Sulfide oxidizing bacteria (SOB) are widely applied in industry to convert toxic H2S into elemental sulfur. Haloalkaliphilic planktonic SOB can remove sulfide from solution under anaerobic conditions (SOB are ‘charged’), and release electrons at an electrode (discharge of SOB). The effect of this electron shuttling on product formation and biomass growth is not known. Here, we study and demonstrate a continuous process in which SOB remove sulfide from solution in an anaerobic ‘uptake chamber’, and shuttle these electrons to the
anode of an electrochemical cell, in the absence of dissolved sulfide. Two experiments over 31 and 41 days were performed. At a sulfide loading rate of 1.1 mmolS/day, electricity was produced continuously (3 A/m2) without
dissolved sulfide in the anolyte. The main end product was sulfate (56% in experiment 1% and 78% in experiment 2), and 87% and 77% of the electrons in sulfide were recovered as electricity. It was found that the current density was dependent on the sulfide loading rate and not on the anode potential. Biological growth occurred, mainly at the anode as biofilm, in which the delta-proteobacterial genus Desulfurivibrio was dominating. Our results demonstrate a novel strategy to produce electricity from sulfide in an electrochemical system.@en

Removal of organic and inorganic sulfur compounds from sour gases is required because of their toxicity and atmospheric pollution. The most common are hydrogen sulfide (H₂S) and methanethiol (MT). Under oxygen-limiting conditions about 92 mol% of sulfide is oxidized to sulfur by haloalkaliphilic sulfur-oxidizing bacteria (SOB), whilst the remainder is oxidized either biologically to sulfate or chemically to thiosulfate. MT is spontaneously oxidized to dimethyl disulfide (DMDS), which was found to inhibit the oxidation of sulfide to sulfate. Hence, we assessed the effect of DMDS on product formation in a lab-scale biodesulfurization setup. DMDS was quantified using a newly, in-house developed analytical method. Subsequently, a chemical reaction mechanism was proposed for the formation of methanethiol and dimethyl trisulfide from the reaction between sulfide and DMDS. Addition of DMDS resulted in significant inhibition of sulfate formation, leading to 96 mol% of sulfur formation. In addition, a reduction in the dominating haloalkaliphilic SOB species, Thioalkalivibrio sulfidiphilus, was observed in favor of Thioalkaibacter halophilus as a more DMDS-tolerant with the 50 % inhibition coefficient at 2.37 mM DMDS.

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This study provides important new insights on how to achieve high sulfur selectivities and stable gas biodesulfurization process operation in the presence of both methanethiol and H₂S in the feed gas. On the basis of previous research, we hypothesized that a dual bioreactor lineup (with an added anaerobic bioreactor) would favor sulfur-oxidizing bacteria (SOB) that yield a higher sulfur selectivity. Therefore, the focus of the present study was to enrich thiol-resistant SOB that can withstand methanethiol, the most prevalent and toxic thiol in sulfur-containing industrial off gases. In addition, the effect of process conditions on the SOB population dynamics was investigated. The results confirmed that thiol-resistant SOB became dominant with a concomitant increase of the sulfur selectivity from 75 mol% to 90 mol% at a loading rate of 2 mM S methanethiol day⁻¹. The abundant SOB in the inoculum – Thioalkalivibrio sulfidiphilus – was first outcompeted by Alkalilimnicola ehrlichii after which Thioalkalibacter halophilus eventually became the most abundant species. Furthermore, we found that the actual electron donor in our lab-scale biodesulfurization system was polysulfide, and not the primarily supplied sulfide.

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In the biotechnological desulfurization process under haloalkaline conditions, dihydrogen sulfide (H ₂ S) is removed from sour gas and oxidized to elemental sulfur (S ₈ ) by sulfide-oxidizing bacteria. Besides S ₈ , the byproducts sulfate (SO ₄ ^2- ) and thiosulfate (S ₂ O ₃ ^2- ) are formed, which consume caustic and form a waste stream. The aim of this study was to increase selectivity toward S ₈ by a new process line-up for biological gas desulfurization, applying two bioreactors with different substrate conditions (i.e., sulfidic and microaerophilic), instead of one (i.e., microaerophilic). A 111-day continuous test, mimicking full scale operation, demonstrated that S ₈ formation was 96.6% on a molar H ₂ S supply basis; selectivity for SO ₄ ^2- and S ₂ O ₃ ^2- were 1.4 and 2.0% respectively. The selectivity for S ₈ formation in a control experiment with the conventional 1-bioreactor line-up was 75.6 mol %. At start-up, the new process line-up immediately achieved lower SO ₄ ^2- and S ₂ O ₃ ^2- formations compared to the 1-bioreactor line-up. When the microbial community adapted over time, it was observed that SO ₄ ^2- formation further decreased. In addition, chemical formation of S ₂ O ₃ ^2- was reduced due to biologically mediated removal of sulfide from the process solution in the anaerobic bioreactor. The increased selectivity for S ₈ formation will result in 90% reduction in caustic consumption and waste stream formation compared to the 1-bioreactor line-up.

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After the first commercial applications of a new biological process for the removal of hydrogen sulfide (H₂S) from low pressure biogas, the need arose to broaden the operating window to also enable the removal of organosulfur compounds from high pressure sour gases. In this study we have selected microorganisms from a full-scale biodesulfurization system that are capable of withstanding the presence of thiols. This full-scale unit has been in stable operation for more than 10 years. We investigated the microbial community by using high-throughput sequencing of 16S rRNA gene amplicons which showed that methanethiol gave a competitive advantage to bacteria belonging to the genera Thioalkalibacter (Halothiobacillaceae family) and Alkalilimnicola (Ectothiorhosdospiraceae family). The sulfide-oxidizing potential of the acclimatized population was investigated under elevated thiol loading rates (4.5-9.1 mM d^-1), consisting of a mix of methanethiol, ethanethiol, and propanethiol. With this biomass, it was possible to achieve a stable bioreactor operation at which 80% of the supplied H₂S (61 mM d^-1) was biologically oxidized to elemental sulfur. The remainder was chemically produced thiosulfate. Moreover, we found that a conventionally applied method for controlling the oxygen supply to the bioreactor, that is, by maintaining a redox potential set-point value, appeared to be ineffective in the presence of thiols. (Chemical Equation Presented).

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