]
temperature pressure gradients are disregard carried out with Aspen Plus show a decent
agreement with outcomes through the
literature.
FBMR 1-D Membrane hydrogen perm-selective constant Comparison with CR, FBMR performs biogas [111]
temperature pressure gradients are discount steam reforming reaction to achieve much
higher hydrogen production.

surface and slow down the decontamination process. Tradi-
tional reforming methods using feedstock as biogas need to
advance catalyst with higher catalytic activity at higher
temperatures, which must be stable chemically and thermally
to prevent carbon (coke) deposition on the surface and slow
down the decontamination process. In terms of treatment of
the reforming process, it needs to reactivate outside or inside
the catalyst bed and require the periodical replacement due to
its permanent deactivation, resulting in slow or stop produc-
tion. This is the main complication in the reforming process
for hydrogen production on a large scale.

Hydrogen utility in fuel cells

Most studied hydrogen production methods are utilized by

Fig. 9 e Ternary CeHeO diagram, CeHeO showing the
possibility of coke formation for biogas internal reforming
in SOFC [2,123].
hydrogen and syngas in fuel cell. A fuel cell is a conversion of
electrochemical devices which convert H2 and O2 into water
(H2O) and produce electricity by the process. Unlike batteries,
fuel cells do not store energy but directly convert the chemical
energy of fuel into electricity without combustion, which is
more efficient and produces very low pollution emissions [2].
It is two times more efficient than turbines and internal
34848 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5
combustion engines and has become the most promising
conversion device [127].
Generally, there are two fuel cells: proton exchange
membrane fuel cells (PEMFCs) and solid oxide fuel cells
(SOFC). PEMFCs contain polymer-based electrolytes such as
Nafion that provide good resistance to gas permeation. The
low operating temperature of the PEMFC allows rapid start-up,
and the use of exotic materials required for other types of fuel
cells is not required for BoP (Plant Balance) because the cells
have no corrosive components [8].
Additional advantages over Alkaline Fuel Cells (AFCs),
Phosphoric Acid Fuel Cells (PAFCs) and Molten Carbonate Fuel
Cells (MCFCs) include limited operating temperatures and a
significant reduction in corrosion problems due to the use of
solid electrolytes. In addition, PEMFCs are very small and light
compared to other fuel cells, making them perfect when size
and portability are leading parameters for applications such
as laptops, computers, automobiles, and cell phones [128].
In contrast, SOFC has more versatile fuel cells and greater
electrical efficiency than nearly 55%. SOFC could be effectively
united with other new technology due to high operating
temperatures like microturbines to allow more generation of
electricity (efficient more than 70%) [129]. It can also be
feasible to provide heat and electricity to coldest region of the
world when used with combination of heat and power plants.
SOFCs are made of ceramic materials and no moving ele-
ments, are free from maintenance and have more reliable
systems [130]. It has more benefits, such as a less expensive
catalyst, suitable for stationary power generation due to its
heavier weight than PEMFCs. Biogas is effectively used to
produce H2 intended for fuel cells [2].
The main key benefits of using biogas in fuel cells are as
follows.
✓ The availability of biogas in huge amounts: Biogas is pro-
duced from renewable biomass and animal waste; there-
fore, the cost of producing this resource is very low.
✓ Fuel cost is low as generated from biogas, so fuel cell power
cost is also low.
✓ Power generated from internal combustion engine via
biogas is reduced due to the presence of CO2 content in
biogas, but there is no need to remove CO2 to generate
energy using fuel cells. Indeed, the presence of CO2 in
biogas is useful for the operation of fuel cells, for example,
SOFC.
✓ More possibility in small scale generation.
✓ The operation is in silent mode due to no moving parts in
fuel cells.
✓ The purification system is simple.
✓ Power generation is also possible in remote area.
✓ Biogas operated fuel cell power plant (2.8 MW) is running in
California, US.
In short, it can be said that biogas can be effectively used in
fuel cells. When biogas is used in fuel cells, removal of CO2 is
not required. CO2 is advantageous for the production of pure
H2. Fuel cells (SOFC) can directly use biogas and produce stable
energy [131]. The biggest drawback of this process is that the
entire process must be stopped for maintenance in the event
of a fuel cell failure. In the hydrogen production process,
carbon from the internal reforming process is deposited on
the anode's surface and affects the fuel cell's life. PEMFC re-
quires external generation of H2. This option is applicable to
supply H2 from SOFC and PEMFC fuel cells.
Recent status of biogas reforming for H2
production from conventional reactors and
membrane reactors
Biogas, created by the decay of organic substances by micro-
organisms, is a renewable fuel that can be used to produce
clean fuels such as hydrogen. There is a growing interest in
hydrogen production through biogas. Recently, hydrogen
production from biogas using conventional reformers has
been extensively studied.
Chattanathan et al. studied biogas reforming for hydrogen
production through the biogas dry reforming (BDR) method
and examined the concentration of H2S as percentage of mol.
such as 0.5,1 and 1.50 and various temperatures like 650,750
and 850  C arrange for the conversion of CH4 and CO2. Con-
version effect of CH4 and CO2 decreased using small amount
of H2S compared to case where there was no H2S as well as H2S
concentration increased with (0e0.5% of mol.) as reduced
conversion of CH4 and CO2 from (67-19%) and (87-22%)
respectively [132].
Izquierdo et al. inspected the various catalysts such as
RheNi and Ni supported cylindrical and disc morphologies for
few reforming techniques using biogas such as tri-reforming
and oxidative reforming and steam reforming in order to
hydrogen production. The disc catalyst was more active at
lower S/C ratios in steam methane process, while cylindrical
catalyst was more active in dry reforming process. Addition-
ally, Rh catalyst showed better performance for all reforming
processes and found RheNi catalyst was a better catalyst in
cylindrical Zeolite [133].
Cipiti et al. considered a mathematical model for SR reactor
using biogas. The molar ratios and inlet temperatures of
reactant by reactor performance were studied and analysed
parameters; then, the experimental results validated this
model using catalyst (Ni/CeO2) and temperature range from
700 to 900  C. The molar ratio H2/CO and CH4 conversion
change from 4.5 to 2.8 and 65.5%e99.6%, respectively, at tem-
peratures above 700  C with a ratio of S/C equal to 3. Moreover,
when increasing S/C ratio from 1 to 5, H2/CO and CH4 conver-
sion change from 1.6 to 3.8, at temperature 900  C [28].
Pawar et al. investigated dry reforming of biogas and
inspected catalyst deactivation due to sulphur poisoning and
coke formation. This study was examined for various pa-
rameters such as temperature (700e800  C), ratio of CH4/CO2
(1.5 and 2), and content of H2S in biogas (0.5 and 10 ppm). The
deactivation of catalyst is more active and faster due to
sulphur content. The deactivation is irreversible at 700  C,
while the catalyst activation is restored by removing sulphur
content from biogas feedstock at 800  C. In addition, the dry
reforming method from biogas under these conditions results
in the formation of carbon in the form of multi-walled nano-
tubes [134].
Tuna et al. studied catalysts (3.1% Ru/geAl2O3 and 7.4% Ni/
NiAl2O4/g-Al2O3) using biogas in steam reformer. This catalyst
 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5 34849

exhibits higher H2 and CO selectivities, higher CH4 conversion,

[132]
[133]

[134]
[135]
[137]
[138]
[139]
Ref.

[28]
higher resistance to carbon formation, low deactivation, and
no CO or CO2 formation. As the CO2 concentration increased,
the H2/CO ratio for catalyst as Ru at 700  C and Ni at 800  C

MR(Fluidized Bed)
Type of reactor
reduced from 3 to 2.4 and 2.9e2.4, respectively [135].

CR (Fixed Bed)
CR (Fixed Bed)
CR (Fixed Bed)
CR (Fixed Bed)
CR (Fixed Bed)
MR(Fixed Bed)
MR(Fixed Bed)
Calgora and Perez-Lopez estimated the catalyst (Ni-M-Al)
in the dry reforming process using synthetic biogas for H2
production. The investigation has been done of various cata-
lyst compositions as Ni-55%, Al-33% and other elements as 3rd
component (La, Ca, M, Mg, Zn, Co, Li). La containing catalysts
offer great stability in reforming reactions due to their high

Composition of Biogas (%)

sintering resistance and high acidity [136].

CO2-39,N2-2
Meanwhile, there is a growing interest on H2 production
using membrane reactors due to several of the aforemen-

CO2-40
CO2-40
CO2-40
CO2-40
CO2-26
CO2-40
CO2-47
tioned advantages over conventional reactors. However,
most research in literature is devoted to producing hydrogen

CH4-59,
CH4-60,
CH4-60,
CH4-60,
CH4-60,
CH4-74,
CH4-60,
CH4-53,
from methane through membrane reactors. Research on the
production of hydrogen from biogas using membrane re-
actors is sparse. For example, Silva et al. established a
mathematical model of a fixed bed membrane reactor (FBMR)
to produce hydrogen from biogas using PdeAg hydrogen se-

1.6,0.9,1.1
lective membranes. The results indicated that the yields of H2

H2/CO
and CO below 600  C are similar with and without hydrogen

3,2.9
0.98
permeation. H2 permeation at 600  C, H2 yields, and CH4

Table 9 e H2 production methods via biogas (CR ¼ Conventional Reactor and MR ¼ Membrane Reactor).

2.8
1.2

e
e
e
conversion were touched 83 and 113.0% higher than the case
without H2 permeation [137]. Iulianelli et al. examined

CH4 conversion (%)

membrane (Pd/Al2O3) in membrane reactor via biogas steam
reforming (BSR) for pure hydrogen production. The study

86,65,90

15e34
30e70
found that permeated H2 was approximately 96% at various

60,60
99.7
conditions such as temperature (380  C), pressure (2 bar) and 67

72

47
H2O/CH4 (3/1), although hydrogen recovery and methane
conversion were more than 20% and 15%, respectively.
Conversely, at temperature (450  C), pressure (3.5 bar) and
H2O/CH4 (4/1) increased the hydrogen recovery and methane 3.1% Ru/geAl2O3 and 7.4% Ni/NiAl2O4/g-Al2O3

conversion 70% and 30%, respectively [138]. Nooijer et al.

established a 1-D and two-phase model of fluidized bed
membrane reactor (FBMR) and studied pure hydrogen pro-
RheNi based on cylindrical Zeolite L

duction using biogas in the steam reforming process. The

model results were validated with experimental values at
Catalyst

temperature 435e535  C, pressure 2e5 bars, and CO2/CH4

ratio up to 0.90 [139]. Summary of various studies on several
Ni (3.31 wt%)/g- Al2O3)

methods of H2 production via biogas in the literature as in

Ni (25 wt%)/Al2O3

Table 9.
(Reformax® 250

7.5 wt%Ni/CeO2
Ni/- Al2O3

Future prospect of biogas reforming in research

direction
e

Broader H2 production from biogas conversion technologies

Temperature ( C)

will require additional efforts on a larger scale. Based on

literature survey, the recommendations or suggestions from
380e450
435e535
700,850

several investigators are the following recommendations for

800
800
900
800

600

possible research directions.

Design and development of reactor and process used in

biogas reforming offer effective hydrogen production with
SR,DR,POR

less energy consumption.

Methods

Assessing the return on investment and operating costs of

industrial scale production facilities requires large-scale
DR

DR
SR

SR
SR
SR
SR

studies of advanced processes.

34850 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 4 7 ( 2 0 2 2 ) 3 4 8 3 1 e3 4 8 5 5

It has been found that operating parameters such as cata-
lyst characteristic and performance, optimum temperature,
presence of impurities and concentration determine the
limits of achieving efficient hydrogen production.

Modeling of CFD and COMSOL multiphysics are open
research areas that can be utilized to validate existing
experimental results.

Some researchers prefer biological methods of H2 produc-
tion to chemical methods due to the possibility of using
sunlight, CO2 and organic waste as substrates to transition
to a green environment in moderate conditions requiring
more consideration.
Conclusion
Large-scale development of H2 energy technologies is needed
for sustainable decentralized power generation in rural and
remote areas. Biogas has abundant potential for inexpensive
and environmentally friendly H2 production, especially in
developing countries like India. Biogas reforming is an
auspicious process for the production of green hydrogen gas
as well as for reducing overburden on natural gas. Currently,
Hydrogen production has become the most important
research area, especially renewable energies due to globally
growing energy demand, depletion of fossil fuels, environ-
mental issues, and progressive fuel cell technology.
Hydrogen production through the chemical reforming
method appears to be more preferred in the coming decades
than other costly and not fully developed processes. The
chemical reforming methods include steam reforming (SR),
partial oxidative reforming (POR), auto-thermal reforming
(ATR), dry reforming (ATR), and dry oxidative reforming (DOR).
However, a traditional reformer with a separation unit for
purification and two separate water-gas shift reactors re-
quires a lot of space, complex control, and lower system effi-
ciency. Thus, an innovative membrane reactor that allows
simultaneous hydrogen production and separation in a single
reactor is more attractive than traditional reforming. The
following conclusions are prepared by evaluation of literature
review.

The main problems with biogas reforming methods,
mentioned in most of the published studies, are associated
with deactivation of catalyst due to coke formation on
surface of catalyst and poisoning effect with sulphur-
containing materials, which can lead to reduction of
hydrogen production.

The biogas refinement phase is very important and needs
to eradicate the destructive effects of (H2S) hydrogen sul-
fide, regardless of the reforming process.

The catalyst must be designed for longer life to prevent
carbon formation on the active catalyst's surface in all
reforming methods used for the hydrogen generation re-
actions. The Catalysts (Nickel-based) are main ideal cata-
lysts for all reforming processes due to low cost.

Auto-thermal reforming methods can be more attractive
because of their high hydrogen yield and conversion effi-
ciency. Though, this process has a difficult management
arrangement.

The biogas reforming methods such DR and DOR have
proven to be more attractive for hydrogen production.
However, these methods are undesirable due to carbon
establishment on catalyst surface and the need for an
additional oxidizing agent.

Most of the H2 production through biogas is carried out via
traditional reformers based on steam reforming processes.
Though, it is also probable to use an innovative membrane
reactor to yield hydrogen through the biogas at a lower
temperature in a single stage (i.e., reforming and separa-
tion process occur in one place). Further research is needed
to develop materials and designs for membrane reactors to
produce hydrogen through biogas.

There is a growing interest on H2 production using mem-
brane reactors due to several of aforementioned advan-
tages over conventional reactors. Additionally, most of the
literature research is devoted to producing hydrogen from
methane and biogas by membrane reactors.

In high-temperature fuel cells such as SOFCs, the tolerance
for CO generated during internal biogas reforming process
decreases above 50 ppm, leading to carbon deposition on
the catalytic electrodic, which requires better control of the
chemical composition of incoming biogas.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
Authors are highly grateful to Department of Mechanical En-
gineering and Center for Energy and Environment, Delhi
Technological University Delhi (India), for providing basic fa-
cilities to compile this work.
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