Conversion Of SO2 Research Articles

Observing the SO2 and Sulfate Aerosol Plumes From the 2022 Hunga Eruption With the Infrared Atmospheric Sounding Interferometer (IASI)

AbstractThe Hunga volcano violently erupted on 15 January 2022, producing the largest perturbation of the stratospheric aerosol layer since Pinatubo 1991, despite the initially estimated modest injection of SO2. This study presents novel SO2 and sulfate aerosol (SA) co‐retrievals from the Infrared Atmospheric Sounding Interferometer, and uses them to quantify the initial progression of the Hunga plume. These observations are consistent with rapid conversion of SO2 (e‐folding time: 17.1 ± 4.3 days) to SA, with an injected burden of >1.0 Tg SO2. This points at larger SO2 injections than previously thought. A long‐lasting SA plume was observed, with two separate build‐up phases, and with a meridional dispersion of marked anomalies from the tropics to the higher southern hemispheric latitudes. A limited (∼20%) SA removal was observed after 1‐year dispersion. The total injected SA mass burden was estimated at 1.6 ± 0.5 Tg in the total atmospheric column, with a build‐up e‐folding time of about 2 months.

Physico-chemical Characteristics and Evolution of NR-PM1 in the Suburban Environment of Seoul

In South Korea, particulate matter (PM) is generated from various emission sources, including domestic air pollutants and long-range transport. Effective air quality policies require an understanding of the chemical characteristics of PM and differences between urban and non-urban areas (suburban and background areas). We analyzed the chemical characteristics of non-refractory submicron aerosols (NR-PM1) in Yongin City, a suburban area southeast of Seoul, using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) in spring/summer. In spring/summer, photochemical reactions resulted in the highest proportion of Organic Aerosol (OA) among NR-PM1. Positive matrix factorization (PMF) revealed four OA sources: Primary OA and Secondary OA (Oxidized Primary OA (OPOA), Less Oxidized Oxygenated OA (LO-OOA), and More Oxidized Oxygenated OA (MO-OOA)). OPOA was formed from the oxidation of emissions from biomass burning and coal combustion; LO-OOA and MO-OOA were correlated with inorganic compounds and influenced by long-range transport. The majority of OA was SOA (82%). High temperatures and humidity accelerated the conversion of SO2 to SO42−, resulting in the proportion of SO42−, second only to OA. Despite favorable conditions for nitrate formation in ammonium-rich conditions, the proportion of NO3− was relatively low due to the decomposition of NH4NO3 into gaseous NH3 and HNO3 at high temperatures. This indicated that while ammonium-rich conditions are conducive to NH4NO3 production, elevated temperatures lead to its decomposition, resulting in lower NO3− concentrations in spring/summer. In the case study, for the case associated with long-range transport, the PM concentration increased due to inorganic compounds such as NO3− and SO42−. Conversely, in cases of domestic air stagnation, the concentration of PM increased primarily due to the presence of OA. These findings provide crucial insights for air quality management in suburban areas and can guide policies to reduce PM levels in spring and summer.

SO3 removal by submicron absorbents synthesized via inhibition method: The product layer grows like parallel peaks

Injecting calcium hydroxide powder into the flue gas is an effective strategy for SO3 removal. However, commercial calcium hydroxide has several disadvantages, including large particle size, low efficiency, and unsuitability for excessive grinding. In this work, sub-micron calcium hydroxide was synthesized by an inhibition method and its performance for SO3 removal from flue gas was investigated on a pilot-scale platform (120 Nm3/h). When the concentration of sodium alginate solution was 100 mg/L, the average particle size of calcium hydroxide decreased from 13.66 µm to 0.84 µm, which improved the SO3 removal (92.1 %) and conversion of the absorbent. The results of the fixed-bed experiments indicate that the absorption kinetics of the reaction is consistent with the Bangham model. In addition, density functional theory verifies that calcium hydroxide captures SO3 by chemisorption. The AFM image shows that the calcium sulfate whiskers produced during the reaction grow like parallel peaks on the adsorbent surface. The calculations suggest that the driving force for SO3 adsorption originates from Ca-p orbital (Ca(OH)2) and O-s orbital (SO3) hybridization. This study complements the island growth mechanism for gas-solid two-phase reactions and provides an effective method for removing SO3 from flue gas in coal-fired power plants. In addition, it will provide an important reference for the development of submicron adsorbents.

Defect-engineered indium-organic framework displays the higher CO2 adsorption and more excellent catalytic performance on the cycloaddition of CO2 with epoxides under mild conditions.

In order to achieve the high adsorption and catalytic performance of CO2, the direct self-assembly of robust defect-engineered MOFs is a scarcely reported and challenging proposition. Herein, a highly robust nanoporous indium(III)-organic framework of {[In2(CPPDA)(H2O)3](NO3)·2DMF·3H2O}n (NUC-107) consisting of two kinds of inorganic units of chain-shaped [In(COO)2(H2O)]n and watery binuclear [In2(COO)4(H2O)8] was generated by regulating the growth environment. It is worth mentioning that [In2(COO)4(H2O)8] is very rare in terms of its richer associated water molecules, implying that defect-enriched metal ions in the activated host framework can serve as strong Lewis acid. Compared to reported skeleton of [In4(CPPDA)2(μ3-OH)2(DMF)(H2O)2]n (NUC-66) with tetranuclear clusters of [In4(μ3-OH)2(COO)10(DMF)(H2O)2] as nodes, the void volume of NUC-107 (50.7%) is slightly lower than the one of NUC-66 (52.8%). However, each In3+ ion in NUC-107 has an average of 1.5 coordinated small molecules (H2O), which far exceeds the average of 0.75 in NUC-66 (H2O and DMF). After thermal activation, NUC-107a characterizes the merits of unsaturated In3+ sites, free pyridine moieties, solvent-free nanochannels (10.2 × 15.7 Å2). Adsorption tests prove that the host framework of NUC-107a has a higher CO2 adsorption (113.2 cm3/g at 273K and 64.8 cm3/g at 298K) than NUC-66 (91.2 cm3/g at 273K and 53.0 cm3/g at 298K). Catalytic experiments confirmed that activated NUC-107a with the aid of n-Bu4NBr was capable of efficiently catalyzing the cycloaddition of CO2 with epoxides into corresponding cyclic carbonates under the mild conditions. Under the similar conditions of 0.10mol% MOFs, 0.5mol% n-Bu4NBr, 0.5 MP CO2, 60°C and 3h, compared with NUC-66a, the conversion of SO to SC catalyzed by NUC-107a increased by 21%. Hence, this work offers a valuable perspective that the in situ creation of robust defect-engineered MOFs can be realized by regulating the growth environment.

Role of Ammonia in Aerosol Liquid Water, pH, and Secondary Inorganic Aerosols Formation at an Ammonia-rich City in Changzhou

Ammonia （NH3） is an important alkaline reactive nitrogen, which, as a precursor of fine particulate matter, raises public health issues. In this study, online NH3, SO2, NO2, PM2.5, and its water-soluble inorganic ions were detected to deduce the influence of NH3 on aerosol liquid water content （AWC） and aerosol pH, including the formation of water-soluble secondary ions in PM2.5 in winter in Changzhou, an ammonia-rich city in the Yangtze River Delta area in winter. The results showed that NH4+ mainly existed in the form of NH4NO3 and （NH4）2SO4, and the remaining NH4+ existed as NH4Cl. Owing to the NH3-NH4+ buffer system, the aerosol pH values were found at 4.2 ± 0.4, which was positively correlated with the NH3 content. The aerosol pH value variation narrowed with the increase in PM2.5 concentration and tended to be between 4 to 5. AWC increased exponentially with the increase in humidity and SNA content, among which NH4NO3, （NH4）2SO4, and NH4Cl contributed 58.5%, 18.4%, and 8.3%, respectively, due to their hygroscopicity. Aerosol pH, AWC, and NH3-NH4+ conversion promoted the gas-to-particle conversion of SO2 and NO2. In Changzhou, rich NH3-NH4+ were found to maintain relatively high pH values, push up AWC, and promote the heterogeneous reaction of SO2, whereas NO3- generation was dominated by a homogeneous reaction, which was accelerated by NH3. According to the simulation results, relatively noticeable changes in aerosol pH and AWC could be found by the reduction of up to 30% of NH3.

Electric Field Generated at the Millisecond Pulse-Polarized Interface Facilitates the Electrolytic Conversion of SO2 into H2S.

Interfacial electric field holds significant importance in determining both the polar molecular configuration and surface coverage during electrocatalysis. This study introduces a methodology leveraging the varying electric dipole moment of SO2 under distinct interfacial electric field strengths to enhance the selectivity of the SO2 electroreduction process. This approach presented the first attempt to utilize pulsed voltage application to the Au/PTFE membrane electrode for the control of the molecular configuration and coverage of SO2 on the electrode surface. Remarkably, the modulation of pulse duration resulted in a substantial inhibition of the hydrogen evolution reaction (HER) (FEH2 < 3%) under millisecond pulse conditions (ta = 10 ms, tc = 300 ms, Ea = -0.8 V (vs Hg/Hg2SO4), Ec = -1.8 V (vs Hg/Hg2SO4)), concomitant with a noteworthy enhancement in H2S selectivity (FEH2S > 97%). A comprehensive analysis, incorporating in situ Raman spectroscopy, electrochemical quartz crystal microbalance, COMSOL simulations, and DFT calculations, corroborated the increased selectivity of H2S products was primarily associated with the inherently large dipole moment of the SO2 molecule. The enhancement of the interfacial electric field induced by millisecond pulses was instrumental in amplifying SO2 coverage, activating SO2, facilitating the formation of the pivotal intermediate product *SOH, and effectively reducing the reaction energy barrier in the SO2 reduction process. These findings provide novel insights into the influences of ion and molecular transport dynamics, as well as the temporal intricacies of competitive pathways during the SO2 electroreduction process. Moreover, it underscores the intrinsic correlation between the electric dipole moment and surface-molecule interaction of the catalyst.

The influence of extratropical cross-tropopause mixing on the correlation between ozone and sulfate aerosol in the lowermost stratosphere

Abstract. The chemical composition of the upper troposphere/lower stratosphere region (UTLS) is influenced by horizontal transport of air masses, vertical transport within convective systems and warm conveyor belts, rapid turbulent mixing, as well as photochemical production or loss of species. This results in the formation of the extratropical transition layer (ExTL), which is defined by the vertical structure of CO and has been studied until now mostly by means of trace gas correlations. Here, we extend the analysis to include aerosol particles and derive the sulfate–ozone correlation in central Europe from aircraft in situ measurements during the CAFE-EU (Chemistry of the Atmosphere Field Experiment over Europe)/BLUESKY mission. The mission probed the UTLS during the COVID-19 period with significantly reduced anthropogenic emissions. We operated a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS) to measure the chemical composition of non-refractory aerosol particles in the size range from about 40 to 800 nm. In our study, we find a correlation between the sulfate mass concentration and O3 in the lower stratosphere. The correlation exhibits some variability exceeding the mean sulfate–ozone correlation over the measurement period. Especially during one flight, we observed enhanced mixing ratios of sulfate aerosol in the lowermost stratosphere, where the analysis of trace gases shows tropospheric influence. However, back trajectories indicate that no recent mixing with tropospheric air occurred within the last 10 d. Therefore, we analyzed volcanic eruption databases and satellite SO2 retrievals from the TROPOspheric Monitoring Instrument (TROPOMI) for possible volcanic plumes and eruptions to explain the high amounts of sulfur compounds in the UTLS. From these analyses and the combination of precursor and particle measurements, we conclude that gas-to-particle conversion of volcanic SO2 leads to the observed enhanced sulfate aerosol mixing ratios.

Photoenhanced sulfate formation by the heterogeneous uptake of SO2 on non-photoactive mineral dust

Abstract. Heterogeneous uptake of SO2 on mineral dust is a predominant formation pathway of sulfates, whereas the contribution of photo-induced SO2 oxidation to sulfates on the dust interfaces still remains unclear. Here, we investigated heterogeneous photochemical reactions of SO2 on five mineral oxides (SiO2, kaolinite, Al2O3, MgO, and CaO) without photocatalytic activity. Light enhanced the uptake of SO2, and its enhancement effects negatively depended on the basicity of mineral oxides. The initial uptake coefficient (γ0,BET) and the steady-state uptake coefficient (γs,BET) of SO2 positively relied on light intensity, relative humidity (RH), and O2 content, while they exhibited a negative relationship with the initial SO2 concentration. Rapid sulfate formation during photo-induced heterogeneous reactions of SO2 with all mineral oxides was confirmed to be ubiquitous, and H2O and O2 played key roles in the conversion of SO2 to sulfates. In particular, triplet states of SO2 (3SO2) were suggested to be the trigger for photochemical sulfate formation. Atmospheric implications supported a potential contribution of interfacial SO2 photochemistry on non-photoactive mineral dust to atmospheric sulfate sources.

Investigation of iron oxide supported on activated coke for catalytic reduction of sulfur dioxide by carbon monoxide

In view of the low utilization rate of by-product in limestone-gypsum wet flue gas desulfurization process, a method of catalytic reduction of SO2 to elemental sulfur was proposed. In this work, supported iron catalyst using activated coke as supporter was prepared and characterized. Moreover, the performance of SO2 reduction using CO as reducing agent at various Fe loadings, temperatures, gaseous hourly space velocities and CO/SO2 molar ratios was studied. Research shows that, compared with other metals, the highest catalytic activity is achieved over Fe-based catalyst. The iron sulfide is the main active component during the catalytic reduction reaction, hence the catalyst needs to be presulfided before use. The micropores of activated coke become more abundant after loading Fe, whereas excessive increase of Fe loading may bloke the mesopores and weaken the catalytic activity. Higher reaction temperature, lower GHSV and a stoichiometric molar ratio are conducive to the improvement of SO2 conversion and S yield. The catalytic performance at lower temperatures was further improved by loading Co. When the Co loading is 4 wt%, the SO2 conversion rate reaches 90.9% at 400 °C because loading Co enhances the redox performance of the catalyst surface. The findings are instructive for the development of cost-effective carbon-based catalysts for resource recovery of sulfur.

Investigating the potential of a waste-derived additive for enhancing coal combustion efficiency and environmental sustainability in a circular economy

This study examines the impact of a waste-derived additive from alumina and shale oil production on the performance of coal combustion. The effects of individual additive components were investigated under oxidant-limited and oxidizing conditions using the isothermal flow reactor (IFR) equipped with gas analysers. The raw materials, as well as fly chars/ashes derived from the IFR, were characterized using standard physicochemical analysis, oxide analysis, oxygen functional group determination, the ash fusion test, thermogravimetry, scanning electron microscopy and energy dispersive X-ray spectroscopy. Results from experiments conducted under oxidant-limited conditions demonstrated that the analysed additive, at a 1% share, increased hydrogen content in char by over 3.5 times (from 600 ppm to 2160 ppm) and enhanced methane conversion by nearly 20%. Under oxidizing conditions, the additive reduced unburned carbon loss by approximately 50%, emissions of NOx from 400-460 ppm to 340–390 ppm and SO2 from 1410-1475 ppm to 1325–1410 ppm. The study emphasized the influence of moisture on thermochemical processes, confirming that a certain amount of water vapour accelerates the conversion of H2, SO2, and NOX. The analysis supported the commercial utilization of the additive from economic, environmental, and operational standpoints.

One-pot synthesis of regenerative calcium counterions from waste chicken eggshells for SO2-to-sulfur reduction

Abating sulfur dioxide (SO2) emissions is increasingly critical for addressing environmental concerns and safeguarding human health. In this study, we propose a novel, sustainable approach utilizing in situ eggshell waste-derived calcium-based materials for the catalytic thermal reduction of SO2 to elemental sulfur. Our research focuses on the facile synthesis of calcium-based compounds, proceeding from chicken eggshells to CaO, CaSO4, and finally CaS, for treating hazardous SO2 gas in a one-pot reactor. The effects of gas hourly space velocity (GHSV), temperature, and catalyst stability were studied. Optimal conditions for sulfur yield (71.32%) and SO2 conversion (43.38%) were achieved at 800 °C with a GHSV of 117 L h/g. Our findings demonstrate that the calcium-based materials exhibit exceptional stability, maintaining activity for 6.5 h. Mechanistically, the synergistic pathways of Mars-Van Krevelen and Eley-Rideal mechanisms underlying the SO2 reduction process were elucidated. This research presents a sustainable solution for converting SO2 into a valuable sulfur commodity, and contributes to achieving Sustainable Development Goal No. 12 on Sustainable Consumption and Production. By harnessing CaS derived from eggshell waste, our work underscores the potential for environmentally friendly practices in addressing industrial emissions and advancing sustainable resource utilization.

Insight studies on the deactivation of sulfuric acid regeneration catalyst

The SAR unit is used for regenerating spent sulfuric acid for alkylation reactions. In the SAR unit, the converter employs a potassium and vanadium-based catalyst for conversion of SO2 to SO3. The multiple bed fixed bed reactor is there to ensure that almost entire amount of SO2 is converted to SO3. On observing the generation of large amounts of fines in the reactor catalyst, the spent catalyst and fines are collected for insight studies. The current study enlightens the possible causes of catalyst deactivation and fines generation. Structural changes in potassium/vanadium based catalyst during the oxidation of sulfur dioxide identified as the major cause of catalyst deactivation. Such structural changes and their impact on catalyst property were determined using various physico-chemical characterization methods like crushing strength, Loss on drying (LOD), XRF, XRD, FTIR and XPS analysis. LOD analysis shows the higher moisture and volatile content in spent and fines compared to fresh catalyst. High moisture content in spent catalyst decreases hardness of catalyst resulting in leaching of vanadium salt and carrier degradation due to thermal cycling. Chemical analysis data found to show the active vanadium content in fines is higher compared to spent which indicates vanadium has leached out from fresh catalyst and is deposited on fines. These observations are further correlated with XRD and XPS results. XPS analysis shows the relative distribution of V4+ and V5+ species on the catalyst surface are altered and found very low concentration of V4+ sites on spent catalyst. The XRD analysis demonstrates the leaching of the active component, potassium vanadyl sulfate K(VO2) (SO4)·3H2O, which then accumulated in the fines fraction. FT-IR and XRD results further shows increase in sulfate accumulation on spent catalyst surface along with phase changes. FTIR analysis of simulated spent catalyst are well correlated with these findings.

Heterogeneous photochemical uptake of SO2 on typical brown carbon species: A significant sulfate source

The heterogeneous reactions of SO2 on organic aerosols (OA) have been proposed as a significant source of sulfates. The photochemical conversion of SO2 to sulfates on the surface of light-absorbing OA, i.e., brown carbon (BrC), remained slight understanding. Herein, the photochemical uptake of SO2 on typical BrC species, including aromatic carbonyl compounds (ACs), polycyclic aromatic hydrocarbons (PAHs) and phenols (PHs), was systematically investigated by a flow tube reactor. Light can significantly promote the uptake of SO2 on all BrC species used here, especially for ACs. The initial and steady-state uptake coefficients (γi and γss) of SO2 exhibited positive relationships with the light intensity, whereas they negatively correlated with the initial SO2 concentration. Significant sulfate formation was clearly observed with in situ attenuated total internal reflection infrared (ATR-IR) spectrometer, and H2O and O2 had obvious enhancement effects on the sulfate production. Photoinduced •OH, which primarily originated from •O2− that was generated through an electron transfer process on BrC under irradiation, was determined to be a key driver for the oxidation of SO2 to sulfates. Finally, SO2 lifetime and sulfate formation rate were evaluated on the basis of experimental results, highlighting potential contributions of BrC photochemistry to atmospheric SO2 loss and sulfate sources.

The WRF-CMAQ Simulation of a Complex Pollution Episode with High-Level O3 and PM2.5 over the North China Plain: Pollution Characteristics and Causes

The problem of atmospheric complex pollution led by PM2.5 and O3 has become an important factor restricting the improvement of air quality in China. In drawing on observations and Weather Research and Forecasting-Community Multiscale Air Quality (WRF-CMAQ) model simulations, this study analyzed the characteristics and causes of a regional PM2.5-O3 complex pollution episode in North China Plain, in the period from 3 to 5 April 2019. The results showed that in static and stable weather conditions with high temperature and low wind speed, despite photochemical reactions of O3 near the ground being weakened by high PM2.5 concentrations, a large amount of O3 generated through gas-phase chemical reactions at high altitudes was transported downwards and increased the O3 concentrations at the ground level. The high ground-level O3 could facilitate both the conversion of SO2 and NO2 into secondary inorganic salts and volatile organic compounds into secondary organic aerosols, thereby amplifying PM2.5 concentrations and exacerbating air pollution. The contributions of transport from outside sources to PM2.5 (above 60%) and O3 (above 46%) increased significantly during the episode. This study will play an instrumental role in helping researchers to comprehend the factors that contribute to complex pollution in China, and also offers valuable references for air pollution management.

The Effect of Mn Doping and Ti3+ Defects at TiO2 Surfaces in NO and SO2 Gas Capture Investigated Using Near-Ambient Pressure X-ray Photoelectron Spectroscopy

The removal of air pollutants is an important research topic in order to improve the environment. In addition, many common pollutants can affect human health to varying degrees. In this work, we investigate NO and SO2 conversion by reaction with a commonly used metal oxide catalyst, TiO2. Rutile TiO2(110) single crystals and industrial powder samples used in sunscreen are studied using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) as a main tool. This allows in situ monitoring of the gas conversion process. We find Ti3+ defects (oxygen vacancies) or Mn oxides/cations (MnO) at the TiO2 surfaces can improve the conversion of NO and SO2 to surface-bound species. MnO and Ti3+ defects at the surface of rutile TiO2(110) exhibit a synergistic effect on the conversion of NO and SO2 that is significantly improved by nearly an order of magnitude. The by-products are mainly in the form of NO3−, SO32−, and SO42−. We find the main oxidation products formed on the single crystals are subtly different from those on the industrial powder samples. For TiO2 nanopowders (undoped and Mndoped), the presence of Mn also shows improvement in toxic gas adsorption capacity. Overall, it is believed that the outcome obtained from NAP-XPS in this research provides useful insights for the future use of TiO2 in pollutant gas capture.

Enhanced Sulfate Formation from Gas-Phase SO2 Oxidation in Non–•OH–Radical Environments

Recent research on atmospheric particle formation has shown substantial discrepancies between observed and modeled atmospheric sulfate levels. This is because models mostly consider sulfate originating from SO2 oxidation by •OH radicals in mechanisms catalyzed by solar radiation while ignoring other pathways of non-radical SO2 oxidation that would substantially alter atmospheric sulfate levels. Herein, we use high-level quantum chemical calculations based on density functional theory and coupled cluster theory to show that monoethanolamine (MEA), a typical alkanolamine pollutant released from CO2 capture technology, can facilitate the conversion of atmospheric SO2 to sulfate in a non–•OH–radical oxidation mechanism. The initial process is the MEA-induced SO2 hydrolysis leading to the formation of HOSO2−•MEAH+. The latter entity is thereafter oxidized by ozone (O3) and nitrogen dioxide (NO2) to form HSO4−•MEAH+, which is an identified stabilizing entity in sulfate-based aerosol formation. Results show that the HOSO2−•MEAH+ reaction with O3 is kinetically and thermodynamically more feasible than the reaction with NO2. The presence of an additional water molecule further promotes the HOSO2−•MEAH+ reaction with O3, which occurs in a barrierless process, while it instead favors HONO formation in the reaction with NO2. The investigated pathway highlights the potential role alkanolamines may play in SO2 oxidation to sulfate, especially under conditions that are not favorable for •OH production, thereby providing an alternative sulfate source for aerosol modeling. The studied mechanism is not only relevant to sulfate formation and may effectively compete with reactions with sulfur dioxide and hydroxyl radicals under heavily polluted and highly humid conditions such as haze events, but also an important pathway in MEA removal processes.

Experimental study and modelling of continuous SO2-depolarized electrolysis in hybrid sulfur cycle for hydrogen production

SO2-depolarized electrolysis (SDE) is the key process in the hybrid sulfur cycle for green hydrogen production, but the detailed SDE characteristics including products generation, current efficiency variation, and side reactions are unclear. Herein, a continuous SDE process was experimentally conducted and theoretically modelled. The H2 and H2SO4 production was accelerated and the current efficiency for both electrodes was improved with a proper increase in current density (50−100 mA/cm2) or temperature (293−318 K), but further increasing current density to 150 mA/cm2 or temperature to 333 K led to a negative trend because of the anode corrosion or declined SO2 solubility. The increasing initial H2SO4 concentration (10−40 wt%) facilitated the cathodic H2 production and current efficiency, while negatively influenced the anodic SO2 conversion. The parasitic reactions occurred at cathode consumed H2 and resulted to the cathodic current efficiency well below 100%. A rigorous mathematical regression model correlating the production rates of H2 and H2SO4 with current density, temperature, and initial H2SO4 concentration was developed, and combined with the analysis of variance, current density was suggested the biggest factor affecting products generation in SDE process. These findings demonstrate a practical avenue for efficient SO2 conversion and H2 production in SDE process of hybrid sulfur cycle.

Continuous multiphase Bunsen reactor of iodine-sulfur thermochemical water splitting cycles for hydrogen production: Experimental, Modelling and Design Insights

Thermochemical water splitting cycles (TWSCs) hold promise for sustainable H2 production in future energy systems, with Iodine-Sulfur (IS) and Nickel-Iodine-Sulfur (NIS) processes standing out as efficient options. The core of both these processes lies in the Bunsen reaction, underscoring the need to identify optimal operational conditions and plant solutions for this crucial reaction section. Thus, in this study, a continuous counter-current flow Bunsen reactor fed with 5 NL h−1 of SO2 was constructed and tested. An inventive aspect was the introduction of solid I2 pellets from the top to enhance saturation at the liquid-liquid interface between sulfuric and hydriodic product phases, promoting segregation. This ingenious design achieved nearly complete SO2 conversion and optimal H2SO4 and HI concentrations in the respective product phases, while avoiding undesirable byproduct formation. The study further advanced the modelling of the experimental reactor by employing innovative kinetic and liquid-liquid equilibrium description approaches, and demonstrating exceptional validation accuracy of R2 = 0.9988. Additionally, with the aim of obtaining design charts as a potential tool for Bunsen reactor design, a microscopic model describing the gas phase trend along bubble or packed Bunsen-type reactors was developed. The model’s dimensionless analysis revealed a characteristic times ratio (Bu) comprehensively describing all the phenomena occurring to the gas phase within the Bunsen reaction section, and identified an optimal Bu value of 0.4 for pure SO2 gas inlet. Overall, the study's innovative strategies and models contribute significantly to the advancement of Bunsen reactor engineering.

Reduction of SO2 to Elemental Sulfur in Flue Gas Using Copper-Alumina Catalysts

This study aims to propose an advanced catalyst for the selective catalytic reduction of SO2, as a sustainable process to mitigate the emission of this toxic gas, which is a significant environmental concern. The conversion of SO2 through catalytic reduction with CH4 to elemental sulfur was investigated using Al2O3-Cu catalysts. The reaction was conducted under atmospheric pressure and at a temperature range of 550–800°C. A remarkable 99.9% SO2 conversion rate and 99.5% sulfur selectivity were achieved using the Al2O3-Cu (10%) catalyst at 750°C. The highest conversion rates of SO2 to elemental sulfur, with minimal production of undesirable by-products such as H2S and COS, were obtained when the SO2/CH4 molar feed ratio was set at 2, which is the stoichiometric ratio. Furthermore, the optimal catalyst exhibited excellent long-term stability for SO2 reduction with methane.

Equilibrium and experimental study on carbothermal reduction of sulfur dioxide to elemental sulfur

In order to solve the problem of low utilization value of flue gas desulfurization by-product, reduction of sulfur dioxide to elemental sulfur has emerged as a new process for resource utilization of SO2 with promising application prospects. Herein, the thermodynamic equilibrium calculation was carried out to study the influence of temperatures and C/SO2 molar ratios on the C-SO2 reaction. The effects of reaction temperature, carbon mass, and CO concentration on SO2 reduction by coke and activated carbon were studied on a fixed bed reaction system. The theoretical results demonstrated that the highest equilibrium S yield occurred when the C/SO2 molar ratio is 1, with higher ratios resulting in the formation of COS, CS2, and CO. Experimental data revealed that at temperatures below 700 °C, both SO2 conversion and S yield are notably low. As the temperature increases, both the conversion and yield gradually increase and approach the thermodynamic equilibrium value. The evolution of carbon surface chemical properties under the action of CO was analyzed by FTIR and XPS, which indicated that the presence of CO promotes the decarboxylation reaction, and then increases SO2 conversion and S yield. The conclusion of this study provides guidance for the development of high efficiency SO2 reduction technology.