REMOVAL OF HYDROGEN SULFIDE (H2S) FROM BIOGAS BY ADSORPTION METHOD

Quyen Huynh1, Viet Q Q Thieu1, Tuan P Dinh1, Sakoda Akiyoshi2

1

Ho Chi Minh City University of Technology (HCMUT), Vietnam

2

The University of Tokyo, Japan

Keywords: Biogas, Hydrogen sulfide (H2S), Removal, Red mud. ABSTRACT In recent years, there has been growing interest in biogas which is a bio-energy source resulting from the conversion of natural biomass. However, in many agricultural countries, agricultural by-products are often the problem of environmental pollution and affect human health. H2S in biogas is very toxic and corrode the equipment. Therefore, there is a critical need for expanding research involving removal of H2S from biogas. Some methods were studied so far: adsorption, absorption, permeation through membrane. However, there are only preliminary studies in Vietnam. The purpose of this study is finding the best material for removing H2S, which must be suitable to practical conditions in Vietnam. Five cheap materials: red mud (waste mud of the aluminum hydroxide production from bauxite ore), activated carbon, silica-gel, iron filings and zeolite (Refinery and Petrochemicals Technology Research Center - Ho Chi Minh City University of Technology - RPTC) were used in our experiments. This study was developed on a traditional adsorption method (red mud and iron filings) for removal of H2S in biogas by iron oxide. The principle of removing H2S reaction is based on reaction between iron oxide in red mud and H2S in biogas. Iron oxide changes H2S into insoluble iron sulfide. The regeneration was carried out by purging air to release sulfur atoms and desorbs iron oxide. All materials were pretreated by drying at 105oC in 12 hours. The experiments were carried out at room temperature. The gas mixture, used in this study, includes H2S (10%) and CO2 (balance). Biogas source was provided from biogas system of the pig farm. The results showed that, iron filings and zeolite materials are not suitable, while the effective time of red mud (390 minutes) is higher than activated carbon (240 minutes) and Silica-gel (210 minutes) on the same experimental conditions. The red mud material cannot be regenerated by purging air on our experiments, but it has the best H2S adsorption capacity (in our experiments). Red mud is the best material (with our experimental procedures) for removal of H2S, and this material should be applied to remove H2S in the biogas processing in Vietnam. We have also proposed a process using fresh red mud (based on non-regeneration principles) to remove H2S in biogas systems. The benefit of this proposed process is not only using cheap material, but also reducing environmental pollution. INTRODUCTION Biogas is produced by the anaerobic digestion or fermentation of biodegradable materials such as biomass, manure, sewage, municipal waste, green waste, plant material, and crops. Biogas comprises primarily methane (CH4), carbon dioxide (CO2) and small amounts of hydrogen sulfide (H2S), moisture and siloxane. Depending on the origins of the gas and the kind of biomass, there are many different names such as: swamp gas (wet gas), marsh gas (moist gas from plants), digester gas (compressed gas), and landfill gas (including 50% methane, 45% carbon dioxide and 5% other gases). Hydrogen sulfide (H2S) is a colorless, very poisonous, flammable gas with the characteristic foul odor of expired eggs, combined with water creates acid sunfuhydric. Acid sunfuhydric is the corrosive acid, causing holes corrosion and brittle cracking of metal due to hydrogen, which can lead to break the tanks or piping. In many agricultural countries, agricultural by-products are often the problem of environmental pollution and affect human health. The biogas systems have contributed to provide energy for daily life, limited waste and offered many realistic applications. However, burning H2S in biogas will form sulfur dioxide, which causes environmental pollution.

Therefore, the removal of H2S is a critical issue, encouraged to protect the device, enhancing safety for technology systems. The standards of H2S component in biogas depend on the intended use, described in table 1. Table 1: H2S concentration Standards depend on the intended use Capstone Turbine Corp.(2002); 2XENERGY (2002); 3STM Power (2002) Application H2S concentration Standards [5] Heating (boiler) 1000ppm, P = 0.8 2.5 kPa, condensed gas. [5] Internal combustion engines 100ppm, P = 0.8 2.5 kPa, condensed gas, siloxane. 1 Turbines 70000ppm, P = 520 kPa, condensed gas, siloxane. Phosphoric acid fuel cells2 20ppm 2 Molten carbonate fuel cells 10ppm 2 Solid oxide fuel cells 1ppm 3 Stirring engines 1000ppm, P = 1 14 kPa
1

Upgrade to the natural gas[1,5]

4 ppm, P > 3000 kPa, siloxane.

Some methods such as adsorption, absorption and permeation through membrane were researched recently. Adsorption of H2S by iron oxide, zinc oxide and zeolite have been published[1,2,3,4]; H2S can be also absorbed in two ways: using chemical solvents (ADIP, MEA, DEA, Econamin, K2CO3, Fe/EDTA) or using physical solvents and synthesis (the Flour process, Selexol, Purizol, Sunfinol, Stretford, and rinse with water). However, there are only preliminary studies in Vietnam. There are two important problems focused on: the feasibility of the method and the conditions to eliminate H2S, effectiveness of the technology by using cheap and available materials in Vietnam. This study used adsorption method for removal of H2S in biogas by iron oxide. Iron oxide transfers H2S into insoluble iron sulfide. Only crystal structure and of Fe2O3 have capability of H2S adsorption selectively[2]. Fe3O4 (Fe2O3.FeO) has also the same activity (Anerousis and Whitman 1985). Chemical reactions are described by equations (1) and (2): Fe2O3 + 3 H2S Fe2S3 + 3 H2O 2 Fe2S3 + 3 O2 Fe2O3 + 6 S MATERIALS AND METHODS Gas mixture was used in this study including H2S (10%) and CO2 (balance), supplied by Messer Vietnam Ltd. Co. Biogas source was provided from biogas systems of pig farm in Binh Duong province. We studied five cheap materials: red mud (waste mud of the aluminum hydroxide production from bauxite ore), activated carbon, silica-gel, iron filings and zeolite (RPTC). H = -22 kJ/g.mol H2S H = -198 kJ/g.mol H2S (1) (2)

Figure 1: Schematic diagram of H2S adsorption experiments

All five materials were pretreated by drying at 105oC in 12 hours. Diagram of technology system was described in Figure 1. The gas inlet was passed through a filter (not shown), controlled by the pump and the flowmeter, and introduced into the H2S treatment column. The experiments were carried out at room temperature; the flow rate of gas inlet was 50ml/min. The concentrations of H2S in gas inlet and gas outlet were measured by chemical method. The airflow was aerated into two erlens, containing excess Pb(CH3COO)2. H2S was retained in the first erlen by equation (3). The experiments must ensure that the creation of precipitated PBS (black) only occurs in the first erlen, no precipitate formation in erlen the second (ensuring retain all of H2S in the first erlen) H2S ( g ) + Pb(CH3COO)2 ( l ) PbS ( r ) + 2 CH3COOH ( 1 ) RESULTS AND DISCUSSION The H2S adsorption capacity of five materials was described in figure 2. The results showed that, iron filings and zeolite materials are not suitable for removal of H2S in our experiments. The effective time of red mud (390 minutes) is higher than those of activated carbon (240 minutes) and silica-gel (210 minutes). In comparison, 3g of each material was used for experiments. The cumulative volume of H2S absorbed by red mud, activated carbon, and silica-gel is respectively 37.7mg, 21.3mg, and 17.7mg (figure 3).The red mud material has the best adsorption capacity (in our experiments). This is explained that red mud material has active surfaces, which are capable of adsorbing H2S by chemical mechanism (Kertamus N J 2004). For further study, the red mud material is considered the most suitable for this system. (3)

Figure 2: H2S removal by various adsorbents

Figure 3: Adsorption capacity of adsorbents

In regeneration, 3g of the red mud was used for each experiment. The flow rate of gas mixture feed, including CO2 (balance) and H2S (10%), is 10 ml/min for adsorption experiments, and the air purge (15 ml/min) was used for regeneration experiments. In figure 4, the effective time of fresh red mud material is 120 minutes, and the slope of the trend line significantly reduced on recycled samples. In figure 5, the H2S adsorption capacity (100% on the fresh sample) is only 72% on the Re1 sample, 53% on the Re2 sample, and cannot almost adsorb H2S on recycled samples over 3 times. Reducing the slope and H2S adsorption capacity on recycled samples suggested that, the red mud material cannot be regenerated by purging air.
mg mg

Figure 4: Ability to adsorb H2S of regenerated red mud samples

Figure 5: Adsorption capacity of regenerated red mud samples.

According to results achieved, subsequent studies would focus on analysis of the red mud material, and its application to biogas processing technology. The red mud material, which is the waste mud of the aluminum hydroxide production from bauxite ore in Tan Binh chemical factory, includes 43% (w/w) of Fe2O3.The results of multi-point BET analysis at RPTC shows that, the surface area of the red mud material is 30.3m2/g, and the micro surface area (DR method) is 45.0m2/g. So, the red mud material can be applied to removal of H2S in biogas. Due to results of biogas component analysis, concentration of H2S in the biogas from swine manure in the province of Binh Duong is 2500ppm. Therefore, the objective of the study is that at least 90% of H2S must be removed. The results of H2S adsorption capacity of the red mud was described in figure 6, the best operation time was 60 minutes, and the adsorbed volume was 77.4/81.7 mg H2S. Therefore, the H2S adsorption capacity of the red mud is 5.45 mg H2S / 1g Red mud, and the average removal efficiency is 94.7% of H2S.
mg

Figure 6: H2S adsorption capacity of red mud

The red mud material, including Fe2O3 as the main component, was considered more suitable than four remains. We have therefore proposed a H2S removal process, which can be applied to biogas systems in Vietnam. We assume a biogas system of 20m3/day with the H2S concentration of 2500ppm. Figure 7 describes the alternative operating system with two adsorption beds, 6.25kg of red mud as adsorbent in each bed. The cycle time is 04 hours with the approximated removal efficiency is 95% of H2S in biogas. The adsorption capacity of recycled red mud materials have significant reductions compared to the fresh red mud. So, we propose using fresh red mud material only. The benefit of this proposed process is not only using cheap material, but also reducing environmental pollution (red mud is contributing cause to seriously environmental pollution in the bauxite mining plants)

Figure 7: Proposed technology process of H2S removal in biogas

CONCLUSIONS Aim to eliminate H2S, we had experiments on five materials, which are cheap and available in Vietnam. The results showed that, the red mud material is the most appropriate and has the best H2S adsorption capacity. Although the red mud material cannot be regenerated by purging air, but it is the waste mud and the cost of using it is only transportation cost. According to study results, we have proposed a process using fresh red mud (based on nonregeneration principles) to remove H2S in biogas systems. The benefit of this proposed process is not only using cheap material, but also reducing environmental pollution (red mud is contributing cause to seriously environmental pollution in the bauxite mining plants). Further study will be directed towards its application to a biogas treatment system. ACKNOWLEDGEMENTS This work was partly supported by JST/JICA-SATREPS, Sustainable Integration of Local Agriculture and Biomass Industries. We gratefully acknowledge JICA Offices financial support and Prof. Sakoda for his precious advices.

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[4]

[5]

Kohl and Neilsen, Gas Purification, (1997) 1 N.J. Kertamus, Removal of H2S on oxidized Iron, 18 (2004) 131 R. Saelee, C. Bunyakan and J. Chungsiriporn, The Removal of H2S in Biogas from Concentrated Latex Industry with Iron(III) chelate in Packed Column, 28 (2008) 10 Steven, Mc. Kinsey, Zicari, Removal of Hydrogen sulfide from biogas using cow-manure compost, (2003) 1 A. Wellinger and A. Linberg, Biogas upgrading and utilization - IEA Bioenergy Task. 24 (2000) 15

Author for correspondence: Mobile: +84.918.610077, Email: tqqviet@hcmut.edu.vn