International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 20 (2016) pp.
10060-10066
© Research India Publications. http://www.ripublication.com
Overview of H2S Removal Technologies from Biogas Production
Nurul Noramelya Zulkeflia,
Department of Chemical and process engineering,
Faculty of Engineering and Built Environment,
University kebangsaan Malaysia, ukm bangi, Selangor
Jamaliah Jahima,b,c
Department of Chemical and process engineering,
Faculty of Engineering and Built Environment,
University kebangsaan Malaysia, ukm bangi, Selangor
Abstract
In the current energy context, the possibility of generating heat or
electricity from renewable sources, such as biogas, increasing
because of high energy demand and environment issues. The
biohydrogen biogas fuel can be directly produced by fermenter and
biomethane steam reforming and use proton exchange membrane
fuel cells to generate the energy. However, pollutants (sulfur
compounds, halogenated hydrocarbons, and siloxanes) can often
be found in production, e.g., hydrogen sulfide (H2S), at range 100
to 10000 ppm. Pollutant concentration is based on the biomass or
the organic waste types. Several purification technologies are used
to remove sulfur compounds, but not all can reduce sulfur to ultra-
low levels. Furthermore, few studies have been reported on biogas
upgrade from sulfur compounds for fuel cell applications. In this
paper, we review and discuss the gas-separation technologies for
H2S removal from biogas production. The mechanism and
operational process of H2S removal unit, including the design,
technique, and material used in absorption/adsorption, are
discussed in terms of performance and efficiency of the separation
system. After all, the techniques of H2S removal via adsorption had
been through recently via modification of cellulose
Nano/microcrystals technologies for adsorption efficiency
enhancement.
Keywords: Biogas, hydrogen sulfide, absorption, adsorption and
membrane.
INTRODUCTION
Biogas is a gas mixture formed by various types of micro-
organisms through the organic matter degradation under anaerobic
conditions. In nature, this process occurs in all places where air is
excluded from organic matter. Anaerobic process degrades the
organic matter by using various types of micro-organisms to form
biogas. Biogas has two major products, which are 60% methane
(CH4) and 40% carbon dioxide (CO2) [1]. Biogases from the dairy
manure waste through the anaerobic digestion have 50%–60%
CH4 [2]. By contrast, Osorio & Torres (2009) found (through
wastewater treatment) that the biogas compositions are between 60
vol.% and 70 vol.% CH4 and between 30 vol.% and 40 vol.% CO2.
Biogas produces minor products, such as hydrogen sulfide (H2S),
ammonia (NH3), hydrogen (H2), nitrogen (N2), carbon monoxide
(CO), water vapor, saturated or halogenated carbohydrates, dust
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Mohd Shahbudin Masdara,b,c*,
Department of Chemical and process engineering,
Faculty of Engineering and Built Environment,
University kebangsaan Malaysia, ukm bangi, Selangor
Edy Herianto Majlanb
Department of Chemical and process engineering,
Faculty of Engineering and Built Environment,
University kebangsaan Malaysia, ukm bangi, Selangor
particles, siloxane, and oxygen gas (O2) [4]. The H2S has been
identified as a problematic compound because of its role in
corrosion [5]. This compound affects the mechanical wear of
equipment and the operation. Hence, biogas-produced H2S
leads to the inefficiency of biogas production. Therefore, H2S
should be removed to avoid any cost-related problem. This
unwanted compound should be removed to increase the
quality of the raw biogas and upgrade a new possible source
of renewable energy.
Biogas purification into possible energy source has gained
wide attention in many countries. Fuel cell technologies are
promising devices specifically for polymer electrolyte
membrane fuel cell (PEMFC). Fuel cell technologies generate
energy or electricity by using this purified biogas for the fuel
supply. PEMFC requires very high purity of H2 up to 99.99%.
Moreover, the CO level should be less than 10 ppm, whereas
H2S should be below 1 ppm because these components
contribute to the corrosion of fuel cell equipment and
poisoning the catalyst of fuel cells. Therefore, impurities
should be removed from the biogas based on fuel cell
requirement.
Based on the information discussed above, this paper focuses
on reviewing and discussing the gas-separation technologies
for H2S removal from biogas production. The technical and
operating processes of absorption and adsorption are discussed
based on the performance and efficiency of the separation
system.
ABSORPTION TECHNOLOGIES
The absorption technique can either be physical or chemical
H2S absorption. In this case, the physical absorption has
dissolved the trace components and is followed by chemical
reaction of the trace component and solvents (common solvent
uses water scrubbing). Normally, physical absorption of H 2S
occurs in water or organic solvent [6].
Kim et al. (2004) and Palmeri et al. (2004) stated that the
chemical absorption benefits the efficiency, reaction rate, and
the operation of H2S removal compared with physical
absorption (water scrubbing) [7,8]. Figure 1 shows the
schematic diagram of the chemical absorption process.
Chemical absorption involves the formation of reversible
chemical bonds between the solute and the solvent. In the
chemical absorption, solvent itself undergoes regeneration,
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 20 (2016) pp. 10060-10066
© Research India Publications. http://www.ripublication.com
which involves bond breaking. To regenerate the solvent, a boiler
system is needed (shown as the heat exchanger unit in Figure 1).
Some chemicals were used in this absorption process. Biswas et al.
(1977) reported that the chemicals used in the process are mono-
ethanolamine (MEA). MEA is part of the alkonamine group. The
other amines are diethanolamine and methyldiethanolamine.
The amine used in chemical absorption is the best process for
anaerobic gas streams. Oxygen can oxidize the amines, can limit
efficiency, and can lead to the necessity of using more materials
[10]. This is due to the amine, which is water soluble and has the
ability to absorb the acid gases. Amine has one hydroxyl group and
one amino group and has the capability to remove H2S by
absorption. After absorption, amine dissolves H 2S in an aqueous
amine stream. In this case, the stream was heated in order to desorb
the acidic components and concentrate the gas stream of H2S
before moving on to the next step of process.
Figure 1. Schematic diagram of chemical absorption [9]
Aqueous ferric solution can be used as another chemical absorbent.
Mohammadtaghi et al. (2012) reported that low Fe2(SO4)3
concentration (up to 0.3 M) increases the absorption rate of H 2S
and vice versa. Ebrahimi et al. (2003) reported that high Fe 2(SO4)3
concentration remarkably increases the ionic strength and viscosity
of the solution, thereby decreasing the solubility, diffusivity,
liquid-side mass-transfer coefficient of H2S, and absorption rate.
The operating parameters increase the efficiency of H2S removal
and energy consumption and help the economical point. Figure 2
shows the effects of (a) temperature and (b) pressure in the
absorption unit. The operating parameters at high temperature of
40 °C and low pressure at 2 atm are the appropriate conditions for
the absorption process [13].
Other chemicals, such as diluted NaOH solution, FeCl2 solution,
and Fe(OH)3, were also used in H2S removal. The operating
parameters such as flow rate, concentration and temperature had
tested to determine the H2S absorption efficiency. The study shows
by increasing the flow rate, concentration and temperature will be
increasing the H2S absorption efficiency [14,15]. Hence, the
chemical absorption via Fe(OH)3, NaOH or FeCl2 are
recommended for furthers study through the high absorption
efficiency.
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ADSORPTION TECHNIQUE
Adsorption techniques are used in the chemically and
physically adsorption process. Generally, the adsorption
process can dehumidify gas, eliminate the odor or pollutants
from the stream, or recover valuable solvent vapors from the
stream. The adsorption process can penetrate the compound in
liquid or gases into pores solid material (adsorbent). The gas
or liquid compound adsorbed in the process is called adsorbate
[16]. For adsorption, gas should be non-combustible or
difficult to burn, and the recovered pollutants should be
valuable and diluted [17]. The adsorption rate depends on the
temperature and concentration of H2S [18].
(a)
(b)
Figure 2. Influence of a) temperature and b) pressure on H 2S
concentration in outlet [11]
A. Adsorption via Metal Oxide
Adsorption can react with some chemicals to adsorb H2S. Iron
oxide, iron hydroxide, and zinc oxide are the commonly used
chemicals. Each chemical has its own specific surface
properties, chemistry, and other factors that make it more
useful for adsorbing H2S. These chemicals react with H2S and
form iron sulfide or zinc sulfide. The chemicals act as catalyst.
Abatzoglou and Boivin (2009) found that the oxidation
reaction of H2S quickens in the presence of Fe. By using iron
oxide as the additive, the process helps with the efficiency of
the reaction. In this process, rust-covered steel wool was used
as the reaction bed. The steel wool has a small surface area.
Hence, impregnated iron oxide can provide larger surface-to-
volume ratio.
Yan et al. (2004) revealed that the H2S is removed at first by
physical adsorption onto the liquid–water film on the
adsorbent surface. H2S and HS- are dissociated, and reaction
occurs between the metal oxides to form sulfides, alkaline
species to provide neutral products, and finally, among surface
oxygen species to create a redox-reaction product. However,
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 20 (2016) pp. 10060-10066
© Research India Publications. http://www.ripublication.com

the physical adsorption through water can be replaced with CO 2 weight reduction leading to adsorption contents was
which deactivates the alkaline-earth-metal-based-reaction site investigated. Hence, the adsorption was analyzed via thermal
which can remove H2S. gravimetric analysis as shown in Figure 3.

B. Adsorption via Activated Carbon Figure 3 shows the effect of temperature on weight reduction
The adsorption through activated carbon has been frequently of PSAC. The reduction of weight is referred as the H 2S
investigated by researchers because the activated carbon has high adsorptions. However, spent PSAC results into a second cycle
surface area, porosity, and surface chemistry [21]. Moreover, this compared with the fresh PSAC. The cycle refers to the
method is a cheap adsorbent that is widely used in the air pollution adsorption content that includes water and H2S or only H2S
technologies. The activated carbon can be used and result in high compounds. This study also reports that the PSAC is a good
adsorption capacity and fast reaction kinetic even in ambient adsorbent because of the high surface area afforded by the
temperature. porous structure.
Activated carbon is divided into impregnated and unimpregnated
types. The impregnated activated carbon refers to the addition of
cation to assist as catalyst in the adsorption process [22]. This
impregnated activated carbon has the highest capability in
removing H2S compared with unimpregnated activated carbon.
The unimpregnated activated carbon is a weak catalyst, and the rate
is limited by complex reaction.
Unimpregnated activated carbon is more interested in the oxidation
of sulfide ion (HS-) to the elemental sulfur. This unimpregnated
activated carbon is dissociated with water film at the carbon surface
[22]. However, the process needs limited water on the media
because it is not practical to increase the water. The excess water
in gaseous state reacts with CO2 and forms carbonates and
sulfurous acid which deactivate the catalytic site. Hence, the
efficiency of H2S adsorption decreases [19]. Nevertheless, a higher
volume of micropores with small volumes upgrades the adsorption
capacity [23]. Figure 3. H2S adsorption via weight reduction at different
Several caustic compounds like sodium hydroxide (NaOH), temperatures [26]
potassium hydroxide (KOH), sodium bicarbonate (NaHCO 3),
sodium carbonate (Na2CO3), potassium iodide (KI), or potassium Choo et al. (2013) studied H2S adsorption by using coconut
permanganate (KMnO4) are added as cations in impregnated shell activated carbon. In this case, the H2S was analyzed
activated carbon. In the study of Bagreev and Bandosz (2002), the through biogas scrubbing with the addition of the three
highest added amount of NaOH in the impregnated activated components of the main gases, which are methane, CO2, and
carbon increases the H2S removal capacity. H2S. Figure 4 shows adsorption system via the studied
Other parameters are required to enhance the efficiency of H2S stimulation. The activated carbon is impregnated with alkaline
removal. Bagreev et al. (2005) reported that the concentration of solutions, such as NaOH, KOH, and K2CO3. The best alkaline
H2S in inlet affects the H2S removal capacity. The decreasing showing the best adsorption of H2S was determined.
concentration of H2S increases the H2S removal. This phenomenon Meanwhile, Figure 5 shows the effect of the alkaline used on
is caused by the low concentration that slows down the oxidation the adsorption capacity performance. K2CO3 was proven to be
kinetic decreasing the surface acidification. Boivin (2009) study the best alkaline-impregnated activated carbon for effective
the surface acidification and observed in the reduction of H2S adsorption capacity.
removal efficiency because H2S cannot be dissociated with acidic Tsai et al. (2001) revealed that this situation is due to the
condition. Moreover, Bagreev et al. (2005) found that the pH < 5 chemical reaction, which is theoretically one molecule of
decreases the H2S adsorption capacity. K2CO3 reacting with one molecule of H2S. The equations (1)
Bagreev et al. (2005) reported that increasing temperature (from 38 and (2) showed the chemical equation of the reaction process,
°C to 60 °C) does not affect the H2S removal. However, Xiao et al. as follows:
(2008) obtained a slight decrease of H2S adsorption capacities
when the temperature increased. H2S + K2CO3 KHS + KHCO3 (Eq. 1)
Moreover, the lignocellulosic sources, such as coconut shell,
corncob, and palm shell, are used as activated carbon. By using by- or
products as sources, the process becomes more economical.
Lee et al. (2013) investigated the impregnated activated carbon H2S + K2CO3 K2S + H2CO3 (Eq. 2)
with palm shell-activated carbon (PSAC) in the H2S removal
technology. The biogas produced from palm oil mill effluent as a
sugar source resulted in economic gain because both are by-
products of palm industries. For comparison, the effect of the fresh
and spent PSACs on the efficiency of H2S adsorption was
investigated. In addition, the effect of temperature parameter to

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© Research India Publications. http://www.ripublication.com
The equation above proved that the highest K2CO3 impregnation
ratio has the highest possibility of removing H2S.
Figure 4. Schematic diagram of adsorption system [27]
Figure 5. Adsorption capacity versus impregnation ratio at
various alkaline solutions [27]
C. Pressure Swing Adsorption (Psa)
PSA has been used to separate the mixture of gases based on the
molecular characteristics and affinity for an adsorbent material.
The gases tend to be attracted to solid surface or are meant to
participate in the adsorption process. The gases can be separated
from the mixture because difference gases can be attracted to
different solid surfaces. Commonly, the adsorptive materials used
zeolites and active carbon as molecular sieves. The process needed
high and low pressure. The target gases adsorbed at high pressure
at first before switching to low pressure. The pressure lowered to
desorb or release the adsorbent material. Moreover, the PSA can
operate at near-ambient temperature [29].
PSA was more efficient for CO2 separation from biogas [30, 31]
than for H2S removal. This phenomenon is due to the addition of a
preliminary step that should enhance the H2S removal efficiency.
The tail gases from PSA also needed further treatment. Hence, it
not economical to use PSA since it makes the process of H2S
removal expensive [32]. Nonetheless, Zhao et al. (2010) had
illustrated the flow diagram of PSA process as in the Figure 6.
Figure 6. Process description of PSA process [29]
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D. Adsorption via Modification of Cellulose Crystals
A study from Heinonen, 2012, a H2S removal via modification
of cellulose nano/micro crystal have been through for two
types of cellulose crystals which are cellulose nanocrystals
(CNC) and micro fibrillated cellulose (MFC). These crystal
have their own characteristic which drive them to adsorb more
H2S gas. The CNC have similar features with activated carbon
but the CNC are easily to modify chemically [35, 36].
Moreover, the CNC/MFC have large specific surface area and
porous structure [37]. The CNC/MFC can replace the activated
carbon since Sabio et al. 2004 had reported the regeneration
are difficult and expensive process.
Therefore, a new study from modification of cellulose crystal
can be investigating and can replace the expensive and
difficult process of activated carbon towards adsorption of H 2S
gas.
MEMBRANE TECHNOLOGY
A previous study on the membrane technology for H 2S
removal focused on purifying the biogas and upgrading to the
natural gas standard. A study of H2S removal by
electrochemical membrane separation by Burke et al. (2002)
had discussed on limitation of H2S removal either via gaseous
diffusion to the cathode-electrolyte interface or by diffusion of
sulfur ion liquid via the electrolytic membrane. Parameters,
such as temperature, H2S concentration, membrane thickness,
and membrane tortuosity, and flow channel design, have been
considered.
As principal of the separation through membrane, some of the
components of raw gases are transported through a thin
membrane while others are retained. Under the membrane
studied, there have several type of membrane had been used as
in the improvement of the technology. Based on the result of
H2S removal, several parameters need to be investigated.
These parameters are pressure, temperature, concentration of
the permeants, and solubility of gases in selective water
swollen polyamide layer [41].
Membrane technologies compete with conventional
technologies, such as pressure swing adsorption, temperature
swing adsorption, or amine scrubbing, in terms of commercial
issues [42, 43]. Moreover, the uptake of biogas through a
membrane usually involves a polymeric membrane. A
previous study used a thin membrane from a thin hydrophilic
composite (TFC) as a separation method. The separation of
H2S by TFC offers future economical possibilities in
comparison with conventional method [40]. The conventional
method decreases in efficiency because of the other extra pre-
treatment steps needed to remove water vapor from the biogas
stream; however, this step was not needed when TFC is used
[41].
Moreover, the type of membrane in water-swollen hydrophilic
thin film composites was investigated under low and high
pressure of a reverse osmosis membrane. The water-swollen
membrane used brass because it can be used to complete the
purification or in the continuous biogas pre-treatment given
that the separation properties can deteriorate when expose for
a long time to H2S [44, 45, 46, 47]. Doljes et al. (2014) showed
that the high-pressure reverse osmosis affected the removal of
H2S, CO2, and methane in the retentate. Increasing pressure
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 20 (2016) pp. 10060-10066
© Research India Publications. http://www.ripublication.com

from 400 kPa to 500 kPa increased the H2S removal from 43 vol.% advantages and disadvantages which lead to the optimum
to 57 vol.%. Moreover, the H2S concentration decreased because efficiency and minimum cost for operational processes.
of the application of increasing pressure from 940 ppm to 540 ppm. However, hollow fibers membrane gas adsorber (HFMGA)
This state of concentration is considered as the ‘safe value’ for shows the best method for removal of H2S through membrane
engines and cogeneration units [49]. technologies.
The methane final product is an issue in upgrading the efficiency. Hence, the table 2 shows the summary of technologies and
The increase of feed pressure and concentration was exaggerated techniques used in biogas purification including their
in the retentate. This result was interpreted in a set of data by Doljes advantages and disadvantages.
et al. (2014) who showed that the methane concentration in
retentate increases to 68 vol.% at 500 kPa, and the lowest number Table 1. H2S efficiency through membrane technique
of methane loss in permeate stream is only 3 vol.%. The high
pressure RO membrane is more preferable than the low pressure Technique Efficiency References
RO membrane. Moreover, more H2S is removed at low pressure.  High pressure RO (500 57 vol.% Dolejs et
The loss of methane in the permeate should be considered. kpa) al. (2014)
Micro-porous hydrophobic had been studied for gas–liquid  Low pressure RO (400 43 vol.%
absorption membrane. Schomaker et al. (2000) had stated the H 2S kpa)
can pass through the membrane, but methane cannot past through.  Micro-porous 98% Wellinger
NaOH solution is used as the absorbing liquid. This process occurs hydrophobic gas-liquid et al.
for three stages, and the micro-porous membrane acts as the absorption membrane (2005)
interface between gas and liquid. The CO2 and H2S are dissolved -High pressure
into liquid, and the methane remains a gas [50, 51]. This process -Low temperature
occurs at high pressure and low temperature (25 °C to 35 °C). (25 °C)
Hence, the concentration of gas can be reduced up to 250 cm 3m-3.  Hollow fibers membrane 100% Mahdavian
Then, Wellinger et al. 2005 recorded the efficiency was >98% and gas adsorber (HFMGA) et al.
as shown in Table 1. Table 1 shows the membrane techniques or -Pressure: 10 atm (2012)
preparation in the biogas purification from H2S with their
efficiency based from several researchers.
Based on the information that was reviewed and discussed above,
different adsorption, absorption, and membrane technologies have

Table 2: Advantages and disadvantages of technologies used for H2S removal

Method Advantages References Disadvantages References
1) Absorption
- Amine - High removal efficiency - Mckinsey (2003) - Portion of amine gas is either lost or - Wang et al. (2008)
- Regenerable degraded
- Expensive process
- Intensive energy to regenerate or replace the
solution
- Complicated flow scheme - Mckinsey (2003)
- Foaming problems
- Other steps required for disposal of foul
regeneration
- Fe2(SO4) - Complete H2S removal - Kim et al. (2004) - Additional chemical input needed - Zhao et al. (2010)
- High efficiency and reaction rate compared with the water - Palmeri et al. (2008) - Pre-treatment of waste
scrubbing
- Use in industrial application and natural gas purification - Ebrahimi et al. (2003)
- Low energy consumption
2) Adsorption
- Chemicals - Dehumidify gas - Wark et al. (1998) - Additional chemical inputs needed - De Hullu et al.
- Remove odor or pollutant from stream - High cost of activated carbon (2008)
- Recover valuable solvent vapors from the stream
- Parameter of temperature and pressure affected the high
efficiency
- Low cost - Mohammadtaghi et al.
- Low energy consumption (2012)
- Catalytic carbon is easy to operate
- Have lower space and maintenance requirements

- Ann et al. (1999)

3) Membrane
- Conventional method - Compact process in light in weight - De Hullu et al. (2008) - Low methane yield - De Hullu et al.
- Low energy consumption - High membrane cost (2008)
- Low-maintenance requirement
- Easy processing
- RO membrane using - High efficiency of H2S at permeate - Dolejs et al. (2014) - Less expensive - Dolejs et al. (2014)
TFC - High selectivity
- Low CH4 at permeate

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 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 20 (2016) pp. 10060-10066
© Research India Publications. http://www.ripublication.com
CONCLUSION
H2S removal technology involves several techniques that require
absorption, adsorption, and membranes. The adsorption through
activated carbon and membrane technology has been studied by
several researchers, and this method was found to be economically
beneficial and gained higher H2S removal efficiency compared
with other techniques. However, the adsorption technique through
the modification of cellulose crystals also been study as much
economical friendly and had look forward for activated carbon
replacement. The appropriate method should be chosen to
maximize the removal efficiency of H2S and unwanted impurities
in biogas fuel. The method increases the quality of the raw biogas,
which could possibly be a new source of renewable energy, such
as fuel cell application.
ACKNOWLEDGEMENTS
This study was partially supported by a grant from University
Kebangsaan Malaysia with the code grant GUP-2014-069 and
UKM – Sime Darby Research Project under code KK-2014-013.
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