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International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 20 (2016) pp.

© Research India Publications.

Overview of H2S Removal Technologies from Biogas Production

Nurul Noramelya Zulkeflia, Mohd Shahbudin Masdara,b,c*,
Department of Chemical and process engineering, Department of Chemical and process engineering,
Faculty of Engineering and Built Environment, Faculty of Engineering and Built Environment,
University kebangsaan Malaysia, ukm bangi, Selangor University kebangsaan Malaysia, ukm bangi, Selangor

Jamaliah Jahima,b,c Edy Herianto Majlanb
Department of Chemical and process engineering, Department of Chemical and process engineering,
Faculty of Engineering and Built Environment, Faculty of Engineering and Built Environment,
University kebangsaan Malaysia, ukm bangi, Selangor University kebangsaan Malaysia, ukm bangi, Selangor

Abstract particles, siloxane, and oxygen gas (O2) [4]. The H2S has been
In the current energy context, the possibility of generating heat or identified as a problematic compound because of its role in
electricity from renewable sources, such as biogas, increasing corrosion [5]. This compound affects the mechanical wear of
because of high energy demand and environment issues. The equipment and the operation. Hence, biogas-produced H2S
biohydrogen biogas fuel can be directly produced by fermenter and leads to the inefficiency of biogas production. Therefore, H2S
biomethane steam reforming and use proton exchange membrane should be removed to avoid any cost-related problem. This
fuel cells to generate the energy. However, pollutants (sulfur unwanted compound should be removed to increase the
compounds, halogenated hydrocarbons, and siloxanes) can often quality of the raw biogas and upgrade a new possible source
be found in production, e.g., hydrogen sulfide (H2S), at range 100 of renewable energy.
to 10000 ppm. Pollutant concentration is based on the biomass or Biogas purification into possible energy source has gained
the organic waste types. Several purification technologies are used wide attention in many countries. Fuel cell technologies are
to remove sulfur compounds, but not all can reduce sulfur to ultra- promising devices specifically for polymer electrolyte
low levels. Furthermore, few studies have been reported on biogas membrane fuel cell (PEMFC). Fuel cell technologies generate
upgrade from sulfur compounds for fuel cell applications. In this energy or electricity by using this purified biogas for the fuel
paper, we review and discuss the gas-separation technologies for supply. PEMFC requires very high purity of H2 up to 99.99%.
H2S removal from biogas production. The mechanism and Moreover, the CO level should be less than 10 ppm, whereas
operational process of H2S removal unit, including the design, H2S should be below 1 ppm because these components
technique, and material used in absorption/adsorption, are contribute to the corrosion of fuel cell equipment and
discussed in terms of performance and efficiency of the separation poisoning the catalyst of fuel cells. Therefore, impurities
system. After all, the techniques of H2S removal via adsorption had should be removed from the biogas based on fuel cell
been through recently via modification of cellulose requirement.
Nano/microcrystals technologies for adsorption efficiency Based on the information discussed above, this paper focuses
enhancement. on reviewing and discussing the gas-separation technologies
for H2S removal from biogas production. The technical and
Keywords: Biogas, hydrogen sulfide, absorption, adsorption and operating processes of absorption and adsorption are discussed
membrane. based on the performance and efficiency of the separation

Biogas is a gas mixture formed by various types of micro- ABSORPTION TECHNOLOGIES
organisms through the organic matter degradation under anaerobic The absorption technique can either be physical or chemical
conditions. In nature, this process occurs in all places where air is H2S absorption. In this case, the physical absorption has
excluded from organic matter. Anaerobic process degrades the dissolved the trace components and is followed by chemical
organic matter by using various types of micro-organisms to form reaction of the trace component and solvents (common solvent
biogas. Biogas has two major products, which are 60% methane uses water scrubbing). Normally, physical absorption of H 2S
(CH4) and 40% carbon dioxide (CO2) [1]. Biogases from the dairy occurs in water or organic solvent [6].
manure waste through the anaerobic digestion have 50%–60% Kim et al. (2004) and Palmeri et al. (2004) stated that the
CH4 [2]. By contrast, Osorio & Torres (2009) found (through chemical absorption benefits the efficiency, reaction rate, and
wastewater treatment) that the biogas compositions are between 60 the operation of H2S removal compared with physical
vol.% and 70 vol.% CH4 and between 30 vol.% and 40 vol.% CO2. absorption (water scrubbing) [7,8]. Figure 1 shows the
Biogas produces minor products, such as hydrogen sulfide (H2S), schematic diagram of the chemical absorption process.
ammonia (NH3), hydrogen (H2), nitrogen (N2), carbon monoxide Chemical absorption involves the formation of reversible
(CO), water vapor, saturated or halogenated carbohydrates, dust chemical bonds between the solute and the solvent. In the
chemical absorption, solvent itself undergoes regeneration,


(2012) reported that low Fe2(SO4)3 concentration (up to 0. To regenerate the solvent. The study shows the reaction. After absorption. the process helps with the efficiency of tested to determine the H2S absorption efficiency. and absorption rate. 10061 . Oxygen can oxidize the amines. MEA is part of the alkonamine group. (2004) revealed that the H2S is removed at first by efficiency. International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11. FeCl2 solution. increasing the H2S absorption efficiency [14. liquid-side mass-transfer coefficient of H2S. Figure 2 oxide. and other factors that make it more 40 °C and low pressure at 2 atm are the appropriate conditions for useful for adsorbing which involves bond breaking. iron hydroxide. and reaction occurs between the metal oxides to form sulfides.3 M) increases the absorption rate of H 2S and vice versa. alkaline species to provide neutral products. The from the stream. thereby decreasing the solubility. amine dissolves H 2S in an aqueous amine stream. By using iron parameters such as flow rate. Number 20 (2016) pp. In this process. Ebrahimi et al. concentration and temperature will be as the reaction bed. a boiler ADSORPTION TECHNIQUE system is needed (shown as the heat exchanger unit in Figure 1). such as diluted NaOH solution. The gas anaerobic gas streams. Adsorption via Metal Oxide The operating parameters increase the efficiency of H2S removal Adsorption can react with some chemicals to adsorb H2S. stream. Hence. The adsorption process can penetrate the compound in The amine used in chemical absorption is the best process for liquid or gases into pores solid material (adsorbent). impregnated iron oxide can provide larger surface-to- chemical absorption via Fe(OH)3. A. were also used in H2S removal. chemistry. and finally. or recover valuable solvent vapors from the other amines are diethanolamine and methyldiethanolamine. absorption. Biswas et al. and zinc oxide are the commonly used shows the effects of (a) temperature and (b) pressure in the chemicals. The operating parameters at high temperature of properties. recommended for furthers study through the high absorption Yan et al. can limit or liquid compound adsorbed in the process is called adsorbate efficiency.15]. However. the stream was heated in order to desorb (a) the acidic components and concentrate the gas stream of H2S before moving on to the next step of process. physical adsorption onto the liquid–water film on the adsorbent surface. and the recovered pollutants should be ability to absorb the acid gases. concentration and temperature had oxide as the additive. http://www. Generally. Schematic diagram of chemical absorption [9] Aqueous ferric solution can be used as another chemical absorbent. For adsorption. These chemicals react with H2S and the absorption process [13]. In this case. Iron and energy consumption and help the economical point. Abatzoglou and Boivin (2009) found that the oxidation and Fe(OH)3. (2003) reported that high Fe 2(SO4)3 Figure 2. The adsorption rate depends on the one amino group and has the capability to remove H2S by temperature and concentration of H2S [18]. The chemicals act as catalyst. NaOH or FeCl2 are volume ratio. process can dehumidify gas. The operating reaction of H2S quickens in the presence of Fe. diffusivity. form iron sulfide or zinc sulfide. the Hence. (b) Figure 1. the adsorption (1977) reported that the chemicals used in the process are mono. Mohammadtaghi et al. Other chemicals. rust-covered steel wool was used by increasing the flow rate. among surface oxygen species to create a redox-reaction product. Adsorption techniques are used in the chemically and Some chemicals were used in this absorption process. and can lead to the necessity of using more materials [16]. Influence of a) temperature and b) pressure on H 2S concentration remarkably increases the ionic strength and viscosity concentration in outlet [11] of the solution. which is water soluble and has the difficult to burn. Amine has one hydroxyl group and valuable and diluted [17]. Each chemical has its own specific surface absorption unit. This is due to the amine. gas should be non-combustible or [10]. eliminate the odor or pollutants ethanolamine (MEA). The steel wool has a small surface area.are dissociated. physically adsorption process.ripublication. 10060-10066 © Research India Publications. H2S and HS.

For 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. the through biogas scrubbing with the addition of the three highest added amount of NaOH in the impregnated activated components of the main gases. KOH. 1) Moreover. and palm shell. The equations (1) Bagreev et al. The activated carbon can be used and result in high compounds. the effect of temperature parameter to 10062 . K2CO3 reacting with one molecule of H2S. Bagreev et al. http://www. Moreover. H2S. Nevertheless. However. Bagreev et al. Xiao et al. the effect of the fresh and spent PSACs on the efficiency of H2S adsorption was investigated. The biogas produced from palm oil mill effluent as a sugar source resulted in economic gain because both are by- products of palm industries. sodium carbonate (Na2CO3). The impregnated activated carbon refers to the addition of cation to assist as catalyst in the adsorption process [22]. 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. are used as activated carbon. Figure 3. °C to 60 °C) does not affect the H2S removal. H2S + K2CO3 KHS + KHCO3 (Eq. and carbon increases the H2S removal capacity. and K2CO3. (2001) revealed that this situation is due to the condition. The best alkaline H2S in inlet affects the H2S removal capacity. (2013) investigated the impregnated activated carbon H2S + K2CO3 K2S + H2CO3 (Eq. Unimpregnated activated carbon is more interested in the oxidation of sulfide ion (HS-) to the elemental sulfur. the lignocellulosic sources. In the study of Bagreev and Bandosz (2002). which are methane. or potassium Choo et al. as follows: (2008) obtained a slight decrease of H2S adsorption capacities when the temperature increased. the process becomes more economical. 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. Figure 4 shows adsorption system via the studied Other parameters are required to enhance the efficiency of H2S stimulation. sodium bicarbonate (NaHCO 3). Boivin (2009) study the best alkaline-impregnated activated carbon for effective the surface acidification and observed in the reduction of H2S adsorption capacity. and the rate is limited by complex reaction. Moreover. CO2. This phenomenon Meanwhile. potassium iodide (KI). which is theoretically one molecule of decreases the H2S adsorption capacity. removal efficiency because H2S cannot be dissociated with acidic Tsai et al. Hence. In addition. the efficiency of H2S adsorption decreases [19]. Hence. temperatures [26] potassium hydroxide (KOH). H2S adsorption via weight reduction at different Several caustic compounds like sodium hydroxide (NaOH). such as coconut shell. concentration of H2S increases the H2S removal. By using by. a higher volume of micropores with small volumes upgrades the adsorption capacity [23]. (2013) studied H2S adsorption by using coconut permanganate (KMnO4) are added as cations in impregnated shell activated carbon. International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11. this compared with the fresh PSAC. The reduction of weight is referred as the H 2S investigated by researchers because the activated carbon has high adsorptions. In this case. B. gravimetric analysis as shown in Figure 3. However. porous structure. However. The decreasing showing the best adsorption of H2S was determined. Lee et al. corncob. Adsorption via Activated Carbon Figure 3 shows the effect of temperature on weight reduction The adsorption through activated carbon has been frequently of PSAC.ripublication. Number 20 (2016) pp. This impregnated activated carbon has the highest capability in removing H2S compared with unimpregnated activated carbon. K2CO3 was proven to be kinetic decreasing the surface acidification. the adsorption was analyzed via thermal which can remove H2S. or products as sources. (2005) reported that increasing temperature (from 38 and (2) showed the chemical equation of the reaction process. Activated carbon is divided into impregnated and unimpregnated types. spent PSAC results into a second cycle surface area. the process needs limited water on the media because it is not practical to increase the water. (2005) found that the pH < 5 chemical reaction. The excess water in gaseous state reacts with CO2 and forms carbonates and sulfurous acid which deactivate the catalytic site. 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. The activated carbon is impregnated with alkaline removal. (2005) reported that the concentration of solutions. and surface chemistry [21]. This unimpregnated activated carbon is dissociated with water film at the carbon surface [22]. porosity. 2) with palm shell-activated carbon (PSAC) in the H2S removal technology. 10060-10066 © Research India Publications. such as NaOH. the H2S was analyzed activated carbon. The unimpregnated activated carbon is a weak catalyst.

46. (2014) showed that the high-pressure reverse osmosis affected the removal of Figure 6. The CNC/MFC can replace the activated carbon since Sabio et al. membrane thickness. Commonly. 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. a new study from modification of cellulose crystal Figure 4. 45. temperature. A study from Heinonen. Increasing pressure 10063 . this step was not needed when TFC is used [41]. Pressure Swing Adsorption (Psa) components of raw gases are transported through a thin PSA has been used to separate the mixture of gases based on the membrane while others are retained. 2004 had reported the regeneration are difficult and expensive process. Parameters. Moreover. Process description of PSA process [29] H2S. the uptake of biogas through a PSA was more efficient for CO2 separation from biogas [30. treatment steps needed to remove water vapor from the biogas stream. Adsorption via Modification of Cellulose Crystals ratio has the highest possibility of removing H2S. studied. International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11.ripublication. concentration of different solid surfaces. some of the C. 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). This phenomenon is due to the addition of a previous study used a thin membrane from a thin hydrophilic preliminary step that should enhance the H2S removal efficiency. and flow channel design. Moreover. A study of H2S removal by electrochemical membrane separation by Burke et al. http://www. These crystal have their own characteristic which drive them to adsorb more H2S gas. Number 20 (2016) pp. and solubility of gases in selective water zeolites and active carbon as molecular sieves. Zhao et al. The pressure lowered to technologies. the PSA can swing adsorption. Based on the result of participate in the adsorption process. such as temperature. such as pressure swing adsorption. and methane in the retentate. high and low pressure. Hence. 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. temperature desorb or release the adsorbent material. 47]. Schematic diagram of adsorption system [27] can be investigating and can replace the expensive and difficult process of activated carbon towards adsorption of H 2S gas. several parameters need to be investigated. or amine scrubbing. Under the membrane molecular characteristics and affinity for an adsorbent material. have been various alkaline solutions [27] considered. 2012. Therefore. issues [42. 43]. Adsorption capacity versus impregnation ratio at and membrane tortuosity. Doljes et al. 36]. the adsorptive materials used the permeants. it H2S by TFC offers future economical possibilities in not economical to use PSA since it makes the process of H2S comparison with conventional method [40]. The process needed swollen polyamide layer [41]. the CNC/MFC have large specific surface area and porous structure [37]. (2010) had method decreases in efficiency because of the other extra pre- illustrated the flow diagram of PSA process as in the Figure 6. CO2. The target gases adsorbed at high pressure Membrane technologies compete with conventional at first before switching to low pressure. in terms of commercial operate at near-ambient temperature [29]. The gases can be separated H2S The equation above proved that the highest K2CO3 impregnation D. Moreover. the type of membrane in water-swollen hydrophilic thin film composites was investigated under low and high pressure of a reverse osmosis membrane. (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. The separation of The tail gases from PSA also needed further treatment. there have several type of membrane had been used as The gases tend to be attracted to solid surface or are meant to in the improvement of the technology. The CNC have similar features with activated carbon but the CNC are easily to modify chemically [35. H2S concentration. A than for H2S removal. Moreover. Nonetheless. composite (TFC) as a separation method. The conventional removal expensive [32]. 31] membrane usually involves a polymeric membrane. Figure 5. from the mixture because difference gases can be attracted to These parameters are pressure. As principal of the separation through membrane. however. 10060-10066 © Research India Publications.

Have lower space and maintenance requirements .Dehumidify gas .Palmeri et al.High removal efficiency . Moreover. (2014) Micro-porous hydrophobic had been studied for gas–liquid  Low pressure RO (400 43 vol. (1999) 3) Membrane . (2003) . This result was interpreted in a set of data by Doljes advantages and disadvantages. Portion of amine gas is either lost or . Number 20 (2016) pp.Low cost .Dolejs et al. This process -Low temperature occurs at high pressure and low temperature (25 °C to 35 °C).Remove odor or pollutant from stream . (2008) .De Hullu et al. This process occurs hydrophobic gas-liquid et al.  High pressure RO (500 57 vol. International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11.Zhao et al.Parameter of temperature and pressure affected the high efficiency . . (2014) . more H2S is removed at low pressure. Moreover.% absorption membrane.De Hullu et al. H2S efficiency through membrane technique of methane loss in permeate stream is only 3 vol.Wark et al. Based on the information that was reviewed and discussed above. However. The CO2 and H2S are dissolved -High pressure into liquid. (2014) who showed that the methane concentration in retentate increases to 68 vol. technologies. 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.Dolejs et al.Mohammadtaghi et al.  Micro-porous 98% Wellinger NaOH solution is used as the absorbing liquid.Ann et al. High membrane cost (2008) .ripublication. . 10060-10066 © Research India Publications. (2004) .RO membrane using . kpa) al.High efficiency and reaction rate compared with the water . Compact process in light in weight .Chemicals .Low energy consumption 2) Adsorption .com from 400 kPa to 500 kPa increased the H2S removal from 43 vol.Kim et al.%.% at 500 kPa. The methane final product is an issue in upgrading the efficiency. of the application of increasing pressure from 940 ppm to 540 ppm.Amine . but methane cannot past through.Foaming problems . 51]. .Additional chemical inputs needed . Wellinger et al.Ebrahimi et al.High cost of activated carbon (2008) . 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.Low CH4 at permeate 10064 . and the lowest number Table 1.Fe2(SO4) . (2008) .Recover valuable solvent vapors from the stream .Regenerable degraded .Additional chemical input needed .% advantages and disadvantages which lead to the optimum to 57 vol. 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]. different adsorption. the concentration of gas can be reduced up to 250 cm 3m-3. (2000) had stated the H 2S kpa) can pass through the membrane.High selectivity . absorption. and membrane technologies have Table 2: Advantages and disadvantages of technologies used for H2S removal Method Advantages References Disadvantages References 1) Absorption .High efficiency of H2S at permeate . et al. Low-maintenance requirement .%. Other steps required for disposal of foul regeneration .Mckinsey (2003) .Low energy consumption (2012) . (2010) . The high pressure RO membrane is more preferable than the low pressure Technique Efficiency References RO membrane.Pre-treatment of waste scrubbing .Complicated flow scheme . (2008) .Mckinsey (2003) . as shown in Table 1. and the micro-porous membrane acts as the absorption membrane (2005) interface between gas and liquid.Conventional method . Schomaker et al. and the methane remains a gas [50. (1998) . the H2S concentration decreased because efficiency and minimum cost for operational processes.De Hullu et al.Intensive energy to regenerate or replace the solution .Use in industrial application and natural gas purification .Complete H2S removal .% Dolejs et The loss of methane in the permeate should be considered. (2014) TFC . 2005 recorded the efficiency was >98% and gas adsorber (HFMGA) et al. for three stages.Wang et al. (25 °C) Hence. Less expensive . Low energy consumption .Catalytic carbon is easy to operate .  Hollow fibers membrane 100% Mahdavian Then. Easy processing . Expensive process . Hence. Low methane yield . http://www.

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