Comparative analysis of microbial communities from different full-scale haloalkaline biodesulfurization systems

In biodesulfurization (BD) at haloalkaline and dO2-limited conditions, sulfide-oxidizing bacteria (SOB) effectively convert sulfide into elemental sulfur that can be used in agriculture as a fertilizer and fungicide. Here we show which bacteria are present in this biotechnological process. 16S rRNA gene amplicon sequencing of biomass from ten reactors sampled in 2018 indicated the presence of 444 bacterial Amplicon Sequence Variants (ASVs). A core microbiome represented by 30 ASVs was found in all ten reactors, with Thioalkalivibrio sulfidiphilus as the most dominant species. The majority of these ASVs are phylogenetically related to bacteria previously identified in haloalkaline BD processes and in natural haloalkaline ecosystems. The source and composition of the feed gas had a great impact on the microbial community composition followed by alkalinity, sulfate, and thiosulfate concentrations. The halophilic SOB of the genus Guyparkeria (formerly known as Halothiobacillus) and heterotrophic SOB of the genus Halomonas were identified as potential indicator organisms of sulfate and thiosulfate accumulation in the BD process. Key points: • Biodesulfurization (BD) reactors share a core microbiome • The source and composition of the feed gas affects the microbial composition in the BD reactors • Guyparkeria and Halomonas indicate high concentrations of sulfate and thiosulfate in the BD process

Insight in ethanethiol degradation kinetics at biocathodes

New technologies to remove organosulfur compounds from industrial sources should focus on the recovery of sulfur rather than incineration and sorption processes. The removal of organosulfur compounds using bio electrochemical systems might form a sustainable alternative. The aim of this study was to analyse ethanethiol degradation at biocathodes under anaerobic conditions. This was done by operating two cells at different loading rates for >360 days. We observed a stable removal efficiency of >70% with a maximum elimination capacity of 2.25 mM/d. Initially, ethanethiol was present in the effluent. However, over time, diethyl disulfide became the dominant organosulfur compound. Sulfate and thiosulfate were formed in small quantities in the biocathode. SEM imaging demonstrated the presence of crystalline structures with the typical bipyramid shape of elemental sulfur. The images also demonstrated the presence of a microbial community in a scattered biofilm on the electrode surface. The biocathodes from the continuous experiments were used in the batch experiments to gain more insight in the degradation kinetics. No electron donor (other than ethanethiol) was added to these serum flasks. The experiments confirmed that the oxidation of ethanethiol into diethyl disulfide was mostly biocatalytic as ethanethiol oxidation rates were much lower in the controls. Dynamic modeling indicated that ethanethiol nor diethyl disulfide were further degraded under these conditions. We hypothesize that the oxidation of ethanethiol forms the first important step in the degradation of this compound and that diethyl disulfide can be further degraded under electrochemically controlled conditions

Development and validation of a physiologically based kinetic model for starting up and operation of the biological gas desulfurization process under haloalkaline conditions

Hydrogen sulfide is a toxic and corrosive gas that must be removed from gaseous hydrocarbon streams prior to combustion. This paper describes a gas biodesulfurization process where sulfur-oxidizing bacteria (SOB) facilitate sulfide conversion to both sulfur and sulfate. In order to optimize the formation of sulfur, it is crucial to understand the relations between the SOB microbial composition, kinetics of biological and abiotic sulfide oxidation and the effects on the biodesulfurization process efficiency. Hence, a physiologically based kinetic model was developed for four different inocula. The resulting model can be used as a tool to evaluate biodesulfurization process performance. The model relies on a ratio of two key enzymes involved in the sulfide oxidation process, i.e., flavocytochrome c and sulfide-quinone oxidoreductase (FCC and SQR). The model was calibrated by measuring biological sulfide oxidation rates for different inocula obtained from four full-scale biodesulfurization installations fed with gases from various industries. Experimentally obtained biological sulfide oxidation rates showed dissimilarities between the tested biomasses which could be explained by assuming distinctions in the key-enzyme ratios. Hence, we introduce a new model parameter α to whereby α describes the ratio between the relative expression levels of FCC and SQR enzymes. Our experiments show that sulfur production is the highest at low α values.</p

Stoichiometry-driven heuristic feedforward control for oxygen supply in a biological gas desulfurization process

In this work, a stoichiometry-driven heuristic feedforward control strategy is proposed for controlling the oxygen supply to a biological gas desulfurization process that treats biogas, landfill, and high-pressure natural gas containing H2S and volatile organic sulfur compounds (VOSC). Traditionally, PI or PID feedback control is used when the feed gas contains H2S only. Because the oxidation–reduction potential (ORP) is mostly dominated by the dissolved sulfide concentration, the feedback controller maintains a constant sulfide concentration in the bioreactor by maintaining an ORP setpoint value through controlling the oxygen supply. However, when the feed gas also contains VOSCs, e.g., thiols, it appears from our research that controlling ORP at a fixed value does not lead to stable process performance. Hence, an alternative control strategy is proposed, which controls the O2/H2S supply ratio based on the stoichiometry of the dominant chemical reaction and experimental experience. The heuristic feedforward control strategy was validated by a fluctuating supply of H2S (26.5 to 126.5 mM S day−1) in the absence and presence of ethanethiol (0.8 to 1.16 mM S day−1). A sulfur selectivity above 95 mol%, and complete removal of H2S, was achieved at an O2/H2S supply ratio of about 0.63 mol mol−1 compared to 56 mol% when a PI/PID controller was used at a randomly varying, stepwise H2S dosing rate This work shows that fluctuations in the H2S loading rate and presence of ethanethiol in the feed gas of full-scale systems can be controlled by applying the heuristic feedforward control strategy. However, online measurements of the H2S concentration in the feed gas are required to implement the proposed strategy in full-scale installations successfully.</p

Properties of sulfur particles formed in biodesulfurization of biogas

In the biodesulfurization (BD) process under halo-alkaline conditions, toxic hydrogen sulfide is oxidized to elemental sulfur by a mixed culture of sulfide oxidizing bacteria to clean biogas. The resulting sulfur is recovered by gravitational settling and can be used as raw material in various industries. However, if the sulfur particles do not settle, it will lead to operational difficulties. In this study, we investigated the properties of sulfur formed in five industrial BD facilities. Sulfur particles from all samples showed large differences in terms of shape, size, and settleability. Both single crystals (often bipyramidal) and aggregates thereof were observed with light and scanning electron microscopy. The small, non-settled particles account for at least 13.6% of the total number of particles and consists of small individual particles with a median of 0.3 µm. This is undesirable, because those particles cannot be removed from the BD facility by gravitational settling and lead to operational interruption. The particles with good settling properties are aggregates (5–20 µm) or large single crystals (20 µm). We provide hypotheses as to how the differences in sulfur particle properties might have occurred. These findings provide a basis for understanding the relation between sulfur particle properties and formation mechanisms

Nutrient recovery and pollutant removal during renewable fuel production : Opportunities and challenges

Stimulated by the desire to achieve a Net Zero energy economy, the demand for renewable fuels is growing rapidly. The production of toxic waste streams that accompanies the transition from fossil fuels to renewable fuels is often overlooked. These waste streams include, among others, thiols and ammonia, and benzene, toluene, and xylene (BTX). When suitable treatment technologies are available, these compounds can be converted to valuable nutrients. In this opinion article, we provide an overview of expected waste streams and their characteristics. We indicate future challenges for associated waste streams, such as the lag in developing resource recovery technologies. Furthermore, we discuss unexploited opportunities to recover valuable nutrients from these waste streams

Bacteria Determine the Measured Oxidation Reduction Potential in the Biological Gas Desulfurization Process

In the biotechnological gas desulfurization process, dissolved sulfide is oxidized into predominantly elemental sulfur (S8) by sulfide oxidizing bacteria (SOB) under strict oxygen limited conditions. An online measurement of the oxidation reduction potential (ORP) is used to control the O2supply to the bioreactor to maximize the selectivity for S8formation and minimize unwanted sulfate formation. While the ORP in the bioreactor is considered to be a measure of mainly sulfide and oxygen concentrations, in practice, none of these components are detectable. In this study, we investigated the sensitivity of stored charge in SOB toward ORP. Stored charge in SOB was measured in an electrochemical cell. These SOB were harvested from the bioreactor of a pilot-scale desulfurization installation. The bioreactor, in which sulfide was not detectable, was operated at different ORP setpoints (-250 to-390 mV vs Ag/AgCl). It was found that more charge was recovered from SOB when the ORP in the aerated bioreactor was lower. These measurements were used to calibrate a model to describe the ORP based on charge storage in SOB, which showed that S8formation increases and sulfate formation decreases when SOB contain more charge. This can be used to further optimize the biotechnological desulfurization process

Bacteria as an Electron Shuttle for Sulfide Oxidation

Biological desulfurization under haloalkaliphilic conditions is a widely applied process, in which haloalkalophilic sulfide-oxidizing bacteria (SOB) oxidize dissolved sulfide with oxygen as the final electron acceptor. We show that these SOB can shuttle electrons from sulfide to an electrode, producing electricity. Reactor solutions from two different biodesulfurization installations were used, containing different SOB communities; 0.2 mM sulfide was added to the reactor solutions with SOB in absence of oxygen, and sulfide was removed from the solution. Subsequently, the reactor solutions with SOB, and the centrifuged reactor solutions without SOB, were transferred to an electrochemical cell, where they were contacted with an anode. Charge recovery was studied at different anode potentials. At an anode potential of +0.1 V versus Ag/AgCl, average current densities of 0.48 and 0.24 A/m2 were measured for the two reactor solutions with SOB. Current was negligible for reactor solutions without SOB. We postulate that these differences in current are related to differences in microbial community composition. Potential mechanisms for charge storage in SOB are proposed. The ability of SOB to shuttle electrons from sulfide to an electrode offers new opportunities for developing a more sustainable desulfurization process.</p

Bacteria as an Electron Shuttle for Sulfide Oxidation

Biological desulfurization under haloalkaliphilic conditions is a widely applied process, in which haloalkalophilic sulfide-oxidizing bacteria (SOB) oxidize dissolved sulfide with oxygen as the final electron acceptor. We show that these SOB can shuttle electrons from sulfide to an electrode, producing electricity. Reactor solutions from two different biodesulfurization installations were used, containing different SOB communities; 0.2 mM sulfide was added to the reactor solutions with SOB in absence of oxygen, and sulfide was removed from the solution. Subsequently, the reactor solutions with SOB, and the centrifuged reactor solutions without SOB, were transferred to an electrochemical cell, where they were contacted with an anode. Charge recovery was studied at different anode potentials. At an anode potential of +0.1 V versus Ag/AgCl, average current densities of 0.48 and 0.24 A/m2 were measured for the two reactor solutions with SOB. Current was negligible for reactor solutions without SOB. We postulate that these differences in current are related to differences in microbial community composition. Potential mechanisms for charge storage in SOB are proposed. The ability of SOB to shuttle electrons from sulfide to an electrode offers new opportunities for developing a more sustainable desulfurization process.</p

Effect of methanethiol on process performance, selectivity and diversity of sulfur-oxidizing bacteria in a dual bioreactor gas biodesulfurization system

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.</p