February 2014, Volume 5, No.

1 International Journal of Chemical and Environmental Engineering

Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

Hamed-Pourzolfaghar; Mohd Halim-Shah Ismail* ; Shamsul-Izhar ; Zahra-MagharehEsfahan Chemical and Environmental Engineering Department, School of Engineering, Universiti Putra Malaysia (UPM), 43400, Selangor, Malaysia
*

Corresponding Author E-mail:

mshalim@upm.edu.my

Abstract:
This review surveys the sorbents that remove Hydrogen Sulfide (H2S) from the biogas generated at low-temperature ranges from different sources. Biomass feedstocks contain low percentages of protein-derived sulfur that is converted primarily into H2S, as well as small amounts of carbonyl sulfide (COS) and organosulfur compounds during fermentation, gasification, etc. These sulfur species must be removed from the raw biogas before it is being used for the downstream fuel synthesis or the power generation because of their disadvantages, among which, acid rains, and human health problems. Several types of sorbents and ceria have been developed over the last two decades which are capable of removing H2S from the biogas at low-temperature ranges. This study has divided the current sorbents into three main categories on the basis of the recent investigations; (1) Activated carbons, (2) Metal based materials, and (3) Microporous and mesoporous silica. Further improvement is essential to develop sorbents appropriating them for desulfurization of the biogas owing to their low efficiency and high price, which present different challenges to eliminate hydrogen sulfide at low-temperature ranges. Keywords: Adsorption; Low temperature; Biogas; Zeolite; Metal Based Adsorbents.

1. Introduction
Growing world demands for fossil fuels and its limited reserves caused finding an alternative fuel sources which is cheap, available, abundant and environmental friendly.Biogas is a renewable fuel which is produced from fermentation of organic compositionssuch as animal waste, crop residue, sewage sludge, household waste, Wastewater and landfill. It is clean, cheap and environmentally friendly.Physical and chemical characteristics of biogas is similar to those of natural gas,hence, it is a suitable alternative for LPG, fuel for heating, lighting, producing electricity or fuel for driving equipment.Biogas composition depends on the organic substrate. Biogas obtained from manure digestion generally consists of Methane (55-80%),Carbon dioxide(20-45%), Nitrogen(0-10%) and trace amounts of H2S and other impurities. H2S concentration in biogas ranges from 10-6000 ppm.To many reasons H2S which is a persistent problem linked with biogas, has to be removed to use as an alternative for fossil fuels.Many industrial processes, such as the Claus process, Anaerobic digestion, and Natural gas sweetening are producing H2S as by-product and it has increased the concern about H2S uptake at low temperatures.H2S is an extremely toxic, odorous and corrosive gas which can cause corrosion to the engine and pipeline and decrease plant lifetime. Also this toxic gas can cause health problems even as low as 1 ppm. Last not least, sulfur compounds produced by H2S oxidation are considered as source of acid rains and strict environmental regulations derived by developing countries governments caused a growing concern over removing H2S from gas streams. This review examines low-temperature sulfur sorbents that have been used recently by researchers for eliminating theH 2S content from biogas generated from different sources.

1.1. Criteria for Selecting Sulfur Sorption Materials

Criteria that a sorbent material must satisfy, for biogas desulfurization to be both economical and operational, are; (1) High adsorption capacity forH2S(2) Fast adsorption kinetics (3) Proper Mechanical properties (4) Stable chemical properties (5) Regenerable through a suitable pathway and (6) Multifunctional operation in terms of removing other contaminants such as HCl and NH3.

2. Activated carbon
Activated carbons (AC) are broadly used as adsorbent to remove hydrogen sulfide (H2S) both as virgin and impregnated activated carbon due to their high specific surface area and porous structure. Several studies informed that the surface properties of carbon (PH,

Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

functional groups, pore size distribution and specific surface area) associated with H2S removal significantly [1-3]. Besides, AC samples including inorganic impurities as catalyst can catalyze H2S oxidation and convert to elemental sulfur in the presence of oxygen [4-8]. The surface area and porosity of carbon depend generally on the activation procedure and the nature of the organic precursor. Although changes in the conditions of the process can regulate the pore sizes of adsorbents, the full control of structural parameters has not yet been developed. Regeneration of consumed AC can be employed using cold/hot water washing or thermal treatment to achieve recycle object, but the H 2S adsorption capacity after regeneration usually decreases remarkably. The cause is endorsed that some sulfur species as elemental sulfur or sulfuric acid is strongly bound with activated sites leading to exhaust irreversibly [9-12].

2.1. Impregnated activated carbon (IAC)

Favorable performance for removing H2S can be achieved by impregnating with caustic materials such as NaOH or KOH [13-19]. Other materials (KI, KMnO4, K2CO3 and Na2CO3) are also used as impregnants for gas desulphurization [15, 19]. Chiang et al.[13]used four alkaline materials (NaOH, Na2CO3, KOH and K2CO3) to impregnate AC, and estimated their performance for H 2S adsorption. They found that the performance of IAC for H2S adsorption was ranked as NaOH >Na2CO3>KOH>K2CO3. It has been reported that the total removal capacity could be increased as much as about 4060 times that of the original carbons, by impregnating with Na2CO3[13-16]. Although caustic materials with acidic gases have a good performance, but impregnation decreases the ignition temperature of the carbon and causes a hazard of self-ignition [20]. Oxidation of hydrogen sulfide to elemental sulfur is another disadvantage of caustic impregnated carbons [2,7], which cannot be removed from carbons by washing with water [11,12]. Moreover, the activity of caustic carbons toward H2S oxidation ends by consuming the caustic and the carbon pores are blocked by sulfur and sodium or potassium salts. The costs also increase expressively by chemical modification of the adsorbent. Latest studies on different impregnants and conditions to improve the adsorption throughput are reviewed in subsequent. In a study by Xiao et al.[21] influence of impregnating the activated carbon with sodium carbonate and operating values such as temperature and inlet H2S concentration for the adsorption process under anoxic conditions in a fix bed is investigated. The stoichiometric ratio between the Na2Co3 and H2S approximately equals to: H2S +Na2CO3NaHS +NaHCO3(1) According to the authors experiences, the equilibrium sorption capacity of H2S increased more than 3 times after

impregnation, though the BET surface area, micropore volume of the activated carbon, was reduced slightly. The results also confirm that after impregnation, H2S is no longer removed mainly by physical adsorption but chemical reaction. Kazczmarczyk et al.[22] studied the influence of the impregnation of commercial activated carbon with copper oxides at C. Various amounts of copper oxides were deposited on the commercial AC by incipient wetness impregnation with copper acetate. To evaluate the performance of studied materials for H2S removal from methane, both static and dynamic tests were used. More detailed investigation by authors, revealed that copper is preferentially located in the smallest pores with width 2-3 nm. Amount of adsorbed methane diminishes with increasing of copper amount deposited on the results in removal of H2S from model biogas in dynamic mode to measure the H2S breakthrough, revealed that copper modified adsorbents exhibit distinctly higher capacity than raw AC. One can estimate that Cu- loaded adsorbents are able storage Ca. 15-24 g H2S per 1 kg. Authors also mentioned that apart of CuOx content, capacity of both adsorbents clearly depends on the size of adsorbents grains. This effect can be explained by increase of external diffusion limitation with increase of particles diameter. Huang et al.[23] investigated the effect of moisture on adsorption efficiency of hydrogen sulfide (H2S) by copper (II) nitrate at 303 K. It was found that either the existence of moisture in the gas stream or IAC pre-moistened significantly affected H2S adsorption capability of the IAC. The moisture effect on H2S adsorption capacity of IAC was attributed to the following causes; (1)the copper (II) species supported on the IAC would be reduced to copper (I) species under moist atmosphere. (2)the competition adsorption occurred when the moisture existed in the H2S gas stream. (3)theH2S adsorption capacity increased when the water film formed onto the IAC. Pipatmanomai et al.[24]Studied the coconut shell based activated carbon adsorption capability which was impregnated with 2% potassium iodine (KI). The adsorption capacity was estimated to be 0.062 kg of H 2S /kg of adsorbent.

2.2. Virgin activated carbon

The search for virgin activated carbons is driven by the disadvantages of caustic impregnated carbons, which are still frequently used as effective H2S adsorbents, as mentioned above. The advantages of virgin activated carbons over caustic carbons are as follows; (1)cost per pound is much lower; (2) capacity for physical sorption is high; (3) activated carbon surface with incorporated heteroatoms (such as oxygen, nitrogen, hydrogen, and phosphorus) can act as a catalyst for oxidation [25], and (4) the deposition of inorganic salts is limited. The use of virgin activated carbon for H2S removal at the ambient temperatures, although a topic of recent studies[1,2,26-

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Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

29] is not yet common. The major difficulty seems to lie in the fact that little is known with certainty about the mechanism of reaction on the carbon surface. Despite of reactions on caustic-impregnated carbons, the reactions on virgin carbons are very complex since they involve the broad spectrum of physical and chemical properties of the adsorbent. Most of the results reported so far have been based on an empirical analysis of specific types of carbon, and sometimes they appear to be inconsistent [4,6,7,26,30]. Recent investigations on virgin activated carbons can be categorized into three main subjects; (1) exploring the effect of dynamic conditions such as concentration of H2S, oxygen content, and humidity [12,20].(2)identifying the surface feature of virgin activated carbons which are important for their performance as adsorbent of hydrogen sulfide [1,2,29,31] and (3) feasibility of virgin activated carbon regeneration by different methods[9-12].

3. Metal based sorbents

Much of the research concerns metal based materials as sorbent that are presumed to remove H2S in low temperatures according to the general reaction: MxOy(s)+yH2S(g)MxSy(s)+yH2O(g) [32,33,34,35] (2) MxOyisinitial metal oxide sorbent and MxSy is metal sulfide after the reaction. Equation 2 describes a solid gas reaction. This reaction is distinct from, and preceded by, a surface reaction that occurs when the time scale for sulfidation is short [36]. According to the several studies stated in the literature, an ideal metal oxide sorbent of H2S present in an industrial gas-stream should have the following characteristics: (1) potential of regenerating the metal sulfide formed into the initial metal oxide, (2) extremely reactive toH2S (3) appropriate morphology and porosity of the pellet to increase the diffusion capability and reactivity and (4) minimizedundesired reactions in adsorption and regeneration conditions. ZnO is the primary component in the mixed metal oxide sorbents for H2S removal at the low temperature in the literature while sulfidation of CuO is much more thermodynamically favorable than that of ZnO [37,38]. Furthermore, mixture of different metal oxides is studied by researchers to find the most proper sorbent and condition in low temperature range. Baird et al.[39] found that the mineral feroxyhite (CO3O4) is an efficient sorbent of H2S at ambient temperature because of its high surface area and the presence of the redox couple of Fe3+/Fe2+. In another study, Baird et al.[37] found that reaction of H2S with ZnO doped with first-row transition metals was restricted to about 0.6 surface monolayers. The main role of the transition metaloxide is to increase the total surface area available for reaction with H2S. Baird et al.[40]also studied Co ZnAlO mixed metal oxides as sorbents of H2S at 8C. A comparison of the H2S uptakes with those of CoZnO

suggested that the presence of aluminum ions in the mixed oxide gave rise to an increased surface area but not of H2S uptake. In another investigation by Davidson et al.[41], the rate of reaction of H2S with a high surface areaof undoped and doped ZnO samples studied at 0-45 C range and theyreported that the fast rates appeared to depend upon thecrystallite size, morphology and coexisting water. Sasaokaet al.[42] Studied the sorption of H2S on ZnO in the presence of CO, CO2 and H2O. They found that CO inhibits sulfidation reaction due to its competitive adsorption for the same active sites, while H2O inhibits the reaction due to promotion of the reaction with ZnS to form H2S and ZnO. In a study by Carnes and Klabunde[43] the sorption of H2S on microcrystalline metal oxides of Zn, Ca, Mg and Al were compared at low temperatures (25-100 C) and higher temperatures (25000 C) and they concluded that at elevated temperature, CaO was the best choice for H2S adsorption and ZnO appeared to be superior at temperatures lower than 100 C. They also found the activity order of the adsorbents as following: ZnO > CaO >Al2O3>>MgO (3)

Xueet al.[44]studied on the performance of a series of metal oxides( Sn-O, Ni-O, Co-O, Ca-O, Mn-O, Ag-O, Zn-O, Cu-O, Zn/Fe, Zn/Ni, Zn/Co, Zn/Mn, Zn/Fe/Zr, Zn/Ti/Zr, Zn/Cu/Zr, Zn/Co/Al, Zn/Al, Zn/AL, Mo) for the removal of H2S at room temperature. Among the adsorbents of single metal oxides, CuO showed a maximum H2S uptake of 283 mg g-1, while the other adsorbents had considerably lower H2S uptakes (2-32 mg g-1). Sample CoO did not show a high adsorptive capacity for H2S, contrary to the results in the literature [45].Adsorbents Zn/Mn, Zn/Co, Zn/Ti/Zr and Zn/Al showed relatively high H2S uptakes (135-152 mg g-1), while Zn/Fe, Zn/Ni and Zn/Fe/Zr relatively low H2S uptakes (66-75 mg g-1). Except for samples Zn/Ti/Zr and Zn/Ni, the adsorbents with smaller crystallite sizes showed a higher H2S adsorptive capacity. This indicated that crystallite size of ZnO has an important role in the chemical reaction of H2S adsorption. They also found that Zn/Ti/Zr has a high H2S adsorptivity although the crystallite size of ZnO is relatively large. Bairdet al.[37]prepared Zn/Co, Zn/Al and Zn/Co/Al adsorbents from metal nitrate solution by a coprecipitation method and reported the degree of reaction for sulfidation to be 46, 9 and 12%, respectively. The results of M. Xueet al. study showed much higher values for Zn/Al and Zn/Co/Al, and a close value to Zn/Co as compared to the data by Stirling et al. The adsorbents exhibited a reactivity trend of CuO > Zn/Mn Zn/Ti/Zr, Zn/Co, Zn/Al. Also they found that The H 2S adsorptive capacity of ZnO could be enhanced considerably by doping it with metal ions such as Mn, Co, Cu, Ti and Zr. The doping of such metal ions produced microcrystalline oxides, which showed considerable high

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Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

H2S uptakes as compared to pure ZnO. Polychronopulouet al. [38] investigated on efficiency of various Zn-Ti based mixed metal oxides towards H2S adsorption in the 25-100C range. The effects of the chemical nature of a third metal additive (Mn, Cu, Mo), nominal chemical composition, and presence of water were studied. The researchers found that the mixed metal oxides with compositions20Zn-80Ti-O and 40Zn-60Ti-O present higher maximum H2S uptakes than ZnO and TiO2 solids also prepared by Sol-gel method. Recently, Jiang et al.[46]studied on one series of Cu-Zn and two series of Cu-Zn-Al hydroxycarbonate precursors with varying metal molar ratios as adsorbents for H2S removal in the range of 25-100C. According to klier[47], addition of aluminum further increased dispersion of Cu and ZnO in the Cu/ZnO/Al2O3 catalysts for methanol synthesis, therefore enhancing their catalytic activities. The influence of Cu, Zn, and Al molar ratios, preparation methods, adsorption process temperature, and specific surface area were investigated by Jiang et al,. The authors concluded that doping zinc with Copper or vice versa and subsequent incorporation of aluminum decreased both the Zno and CuO mean crystalline sizes in the Cu-Zn and/or Cu/Zn/Al mixed metal oxides by decreasing of mean crystalline sizes of hydroxyl- carbonate phase. The small mean crystalline sizes and high specific surface area of ZnO and/or CuO contributed to the increase of breakthrough sulfur capacity at the low temperature by reducing the thickness of potential sulfur shell on the outer layer of the oxide crystalline grains and increasing the area of the interface for the exchange of Hs/S2- and O2 .Jiang et al. also found Cu-rich adsorbents more suitable for removing H2S at the low temperature than Zn-rich adsorbents due to faster sulfidation rate of the CuO than that of the ZnO because of less rearrangement of the union lattice.

4. Microporous and Mesoporous silica

Silica based materials have been used recently for H2S elimination from biogas can be divided into the two main categories: (1) Microporoussilica (zeolites)which have pores with diameters less than 2 nm. (2) Mesoporous silica whichhave pore diameters between 2 and 50 nm.

4.1. Microporous silica (zeolites)

Zeolites are microporous, aluminosilicateminerals that have been considered for separation and purification of gases as of their characteristic ability for polar compounds adsorption[48]_ENREF_3. As of November 2010, 194 unique zeolite frameworks have been identified, and over 40 naturally occurring zeolite frameworks are known [49]. Currently there is a growing demand on natural zeolites for gas separation, such as Mordenite, Clinoptilolite, Erionite, Phillipsite, and Ferrierite[48,50,51].On the adsorption processes Natural zeolites usually require previous activation and packaging steps which not always makes their use

economical_ENREF_8 [52]. Because of this reason, natural zeolites must demonstrate unique or better properties to replace synthetic ones in commercial separations. Though the adsorption capacity of H2S by zeolites are low comparing to other mixed oxide sorbents the regeneration of them are much easier and also lowcost. Advantages of Zeolite adsorption involve in the reversibility of the adsorption-desorption processes, low cost, long-term chemical and thermal stability of adsorbents, and most importantly high selectivity for H2S separation_ENREF_6 [50]. Early works with zeolites investigated the Chemical reactions during the process, best activation method for increasing the adsorption capacity, and finding a zeolite with high selectivity. Paolo cosoli et al._ENREF_9 [53] studied hydrogen sulfide (H2S) removal from biogas in low temperature by grand canonical monte carlo (GCMC) and molecular dynamics (MD) molecular simulation techniques. They used different zeolites simulated frameworks like FAU NAY, FAU NAX, LTA, and MFI. Considering simulated adsorption isotherms of different zeolites, the authors found that FAU NAY characterized by the highest selectivity towards H2S and MFI by the lowest one. This proves that hydrophilic zeolites are more indicated for adsorption of H2S from biogas. In a separate publication, Paolo cosoli et al.[54] tried by simulation techniques on the adsorption of low pressure hydrogen sulfide in zeolites (NAY) in depth and found more details about the process. Much more affinity of polar H2S to the hydrophilic zeolite framework than CH4, influence of different number and type of molecules of biogas inserted in the cell on the adsorption process, and favored H 2S adsorption over CH4 when P(H2S) is increasing are some of their findings from this study. Gillard, M et al._ENREF_11 [55]studied on NAY zeolite in order to determine dissociation amount of H2S on adsorbent framework. They used In-situ combination of infrared and solid-state NMR spectroscopy. Previous investigation by karge et al._ENREF_12 [56]stated that on NAY zeolite, the adsorption of H2S is almost non dissociative. Alonso-Vicario et al._ENREF_8 [52]studied on cleaning and upgrading of biogas by PSA technique on a natural zeolite ,Clinoptilolite, and two synthetic molecular sieves (5A and 13X). They determined that Clinoptilolite possess unique adsorption properties for simultaneous biogas purification and upgrading of methane, although many researchers claimed that the good attributes of natural zeolite may not offset the effect of impurities and inconsistency of properties relative to the more uniform synthetic ones. They also demonstrate the importance of the selection of the optimal activation method for each zeolite to overcome the mentioned drawback.

4.2. Mesoporous silica

Mesoporous silica is a form of silica and a recent development in nanotechnology. The most common types of mesoporous nanoparticles are MCM-41 and SBA-15. Microporous materials such as zeolites present severe

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Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

mass transfer limitations when large reactant molecules are involved. This drawback of microporous materials, forced scientists to a new field of material research and was opened up due to the discovery of mesoporous material, MCM-41 in 1992. The narrow and uniform pore size of mesoporous materials with extremely high surface area holds much promise for the development of novel solid catalysts. In continue, the recent studies on most efficient mesoporous silica materials to adsorbing H2S from biogas in an ambient temperature are reviewed. Wang et al. [57] studied on H2S removing capacity of Mesoporous silica SBA-15 with adding zinc oxide (ZnO) nanoparticles through via incipient wetness impregnation and ultrasonic method. According to the experiments results, the authors concluded that the prepared materials have a superior ability to remove H2S down to parts per billion (ppb) from gas stream at lower temperature (25 C),and the highest H2S breakthrough capacity, 436 mg/g S adsorbent, observed for SBA-15 with 3.04 wt% zinc loading.Their interpretation of enhancement ofH2S removal
capacity by this material was to the integration of the high surface area of the mesoporous material and the promising

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desulphurization properties of ZnO nanoparticles. Wang et al. [5]in another study investigated the removal of H2S from the gas streams with high concentration of H2S (4000 ppm) over the molecular sieve sorbent, and their sorption performances in detail in a fixed-bed flow system. The authors synthesized a series of sorbents with a linear PEI supported on MCM-41, SBA- 15 and MCM48 molecular sieves. The sorption was conducted at a temperature range of 227 C.They studied the effects of the operating temperature, GHSV, the amount of PEI loading and the different molecular sieve supports. The authors observed that Loading 50 wt% PEI on SBA- 15 gives the best breakthrough capacity, while loading 65 wt% PEI on SBA-15 has the highest saturation capacity. They concluded that mesoporous molecular sieve with large pore size and three-dimensional channel structure favors increasing the kinetic capacity of the supported PEI sorbent. In addition, the developed sorbents can be regenerated easily at mild conditions (temperature range of 75 100 C) and have excellent regenerability and stability.

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5. Conclusions
This review has identified several different sorbent systems that can potentially be used to effectively remove H2S from biogasproduced from different sources at lowtemperature ranges.The optimum sorbent depends on the process conditions and also target sulfur levels. Pilot scale testing of such sorbents will provide results and experience for eventual commercialization. As more scientific data on low temperature sulfur sorbent becomes available, techno economic analysis and systems modeling to determine the potential improvements in thermal efficiency, environmental benefits, and process economics through use of such sorbent systems will be critical.

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Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

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