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Research Paper

Hydrogen sulde removal from biogas by bio-based iron sponge

Phil Cherosky, Yebo Li*
Department of Food, Agricultural, and Biological Engineering, The Ohio State University, Ohio Agricultural Research and Development Center, 1680 Madison Ave., Wooster, OH 44691-4096, USA

article info
Article history: Received 7 June 2012 Received in revised form 19 October 2012 Accepted 31 October 2012 Published online 30 November 2012

The iron sponge process, a technology used for removing hydrogen sulphide (H2S) from biogas, can potentially use various biodegradable wastes as the supporting material for the H2S adsorption media, providing improved exibility and cost-effectiveness. In this study, ground garden waste, digested garden waste, and spent tobacco were evaluated as supporting materials of the H2S adsorption media. It was found that both particle size and moisture content had signicant effects on H2S removal performance when ground garden waste was used. The optimum moisture content of the ground garden waste system was determined to be 15%. The optimum moisture content for the digested garden waste system was found to be 25%. Iron sponge with either ground garden waste or digested garden waste at their optimum conditions had an H2S removal performance comparable to a commercial product (SulfaMaster). Iron sponge using spent tobacco, however, was found to be only about 20% as efcient as SulfaMaster. Ground or digested garden waste could be an alternative supporting material for the iron sponge system. 2012 IAgrE. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Hydrogen sulphide, a major contaminant in biogas produced from anaerobic digestion of organic materials, can cause corrosion of metal parts, degrade engine oil, and form poisonous sulphur dioxide (H2S) during combustion for electricity production (Hamilton, 1985; Muche & Zimmerman, 1985; Sublette & Sylvester, 1987). In order to increase the practical use of biogas, H2S must be economically removed. Several methods for H2S removal are available, including biological, physical and chemical methods. One of the most well-known methods is an iron sponge process which uses an H2S adsorption media, typically ferric oxide or hydroxide, coated onto a supporting material traditionally comprised of wood chips or wood shavings (Walsh, Ross, Smith, Harper, &

Wilkins, 1988). As the biogas ows through the iron sponge, the hydrated iron oxide reacts with H2S forming iron sulphide, thus removing H2S from the gas (Dillon, 1990). Commercial products, such as SulfaMaster, Sulfur-Rite, Media-G2 (Zicari, 2003, pp. 120) and SulfaTreat (Harman, 2011), are major iron sponge systems in which the iron hydroxides are coated onto different supporting materials including dried manure, ceramic beads, diatomaceous earth, or unspecied proprietary materials. Most of these are produced at central locations requiring expensive shipment, except SulfaTreat which can use dried digested dairy manure as the supporting material. The produced sponge can be used on-site for purication of biogas from anaerobic digesters fed with dairy manure (Harman, 2011). Another advantage of SulfaTreat is its biodegradability, which minimizes landll demand for

* Corresponding author. Tel.: 1 330 263 3855. E-mail address: li.851@osu.edu (Y. Li). 1537-5110/$ e see front matter 2012 IAgrE. Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.biosystemseng.2012.10.010

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disposal of the spent iron sponge media. Therefore, it is reasonable to envisage that other materials, especially low cost biodegradable wastes, might potentially be used for the iron sponge system, making this technology more adaptable to different locations. Garden waste (or in US terminology yard trimmings) is a desired feedstock for biogas production via anaerobic digestion because it is widely available and tipping fees are commonly associated with its disposal (Yazdani, Barlaz, Augenstein, Kayhanian, & Tchobanoglous, 2012). Spent tobacco is another abundant biomass available as a feedstock for biogas production (Kapadiya, Shilpkar, & Shah, 2010). However, to date, no studies have been conducted to investigate H2S removal performance of iron sponge using spent tobacco or garden wastes as supporting materials of the H2S adsorption media. The active element of an iron sponge is the hydrated iron oxide/hydroxide which must be maintained in a moist state to ensure that the iron will remain in hydrated form (Anerousis & Whitman, 1985). Supporting materials of the H2S adsorption media used in an iron sponge must absorb moisture and have enough surface area to support the iron oxide/hydroxide (Anerousis & Whitman, 1985). Therefore, moisture content and particle size should be optimised to improve the performance of the iron sponge media. In this study, ground garden waste, digested garden waste, and spent tobacco were used as supporting material of the iron sponge. The effects of particle size and moisture content on H2S removal were investigated to obtain optimal operating conditions for each supporting material. The H2S removal performance of iron sponges with each supporting material was compared with the commercial product SulfaMaster.

Table 1 e Characteristics of supporting materials tested. Test material Particle size

mm mm mm mm mm mm

Moisture contents tested

9%, 46%, 55% 4%, 15%, 25%, 35% 4%, 15%, 25%, 35% 4%, 15%, 25%, 35% 25%, 35%, 45% 15%, 25%, 35%

Control (SulfaMaster) 2.4 mme1.4 Garden waste 19.1e6.4 mm 19.1 mme6.4 Garden waste 4.8e2.4 mm 4.8 mme2.4 Garden waste 2.4e0.5 mm 2.4 mme0.5 Digested garden waste 2.4 mme0.5 Spent tobacco 2.4 mme0.5

effect on the H2S removal process. The reaction equation is: FeCl3 3NaOH / Fe(OH)3 3NaCl. Once the reaction completed, the solution was allowed to cool and was combined with each supporting material under constant mixing to reach an iron concentration of 12.5% (by dry weight), the same as the control media (SulfaMaster). Because NaCl has no effect on H2S absorption, washing or cleaning was not necessary. After the new supporting material was thoroughly mixed, it was placed in a drying oven at 40  C for 24e48 h. The total solids (TS) content was determined via drying the sample in an oven at 103  C for 24 h, then distilled water was added to the media to bring it to the desired moisture content. Table 1 shows the characteristics of each media tested.

2.3.

Experimental setup

2.
2.1.

Materials and methods

Supporting materials of H2S adsorption media

Fresh garden wastes collected in August 2011 were tree trimmings from the Ohio Agricultural Research and Development Center (OARDC) campus in Wooster, OH. The garden waste was oven dried at 40  C for 7 days to obtain a moisture level of less than 10%. The samples were then ground and separated using a hammer mill and respective screens. Digested garden waste was the digestate from a solid-state anaerobic digester which had been ground prior to digestion. After digestion the digested garden waste was dried and run through a series of sieves to determine particle size. The spent tobacco was a waste product used for pesticide research and was supplied by quasar energy group (Cleveland, OH, USA). The spent tobacco was neither ground nor dried prior to iron sponge formulation as it was initially at a ne particle size and had a moisture content of < 10%. Table 1 gives the particle sizes tested for each supporting material.

Four laboratory scale biogas purication columns (setup in parallel) were made using clear plastic piping. The laboratory columns had an interior diameter of 51 mm and a total height of 152 mm. The media was lled in the columns to a height of 69 mm. Rubber caps on each end created an air tight seal allowing biogas to ow through the designated ports only. The iron sponge was held in place within the columns by a wire mesh that allowed for gas ow without media loss. A 25 mm long by 6 mm diameter tube was located in the centre of the mesh to help distribute biogas into the centre of the media. A schematic diagram of the system is shown in Fig. 1. Biogas was collected in 100 l Tedlar bags from the quasar energy group digester located in Wooster, OH. The digester was fed with food processing wastes and operated under mesophilic conditions with a hydraulic retention time of 28 days. The concentration of H2S in the biogas was measured prior to entering the columns. A vacuum pump, with attached ow meter, was connected to the columns via a series of tubes. The biogas was pumped through the columns at 1.0 l min1, allowing the biogas to have a contact time with the media of 8.3 s. Experiments were conducted over an extended time with approximately 350 l of biogas passing through to ensure that H2S removal efciencies did not dramatically change during continuous operation. Biogas was sampled before and after it owed through the iron sponge, and the removal efciency was determined as the average percentage of H2S removed from the biogas of three replicates.

2.2.

Preparation of iron sponge media

2.4.

Analytical methods

The iron sponge was developed by combining iron chloride (FeCl3) with aqueous sodium hydroxide (NaOHaq) to form iron hydroxide (Fe(OH)3) and sodium chloride (NaCl). NaCl has no

The percentage of TS of iron sponge media were analysed according to the Standard Methods for the Examination of Water and Wastewater (APHA, 2005). H2S concentrations in

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152 mm 69 mm

51 mm
Fig. 1 e Schematic diagram of laboratory-scale biogas purication columns.

biogas were measured by bubbling 20 ml of gas through 20 ml of 2 N Zinc Acetate solution to remove all H2S. The solution was then analysed using the methylene blue method for sulphide determination with a HACH spectrophotometer (HACH, 2010). This method was veried using Drager Tubes and was shown to be accurate within 2%. The iron concentration in the SulfaMaster media was determined using inductively coupled plasma-mass spectrometry (ICP-MS) (Agilent 7500, Agilent Technologies, Wilmington, DE, USA). Samples for ICP-MS analysis were prepared by digestion using a microwave digester (MARSXpress, CEM Corporation, Matthews, NC, USA) programmed with a 15-min ramp-up time to 200  C and then maintained for 15 min.

2.5.

Statistical analysis

Statistical signicance was determined by analysis of variance (ANOVA) using SAS software (Version 8.1, SAS Institute Inc., Cary, NC, USA) with a threshold p-value of 0.05.

3.

Results and discussion

moisture conditions were much higher than those under high moisture conditions. Although the surface area was increased compared to the largest particle size (19.1e6.4 mm), it was still not enough to signicantly improve the absorption of water and retention of iron hydroxide at high moisture contents. Moreover, the H2S removal efciency at 25% moisture was even lower than that for the largest particle size, because the particles were clumped together by the excess unabsorbed water, which caused portions of the gas to ow around the media and partially short circuit the system. At the nest particle size (2.4e0.5 mm) for the ground garden waste, the media operated better (82% of H2S removed) at high moisture contents than it did at larger particle sizes. The most signicant improvement ( p < 0.05) in H2S removal efciency, compared to ground garden waste at 19.1e6.4 mm and 4.8e2.4 mm particle sizes, was found at a 35% moisture content. The possible reason is the ability to absorb water was further increased by the smaller particle size, while the unabsorbed water was enough to facilitate the H2S Fe(OH)3 reaction but not enough to cause clumping or iron hydroxide removal. At the lower moisture content (4%), most of the water was absorbed by the media, leaving little water on the surface to properly facilitate the conversion of H2S to Fe2S3,

3.1. Effect of particle size and moisture content on H2S removal by iron sponge
Fig. 2 shows the effects of particle size and moisture content on H2S removal using ground garden waste as a supporting material of the H2S adsorption media. At the largest particle size (19.1 mme6.4 mm), the material was not able to effectively absorb water and retain the impregnated iron hydroxide due to the low total surface area and ridged structure of the garden waste. When more water was added, some of the iron hydroxide bound to the surface of the material was removed in the water. The coarse garden waste based adsorption media operated most effectively at 4% and 15% moisture removing 84e85% of H2S, but showed signicantly decreased performances at higher moisture contents. At the medium particle size (4.8e2.4 mm), similar results were obtained. H2S removal efciencies (85e87%) under low

Fig. 2 e Effect of moisture content (m.c.) of ground garden waste on H2S removal at various particle sizes (initial H2S concentration 700e1000 ppm; 350 l of biogas passed).

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100% 90% 80% H2S Removal 70% 60% 50% 40% 30%

Control

15% m.c.

25% m.c.

35% m.c.

20%
10% 0% 69 129 205 271 Biogas Volume Passed (L) 350

Fig. 3 e Effect of moisture content of tobacco on H2S removal (initial H2S concentration 700e1000 ppm).

and causing a signicant decrease in H2S removal performance. As shown in Fig. 2, at 4.8e0.5 mm particle size and 15% moisture, the ground garden waste material had its best performance, removing 87% of the H2S which was comparable to the control (SulfaMaster).

3.2.

Effect of supporting material on H2S removal

The spent tobacco was a very poor material for binding with iron hydroxide. Once impregnated with iron hydroxide and dried, the spent tobacco crumbled and fell apart, resulting in the separation of iron hydroxide from the supporting material. When moisture was added to the media, the tobacco quickly absorbed all of the water and became saturated. This caused the media to easily clump, even at low moisture levels, which in turn led to ineffective H2S removal. The spent tobacco had substantially lower H2S removal efciency than the control at all moisture contents tested (Fig. 3), removing between 10% and 25% H2S. For biogas volumes of 129 l and 350 l passed through the system, H2S removal improved as the moisture content of the tobacco increased; however, this result was not found for biogas volumes of 69 l, 205 l, and 271 l. The digested garden waste performed at a much higher efciency compared to the tobacco based media (Fig. 4). At 25% moisture, the digested garden waste media removed 89e92% of the H2S, which was not signicantly different

( p > 0.05) from the control. Increasing moisture content to 35% and 45% had signicantly negative effects on H2S removal efciency ( p < 0.05) due to saturation and clumping. At 25% moisture, as the total volume of biogas passing through the system was increased to 350 l, the materials ability to remove H2S did not decrease despite the increased accumulation of Fe2S3. In order to gain an accurate comparison of all supporting materials, the materials and conditions with the best performance from each experiment were tested simultaneously. Fig. 5 shows the results of H2S removal by iron sponge with different media concurrently tested with the same biogas owing through all columns. The materials tested were: digested garden waste at 25% moisture; ground garden waste at a particle size 4.8 mm and 15% moisture; tobacco at 25% moisture; and SulfaMaster (control). The digested garden waste and the control material each removed up to 91% of the H2S from the biogas. Ground garden waste also performed similarly to the control, removing up to 89% H2S. There was no signicant difference between the control, ground garden waste, and digested garden waste ( p > 0.05). The spent tobacco system was not effective, removing only 12e22% of the H2S. After a total volume of 371 l of biogas passed through the system, the performance of all of the iron sponges on H2S removal had not deteriorated signicantly ( p > 0.05). Therefore, iron sponges with ground garden waste or digested garden waste can be alternatives to the control. Considering that garden waste is also a feedstock for the production of biogas, it may be more cost-effective to also use it after digestion.

3.3. H2S removal by digested garden waste system at different H2S concentrations
The digested garden waste was further tested along with the control at various H2S concentrations. The purpose of these tests was to determine the effectiveness of the iron sponge media over a wide range of initial H2S concentrations. As shown in Fig. 6, at low H2S concentrations (250e550 ppm), the control performed better than the digested garden waste based media by up to 2%. The removal efciencies of

100% 90% 80% 90% 80%

H2S Removal
H2S Removal

Control

Dig. Yd Waste

Yd Waste

Tobacco

100%

Control

25% m.c.

35% m.c.

45% m.c.

70% 60% 50% 40% 30% 20% 10% 0% 76 163 225

Biogas Volume Passed (L)

70% 60% 50% 40% 30% 20% 10% 0% 65 132 202 278 Biogas Volume Passed (L) 350

308

371

Fig. 4 e Effect of moisture content of digested garden waste on H2S removal (initial H2S concentration 700e1000 ppm).

Fig. 5 e Effect of supporting material on H2S removal (initial H2S concentration 700e1000 ppm). Supporting material tested: digested garden waste (Dig. Yd Waste), ground garden waste (Yd Waste), tobacco, and SulfaMaster (control).

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100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

Control

Dig. Yd Waste

H2S Removal

removal. Digested garden waste may be the best alternative supporting material of iron sponge for H2S removal, particularly considering that garden waste is also a feedstock for the production of biogas.

references

Initial H2S (ppm) Concentration

Fig. 6 e Effect of initial H2S concentration on H2S removal by iron sponge media with digested garden waste.

both materials signicantly increased at concentrations higher than 450 ppm H2S. At H2S concentrations of 550e1150 ppm, the digested garden waste-based media slightly outperformed the control. Statistically, there was no signicant difference between the digested garden waste and the control at either the low or high H2S concentrations ( p > 0.05). As a result, the iron sponge media with digested garden waste appears to be a good alternative to the control commercial product at a wide range of H2S concentrations (250e1150 ppm).

4.

Conclusion

The H2S removal performance of garden waste based media was affected by both particle size and moisture content. Compared to a commercial product (SulfaMaster), iron sponge with either ground garden waste or digested garden waste as the media support material had comparable H2S removal performance at their optimum particle size and/or moisture content. Meanwhile, iron sponge with the spent tobacco support material showed a poor performance for H2S

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