Sulfide Removal Research Articles

Effect of glucose addition on the morphology and activity of ZnO supported on mesoporous zeolite SBA-15 for the removal of hydrogen sulfide

Zinc oxide with its high equilibrium constant for sulfidation, can be utilized to purify H2S-containing gases, but its low kinetics at room temperature limits its sulfur loading capacity. This study use glucose as an organic additive and carbon source to prepare carbon doped ZnO adsorbents with different ZnO loadings (5-20wt%) through initial wet impregnation. It was observed that the sulfur capacity of 15wt% Zn/SBA-15-G (10.9mg/g) was approximately 1.65 times higher than that of 15wt% Zn/SBA-15 (6.6mg/g). This improvement was attributed to the use of glucose, which led to better ZnO dispersion, a narrower distribution of ZnO particle size, and the formation of C-O-Zn bonds that increased the number of hydroxyl groups on the ZnO surface. DFT calculations also indicated that carbon doping could lower the activation energy of the reaction between ZnO and H2S and shorten the reaction pathway. Consequently, the prepared ZnO adsorbent demonstrated enhanced desulfurization efficiency at room temperature. Furthermore, regeneration experiments conducted on the desulfurizer after use revealed that achieving complete regeneration is a challenge.

A Review of the Thiopaq Process for Biological Hydrogen Sulfide Removal from Sour Gases

A Review of the Thiopaq Process for Biological Hydrogen Sulfide Removal from Sour Gases

Electrochemical and bioelectrochemical sulphide removal: A review

AbstractThe increased demand for energy worldwide and the focus on the green shift have raised interest in renewable energy sources such as biogas. During biogas production, sulphide (H2S, HS− and S2−) is generated as a byproduct. Due to its corrosive, toxic, odorous, and inhibitory nature, sulphide is problematic in various industrial processes. Therefore, several techniques have been developed to remove sulphide from liquid and gaseous streams, including chemical absorption, chemical dosing, bioscrubbers, and biological oxidation. This review aims to elucidate electrochemical and bioelectrochemical sulphide removal methods, which are gaining increasing interest as possible supplements to existing technologies. In these systems, the sulphide oxidation rate is affected by the reactor design and operational parameters, including electrode materials, anodic potential, pH, temperature and conductivity. Anodic and bioanodic materials are highlighted here, focusing on recent material developments and surface modification techniques. Moreover, the review focuses on sulphide generation and inhibition in biogas production processes and introduces the prospect of removing sulphide and producing methane in one single bioelectrochemical reactor. This could introduce BESs for combined biogas upgrading and cleaning, thereby increasing the methane content and removing pollutants such as sulphide and ammonia in one unit.

Thermally Stable High-Entropy Layered Double Hydroxides for Advanced Catalysis.

Layered double hydroxides (LDHs), especially high-entropy LDHs (HE-LDHs), have gained increasing attention. However, HE-LDHs often possess poor thermal stability, restricting their applications in thermo-catalysis. Herein, a novel complexing nucleation method is proposed for engineering HE-LDHs with enhanced thermal stability. This approach precisely controls the nucleation of metal ions with different solubility products, achieving homogeneous nucleation and effectively mitigating phase segregation and transformation at elevated temperatures. The prepared HE-LDH sample demonstrated exceptional thermal stability at temperatures up to 300°C, outperforming all previously reported LDHs. Importantly, these HE-LDHs preserve both Lewis and Brønsted acidic sites, enabling the 100% removal of aromatic sulfides and alkaline nitrogen compounds from fuel oils in thermo-catalytic oxidation reactions. Experimental and characterization findings reveal that the metal-hydroxide bonds in the prepared HE-LDHs are strengthened by associated hydroxyl groups, inducing negative thermal expansion and augmenting the presence of acidic sites, thereby ensuring structural stability and enhancing catalytic activity. This study not only proposes a strategy for engineering HE-LDHs with remarkable thermal stability but also highlights potential applications of LDHs in thermo-catalysis.

Enhanced Hydrolysis of Carbonyl Sulfide in Coking Oven Gas Utilizing an Efficient Ca-Ba-γ-Al2O3 Catalyst

China possesses a substantial capacity for coke production, resulting in the annual generation of over 100 billion standard cubic meters of the by-product coke oven gas. The comprehensive utilization of this gas has emerged as a matter of significant concern within the coking industry. The removal of carbonyl sulfide (COS) from coke oven gas is crucial for enhancing gas quality, mitigating equipment corrosion, minimizing environmental pollution, elevating the quality of recovered products, and fostering the production of high-quality steel. A novel Ca-Ba-γ-Al2O3 catalyst has been devised, employing γ-Al2O3 as the catalyst matrix and integrating calcium hydroxide (Ca(OH)2) alongside barium hydroxide octahydrate (Ba(OH)2·8H2O) as the alkaline activating components. The impact of various factors, including reaction temperature, humidity, and the number of activating components loaded, on the hydrolysis efficiency of COS has been meticulously investigated. Furthermore, the catalytic reaction mechanism has been elucidated utilizing advanced characterization techniques such as X-ray diffraction (XRD) and Brunauer–Emmett–Teller (BET) analysis. The outcomes of this research reveal that, under optimal conditions of a reaction temperature of 55 °C and a humidity of 56%, the Ca-Ba-γ-Al2O3 catalyst achieves a remarkable COS hydrolysis efficiency of 95.22%.

Enhancement and sulfur poisoning mechanism of Ce doped ZrO2 catalyst in COS hydrolysis at low-temperature

In order to achieve efficient and longer-lifespan removal of carbonyl sulfide (COS), a high-performance catalyst for hydrolysis is needed urgently. In this study, Ce doped ZrO2 oxides are used to remove COS with or without H2O. The results showed that the doping of Ce significantly improves the removal of COS by ZrO2 and obtains a sulfur capacity of 155.4 mgS/g at 70 °C, but there is still accompanied by sulfur poisoning. The characterization reveals that CeO2 has a cubic phase, ZrO2 has a mixed phase of tetragonal and monoclinic, and Ce-doped Zr with different ratio of Ce/Zr forms a Ce-Zr solid solution. Ce and Ce-Zr oxides have Ce3+/Ce4+ pairs, adsorbed oxygen species and surface oxygen vacancies, while ZrO2 has adsorbed oxygen and surface oxygen vacancies, the presence of which can promote the dissociation of H2O and surface adsorption of COS. ZrO2 has abundant medium-strong basicity while CeO2 has abundant weak and strong basicity, and different proportions of Ce/Zr adjust the surface basic strength, basic amount and surface redox property of Ce-Zr solid solution, which changes the adsorption and hydrolysis of COS and H2O and related oxidation reactions on Ce and Zr, thereby changing the sulfur poisoning. Ce has abundant –OH groups, which can rapidly adsorb COS, leading to hydrolysis and direct oxidation of COS in the absence of H2O, while the OH groups on ZrO2 promote the hydrolysis of COS to H2S. Although suitable Ce-doped ZrO2 improves the removal efficiency of COS, it still inevitably leads to the sulfur poisoning, but the presence of Zr could change the sulfation degree of CeO2 and the Claus reaction.

Integration of Moving Bed Biofilm Reactor (MBBR) and algal PhotoBioReactors (aPBR) for achieving carbon neutrality in wastewater treatment

Carbon neutrality is a primary goal for wastewater treatment plants (WWTPs), as they are responsible for significant greenhouse gas (GHG) emissions as well as unpleasant odour emissions.The paper shows a new modular biotechnology that enables simultaneous treatment of gaseous emissions and biofixation of CO2.A comparative assessment of system performances in removing target pollutants (toluene, p-xylene and hydrogen sulphide) was implemented. Results showed that the highest removal efficiency (RE) was recorded for the toluene, equaling 99.9 ± 0.1 %, for an inlet load (IL) of 9.91 ± 3.44 g m−3 d−1. During the experimental tests regarding hydrogen sulphide removal, the system recorded the highest CO2 assimilation, equal to −3.03 ± 0.93 g m−3 d−1. However, this assimilation rate did not correspond to the maximum volumetric biomass productivity (MVBP), equal to 1.3 g L−1 d−1, recorded with toluene treatment, with a maximum lipid productivity (MLP) of 450 mg L−1 d−1.The results demonstrated the complete adaptability of the investigated system, which can help to fill the gaps in the current technological landscape, providing an innovative biotechnology that can be directly implemented and environmentally sustainable.

Synthesis of Copper-Doped Metal Nanoferrites for Efficient Removal of Pharmaceutical Wastewater Pollutants in Membrane Bioreactor System

Pharmaceuticals present in the aquatic environment can poison aquatic species and humans through drinking water and cause harmful bacteria to become resistant. The role of transition metal doped metal nanoferrites for the enhanced efficiency of degradation process is widely achieved. In this work, copper doped magnesium ferrite (Cu-MgFe2O4) and copper doped zinc ferrite (Cu-ZnFe2O4) nanoparticles were synthesized using a sol-gel method. X-ray diffraction (XRD) analysis confirmed the formation of the spinel structure for both samples, with crystal sizes of 16.72 nm and 59.05 nm, respectively. The magnetic properties of the samples were studied using a vibrating sample magnetometer (VSM), which revealed that the addition of Cu2+ ions has a significant impact on the magnetic properties of the nanoparticles. The saturation magnetisation (Ms), retentivity (Mr) and coercivity value (Hc) for the Cu-MgFe2O4 sample were found to be 0.18453 emu, 39.584 × 10-3 emu and 139.61 Oe, respectively, while for the Cu-ZnFe2O4 sample, the values were 0.21271 emu, 71.022 × 10-3 emu and 285.91 Oe, respectively. The impact of copper doped nanoferrites on pollutant removal from pharmaceutical wastewater using the membrane Bioreactor (MBR) system has also been accomplished. The results demonstrated the effectiveness of ferrites in reducing concentrations of heavy metals, including lead and cadmium, within acceptable ranges for inland surface water and public sewers. Furthermore, the MBR system with ferrites exhibited efficient removal of fluoride, sulphide and radioactivity, ensuring compliance with the specified standards. Although the study exhibited the potential of ferrites in pollutants removal, further optimization is necessary to achieve complete compliance with water quality standards.

TECHNOLOGICAL SOLUTION FOR COMBATING HYDROGEN SULFIDE AT THE FIELD

One of the urgent problems in the production of hydrogen sulfide-containing oils is the problem of increasing the efficiency of hydrogen sulfide removal. Optimization of costs associated with the production, transportation and preparation of oil is very important at the present time. In order to reduce the costs of oil preparation, the use of a differentiated approach to solving the problem of its purification from hydrogen sulfide at the Kashagan field depends on the volumes of oil preparation, the mass fraction of hydrogen sulfide in the oil, the presence of gas near the high-sulfur oil preparation unit (UPVSN) that does not contain hydrogen sulfide, the presence of a gas collection system and the possibility of transporting increased volumes of hydrogen sulfide-containing gas to the sulfur purification unit. Taking these factors into account, it is necessary to identify the maximum values ​​​​of the volume fractions of methane, ethane, nitrogen and carbon dioxide in the composition of the stripping gas, at which the mass of oil will be preserved, as well as the conditions under which it will be purified from hydrogen sulfide in the conditions of the Kashagan field. Studies have shown that with an increase in the oil heating temperature and a decrease in the pressure in the desorption column, the maximum total volume fraction of methane and nitrogen in the mixture in the composition of the stripping gas decreases. A decrease in the mass fraction of hydrogen sulfide in oil below 100 ppm and maintaining the mass yield of oil depending on the proportion of these components in the composition of the stripping gas is possible if the oil temperature and pressure in the column are optimized. An increase in the total volume fraction of methane and nitrogen in the composition of the stripping gas leads to a decrease in its required consumption to achieve a certain efficiency of oil purification from hydrogen sulfide at specified operating parameters of the column.

Atomically Permeated MoP‐WOx Core‐Shell Catalysts for Efficient and Selective Oxidation of Thiophenic Sulfides in Fuels via Direct Electron Transfer Mechanism

AbstractHeterogeneous interfaces designed rationally in catalysts can induce geometrical, compositional, and electronic effects that can be applied to modulate catalytically active sites and consequently accelerate reaction kinetics. Here, a core‐shell heterostructure catalyst consisting of crystalline molybdenum phosphide (MoP) cores and amorphous tungsten oxide (WOx) shells on porous carbon nanosheets (PCN) is developed for oxidative desulfurization (ODS) of fuels. The strongly coupled core‐shell heterogeneous interface triggers a distinctive atomic permeation effect that induces substantial electron transfer from MoP to WOx and subsequent generation of electron‐rich W sites, consequently optimizing the adsorption of intermediates and substrates. The resulting catalyst (WOx@MoP/PCN) demonstrates a turnover frequency as high as 768.1 h−1 for ODS at 60 °C, exceeding that of almost all the state‐of‐the‐art ODS catalysts by 1–2 orders of magnitude. Moreover, a novel surface oxidation pathway based on direct electron transfer is identified in the WOx@MoP/PCN‐H2O2 system, which bypasses the formation of reactive oxygen species, consequently endowing the system with a moderate redox potential. Thus, WOx@MoP/PCN exhibits unprecedented selectivity, achieving 100% removal of thiophenic sulfides from real diesel with minimal consumption of oxidant.

Domestic wastewater treatment towards reuse by “self-supplied” microbial electrochemical system assisted UV/H2O2 process

Domestic wastewater is a potential source of water for non-potable reuse that may help address the global water, energy, and resource challenges. Herein, a “self-supplied” process through integrating microbial electrochemical system (MES) with UV/H2O2 was developed and investigated for wastewater treatment. H2O2 was “self-supplied” from MES while the MES catholyte was “self-supplied” from the final effluent of UV/H2O2. It was found that the MES accomplished > 80 % degradation of chemical oxygen demand (COD) through bioanode degradation, and produced 18 - 20 mg L−1 H2O2 via oxygen reduction reaction in the gas diffusion cathode. The MES effluent was further treated by the UV/H2O2 process, which achieved the complete removal of recalcitrant diclofenac and > 6 log inactivation of Escherichia coli. The enhanced treatment performance of UV/H2O2 was demonstrated via a comparison with the control experiments (UV or H2O2 treatment) and benefited from ·OH generation and sulfide removal. When treating the actual wastewater, the proposed system exhibited consistent treatment performance for the organic compounds and recalcitrant contaminants, and the quality of the treated water would meet the non-potable water reuse guidelines. The results of this study encourage the further exploration of emerging contaminant removal, system coordination, and use of renewable energy by the cooperation between MES and UV/H2O2.

Electrochemical production of HO2- and O2 for sulfide removal from sewage

In this study, a comparative analysis of two electrochemical methods for sulfide control in sewer networks was performed for the first time. In addition, the mechanism of sulfide control by HO2- was elucidated, and an analysis of the device operation and electrolyte selection was performed. The two-electron oxygen reduction reaction (2e--ORR) using untreated gas diffusion electrode (GDE) was superior to the hydrogen evolution reaction (HER) using stainless-steel mesh in terms of cell voltage, product formation, and sulfide suppression. The GDE maintained a stable HO₂⁻ production capacity, achieving a concentration of 4566.6 ± 173.3 mg L⁻¹ with a current efficiency (CE) of 84.13 ± 3.5 %. During the electrolysis period, a stable dissolved oxygen (DO) level in sewage was consistently observed due to continuous in-situ oxygen production in anode. HO2- exhibited a notable increase in sewage pH (10.20 ± 0.01), effectively inhibiting the release of 99.93 % of sulfides. Moreover, the combined treatment of HO2- and DO significantly surpassed that of individual treatments. Seawater treated with cation exchange resin (CER) emerged as the most promising alternative to freshwater as the electrolyte. Overall, this study demonstrates that in-situ generation of HO₂⁻ and oxygen is a more effective strategy for sulfide control in sewer systems.

The Efficiency of Chemical and Electrochemical Coagulation Methods for Pretreatment of Wastewater from Underground Coal Gasification

This article compares chemical coagulation with electrocoagulation, two popular methods for the primary treatment of wastewater generated in the process of underground coal gasification (UCG). The primary aim was to determine which method is more effective in the removal of cyanide and sulphide ions, metals and metalloids, as well as organic compounds. In both cases, experiments were conducted in batch 1 dm3 reactors and using iron ions. Four types of coagulants were tested during the chemical coagulation study: FeCl2, FeSO4, Fe2(SO4)3, and FeCl3. In the electrocoagulation experiments, pure iron Armco steel was used to manufacture the sacrificial iron anode. Both processes were tested under a wide range of operating conditions (pH, time, Fe dose) to determine their maximum efficiency for treating UCG wastewater. It was found that, through electrocoagulation, a dose as low as 60 mg Fe/dm3 leads to >60% cyanide reduction and >98% sulphide removal efficiency, while for chemical coagulation, even a dose of 307 mg Fe/dm3 did not achieve more than 24% cyanide ion removal. Moreover, industrial chemical coagulants, especially when used in very high doses, can be a substantial source of cross-contamination with trace elements.

New two fold interpenetrating 3D polyoxovanadate-based metal–organic framework as bifunctional catalyst for the removal of 2-chloroethyl ethyl sulfide and phenolic compounds

New two fold interpenetrating 3D polyoxovanadate-based metal–organic framework as bifunctional catalyst for the removal of 2-chloroethyl ethyl sulfide and phenolic compounds

Optimum Tuning for the High-efficiency Removal of Malodorous Gas Containing Hydrogen Sulphide Using Biological Treatment

Hydrogen sulfide, as the main pollutant causing stench, has always been one of the main problems in environmental protection. In order to promote the practical application, a pilot study was carried out in this work on the biological treatment of hydrogen sulfide malodorous gas by the combined process of biological drip filtration on the basis of our previous laboratory-scale experiments. After enlarging the reactor in pilot experiment, various factors affecting the deodorization efficiency are compared in pilot scale and laboratory scale, and the optimum pilot condition are obtained. Furthermore, the mechanism of biological deodorization is analyzed. Based on the results of the comparison between the previous laboratory-scale and the pilot-scale of this work, possible bottlenecks and challenges of biological deodorization technology from pilot to industrial application are discussed. The technical approach proposed in this work provides an economical and efficient feasible scheme for biological deodorization in the industrial practice.

Insights into response of seagrass (Zostera marina) to sulfide exposure at morphological, physiochemical and molecular levels in context of coastal eutrophication and warming.

Sulfide in sediment porewaters, is toxic to rooted macrophytes in both marine and freshwater environments. Current research on sulfide stress in seagrasses primarily focuses on morphological and physiological aspects, with little known about the molecular response and resistance mechanisms. This study first investigated the damage caused by sulfide to eelgrass (Zostera marina L.) using transcriptomic, metabolomic, and other physiological and biochemical indicators and explored the potential resistance of eelgrass at molecular level through laboratory simulated and in-situ sulfide stress experiments. Comprehensive results showed that sulfide stress severely inhibited the growth, photosynthesis, and antioxidant enzyme activities of eelgrass. Importantly, transcriptome analysis revealed significant activation of pathways related to carbohydrate and sulfur metabolism. This activation served a dual purpose: providing an energy source for eelgrass stress response and achieving detoxification through accelerated sulfur metabolism-a potential resistance mechanism. The toxicity of sulfide increased with rising temperature as evidenced by a decrease in EC50. Results from recovery experiments indicated that when Fv/Fm reduced to about 0 under sulfide stress, the growth and photosynthesis of eelgrass recovered to normal level after timely removal of sulfide. However, prolonged exposure to sulfide resulted in failure to recover, leading ultimately to plant death. This study not only enhances our understanding of the molecular-level impacts of sulfide on seagrasses but also provides guidance for the management and ecological restoration of seagrass meadows under sulfide stress.

Anaerobic hybrid-photobioreactor using phototrophic purple and green bacteria treating piggery wastewater with sulfur recovery and biogas polishing

An anaerobic hybrid-photobioreactor (AnHPBR) was performed for biogas polishing during piggery wastewater treatment. AnHPBR was exposed to high (4.45 × 105 lx) and low (450 lx) light intensities for growing purple and green sulfur phototrophs separately in each chamber of AnHBBR for soluble sulfide removals. Four phases of hydraulic retention times (HRT, h): 24, 48, 96, and 96 (with added sulfate) of piggery wastewater were operated consecutively for 351 days. Metagenomic analysis of the AnHPBR biomass confirmed that purple and green bacteria were 63–82 %, of which the species varied by HRT and sulfate loadings. In sum, 96 h HRT for AnHPBR presented the highest efficacies in removals of COD (92 %), sulfate (73 %), and sulfide (59 %). Its biogas contained high methane (75 %) and low hydrogen sulfide (0.3 %). Additionally, AnHPBR produced outflow biosolids with a stable sulfur content of 1.88 %.

Seawater barium and sulfide removal improved marine habitability for the Cambrian Explosion of early animals.

An increase in atmospheric pO2 has been proposed as a trigger for the Cambrian Explosion at ∼539-514Ma but the mechanistic linkage remains unclear. To gain insights into marine habitability for the Cambrian Explosion, we analysed excess Ba contents (Baexcess) and isotope compositions (δ138Baexcess) of ∼521-Myr-old metalliferous black shales in South China. The δ138Baexcess values vary within a large range and show a negative logarithmic correlation with Baexcess, suggesting a major (>99%) drawdown of oceanic Ba inventory via barite precipitation. Spatial variations in Baexcess and δ138Baexcess indicate that Ba removal was driven by sulfate availability that was ultimately derived from the upwelling of deep seawaters. Global oceanic oxygenation across the Ediacaran-Cambrian transition may have increased the sulfate reservoir via oxidation of sulfide and concurrently decreased the Ba reservoir by barite precipitation. The removal of both H2S and Ba that are deleterious to animals could have improved marine habitability for early animals.

Process and kinetics of ammonium sulfide removal of zinc, nickel and cobalt from manganous sulfate electrolyte

In producing electrolytic manganese and manganese-based lithium batteries, Manganous sulfate solution serves as a crucial intermediate material. During the preparation of manganese sulfate solution by acid leaching, the removal of impurities such as zinc, nickel, and cobalt ions by sulfide precipitation is essential for obtaining high-quality metallic manganese and high-purity manganese sulfate. The results show that when the temperature is 45 °C, the pH is 5.60, the ammonium sulfide dosage is 40 %, the time is 5 min, and the rotation speed is 650 rpm, the sulfidation rates of zinc, nickel and cobalt are 99.07 %, 89.30 %, and 87.70 % respectively. At this time, the loss rate of manganese in the solution after sulfide impurity removal is 11.45 %, and the manganese-impurity ratio is 80.00. Response surface methodology analysis revealed that temperature, pH, and ammonium sulfide concentration significantly affected the manganese loss rate. After process optimization, at a temperature of 32.70 °C, a pH of 5.20, and an ammonium sulfide concentration of 32.73 %, the manganese loss rate decreased to 6.05 %, while the removal rates of Ni, Co, and Zn were 75.35 %, 60.80 %, and 99.51 %, respectively. In the Manganous sulfate electrolyte with or without ammonium sulfate, the sulfide precipitation processes of zinc, nickel and cobalt ion are all first-order reactions, and the reaction order is zinc > nickel > cobalt. More importantly, the density functional theory (DFT) calculation results also confirmed the formation sequence of zinc sulfide > nickel sulfide > cobaltous sulfide, which supported the experimental results well. This study will lay the foundation for process optimization and mechanism elucidation of impurity ions in ammonium sulfate electrolyte precipitated by ammonium sulfate.

Novel multineedle-to-cylinder plasma coupled with bimetallic catalysts for efficient removal of sulfides and ammonia in odor gases

Dielectric barrier discharge (DBD) plasma is a promising technology for treating odor gases. This study developed an innovative multineedle-to-cylinder (MC) configuration DBD plasma reactor and investigated its synergistic effect with bimetallic catalysts. The results demonstrated that MC-DBD plasma achieved complete elimination of ammonia and organic sulfides, while the removal efficiencies of inorganic H2S and CS2 reached 44.0 % and 53.0 % respectively. Compared with conventional plasma, the specific energy input (SEI) of MC-DBD was significantly reduced to 4.44 J/L. Furthermore, with the incorporation of Mn-Ce/ZSM-5 catalyst, optimal removal efficiencies of H2S and CS2 were significantly improved to 82.6 % and 90.7 %, and the SEI was reduced by 18 %. The electrical performance revealed that the low energy consumption was mainly attributed to stable fast-pulse micro-discharge channels and significantly enhanced inhomogeneous electric fields achieved by the filament discharge mode. Catalyst characterization (X-ray photoelectron spectroscopy and O2-temperature programming desorption) confirmed that surface catalytic reaction mainly follows the Mars-van Krevelen mechanism, where increased lattice oxygen content and the electron transfer between Mn and Ce play crucial roles in enhancing malodor degradation performance. This work proposes an efficient solution for degrading mixed malodors and provides an experimental and theoretical basis for optimizing plasma structure as well as researching treatment of mixed pollutants.