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Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

Review of H2S Sorbents at Low-Temperature Desulfurization of Biogas

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Published by Hamed Hp
In this paper, the recent investigations on using different mediums to remove H2S from Biogas in Low temperature ranges has been reviewed.
In this paper, the recent investigations on using different mediums to remove H2S from Biogas in Low temperature ranges has been reviewed.

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Published by: Hamed Hp on Apr 18, 2014
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February 2014, Volume 5, No.1 International Journal of Chemical and Environmental Engineering
Review of H
2
S 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 (H
2
S) 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 H
2
S, 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 H
2
S 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 H
2
S and other impurities. H
2
S concentration in biogas ranges from 10-6000 ppm.To many reasons H
2
S 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 H
2
S as by-product and it has increased the concern about H
2
S uptake at low temperatures.H
2
S 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 H
2
S oxidation are considered as source of acid rains and strict environmental regulations derived by developing countries governments caused a growing concern over removing H
2
S from gas streams. This review examines low-temperature sulfur sorbents that have been used recently by researchers for eliminating theH
2
S 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 forH
2
S(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  NH
3
.
2.
 
Activated carbon
Activated carbons (AC) are broadly used as adsorbent to remove hydrogen sulfide (H
2
S) 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 H
2
S Sorbents at Low-Temperature Desulfurization of Biogas
 
23
functional groups, pore size distribution and specific surface area) associated with H
2
S removal significantly [1-3]. Besides, AC samples including inorganic impurities as catalyst can catalyze H
2
S 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
2
S 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 H
2
S can be achieved  by impregnating with caustic materials such as NaOH or KOH [13-19]. Other materials (KI, KMnO
4
,
2
CO
3
 and  Na
2
CO
3
) are also used as impregnants for gas desulphurization [15, 19]. Chiang et al
.
[13]used four alkaline materials (NaOH, Na
2
CO
3
, KOH and K 
2
CO
3
) to impregnate AC, and estimated their performance for H
2
S adsorption. They found that the performance of IAC for H
2
S adsorption was ranked as NaOH >Na
2
CO
3
>KOH>K 
2
CO
3
. It has been reported that the total removal capacity could be increased as much as about 40
 – 
60 times that of the original carbons, by impregnating with Na
2
CO
3
[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 H
2
S 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 H
2
S concentration for the adsorption process under anoxic conditions in a fix  bed is investigated. The stoichiometric ratio between the  Na
2
Co
3
 and H
2
S approximately equals to:
H
2
S +Na
2
CO
3
NaHS +NaHCO
3
(1)
According to the authors’ experiences, the equilibrium
sorption capacity of H
2
S 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, H
2
S 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  
. 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 H
2
S 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 H
2
S from model biogas in dynamic mode to measure the H
2
S 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 H
2
S per 1 kg. Authors also mentioned that apart of CuO
x
 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 (H
2
S) 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 H
2
S adsorption capability of the IAC. The moisture effect on H
2
S 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 H
2
S gas stream. (3)theH
2
S 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
2
S /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 H
2
S 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 H
2
S removal at the ambient temperatures, although a topic of recent studies[1,2,26-
 
Review of H
2
S Sorbents at Low-Temperature Desulfurization of Biogas
 
24
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 H
2
S, 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 H
2
S in low temperatures according to the general reaction:
M
x
O
y
(s)+
y
H
2
S(g)M
x
S
y
(s)+
y
H
2
O(g) [32,33,34,35] (2)
M
x
O
y
isinitial metal oxide sorbent and M
x
S
y
 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 H
2
S 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 toH
2
S (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 H
2
S 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 (CO
3
O
4
) is an efficient sorbent of H
2
S at ambient temperature  because of its high surface area and the presence of the redox couple of Fe
3+
/Fe
2+
. In another study, Baird et al
.
[37] found that reaction of H
2
S 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 H
2
S. Baird et al.[40]also studied Co
 – 
Zn
 – 
Al
 – 
O mixed metal oxides as sorbents of H
2
S at 8˚
. A comparison of the H
2
S uptakes with those of Co
 – 
Zn
 – 
O suggested that the presence of aluminum ions in the mixed oxide gave rise to an increased surface area but not of H
2
S uptake. In another investigation by Davidson et al.[41], the rate of reaction of H
2
S with a high surface areaof undoped and doped ZnO samples studied at 0-45
˚
 range and theyreported that the fast rates appeared to depend upon thecrystallite size, morphology and coexisting water. Sasaokaet al
.
[42] Studied the sorption of H
2
S on ZnO in the presence of CO, CO
2
 and H
2
O. They found that CO inhibits sulfidation reaction due to its competitive adsorption for the same active sites, while H
2
O inhibits the reaction due to promotion of the reaction with ZnS to form H
2
S and ZnO. In a study by Carnes and Klabunde[43] the sorption of H
2
S on microcrystalline metal oxides of Zn, Ca, Mg and Al were compared at low temperatures (25-100
˚
) and higher temperatures (250-
00 ˚
) and they concluded that at elevated temperature, CaO was the best choice for H
2
S adsorption and ZnO appeared to be superior at temperatures lower than 100
˚
. They also found the activity order of the adsorbents as following:
ZnO > CaO >Al
2
O
3
>>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 H
2
S at room temperature. Among the adsorbents of single metal oxides, Cu
 – 
O showed a maximum H
2
S uptake of 283 mg g
-1
, while the other adsorbents had considerably lower H
2
S uptakes (2-32 mg g
-1
). Sample Co
 – 
O did not show a high adsorptive capacity for H
2
S, contrary to the results in the literature [45].Adsorbents Zn/Mn, Zn/Co, Zn/Ti/Zr and Zn/Al showed relatively high H
2
S uptakes (135-152 mg g
-1
), while Zn/Fe, Zn/Ni and Zn/Fe/Zr relatively low H
2
S uptakes (66-75 mg g
-1
). Except for samples Zn/Ti/Zr and Zn/Ni, the adsorbents with smaller crystallite sizes showed a higher H
2
S adsorptive capacity. This indicated that crystallite size of ZnO has an important role in the chemical reaction of H
2
S adsorption. They also found that Zn/Ti/Zr has a high H
2
S 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 Cu
 – 
O > Zn/Mn
≥ Zn/Ti/Zr, Zn/Co, Zn/Al. Also they found that The H
2
S 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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