Research progress on catalysts for organic sulfur hydrolysis: Review of activity and stability

The removal of organic sulfur through catalytic hydrolysis is a significant area of research in the field of desulfurization.This review provides an overview of recent advancements in catalytic hydrolysis technology of organic sulfur,including the activity,stability,and atmosphere effects of hydrolysis catalysts.The emphasis is on strategies for enhancing hydrolysis activity and anti-oxygen poisoning property of catalysts.Surface modification,metal doping and nitrogen doping have been found to improve the activity of catalysts.Alkaline components modification is the most commonly used method,the formation of oxygen vacancies through metal doping and creation of nitrogen basic sites through nitrogen doping also contribute to the hydrolysis of organic sulfur.The strategies for anti-oxygen poisoning are discussed in a systematic manner.The structural regulation of catalysts is beneficial for the desorption and diffusion of hydrogen sulfide(H_(2)S),thereby effectively inhibiting its oxidation.Nitrogen doping and the addition of electronic promoters such as transition metals can protect active sites and decrease the number of active oxygen species.These methods have been proven to enhance the anti-poisoning performance of catalysts.Additionally,this article summarizes how different atmospheres affect the activity of hydrolysis catalysts.The objective of this review is to pave the way for the development of efficient,stable and widely used catalysts for organic sulfur hydrolysis.

Molecular investigation into the transformation of recalcitrant dissolved organic sulfur in refinery sour water during stripping process

Refinery sour water primarily originates from the tops of towers in various units and coker condensate,and cannot be discharged directly to a wastewater treatment plant due to high levels of chemical oxygen demand(COD)and organic sulfur contents.Even after the recovery of H_(2)S from the sour water by the stripping process,the effluent still contains a high concentration of dissolved organic sulfur(DOS),which can have a huge bad influence.While chemical composition of dissolved organic matter(DOM)in refinery wastewater has been extensively studied,the investigation of recalcitrant DOS from sour waters remains unclear.In the present study,chemical composition of sour water DOMs(especially DOS)was investigated using fluorescence spectroscopy(excitation-emission matrix,EEM)and mass spectrometry,including gas chromatography-mass spectrometry(GC-MS)and high-resolution Orbitrap MS.The GC-MS and EEM results showed that volatile and low-aromaticity compounds were effectively removed during the stripping process,while compounds with high hydrophilicity and humification degree were found to be more recalcitrant.The Orbitrap MS results showed that weak-polar oxygenated sulfur compounds were easier to be removed than oxygenated compounds.However,the effluent still contained significant amounts of sulfur-containing compounds with multiple sulfur atoms,particularly in the form of highly unsaturated and aromatic compounds.The Orbitrap MS/MS results of CHOS-containing compounds from the effluent indicate that the sulfur atoms may exist as sulfonates,disulfide bonds,thioethers.Understanding the composition and structure of sour water DOS is crucial for the development of effective treatment processes that can target polysulfide compounds and minimize their impact on the environment.

Effects of Coal Rank and High Organic Sulfur on the Structure and Optical Properties of Coal-based Graphene Quantum Dots

Coal-based graphene quantum dots(GQDs) were successfully produced via a one-step chemical synthesis from six different coal ranks, from which two superhigh organic sulfur(SHOS) coals were selected as natural S-doped carbon sources for the preparation of S-doped GQDs. The effects of coal properties on coal-based GQDs were analyzed by means of high-resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), ultraviolet-visible(UV-Vis) absorption spectroscopy, and fluorescence emission spectra. It was shown that all coal samples can be used to prepare GQDs, which emit bluegreen and blue fluorescence under ultraviolet light. Anthracite-based GQDs have a hexagonal crystal structure without defects, the largest size, and densely arranged carbon rings in their lamellae; the highrank bituminous coal-based GQDs are relatively reduced in size, with their hexagonal crystal structure being only faintly visible; the low-rank bituminous coal-based GQDs are the smallest, with sparse lattice fringes and visible internal defects. As the metamorphism of raw coals increases, the yield decreases and the fluorescence quantum yield(QY) initially increases and then decreases. Additionally, the surface of GQDs that were prepared using high-rank SHOS coal(high-rank bituminous coal) preserves rich sulfur content even after strong oxidation, which effectively adjusts the bandgap and improves the fluorescence QY. Thus, high-rank bituminous coal with SHOS content can be used as a natural S-doped carbon source to prepare S-doped GQDs, extending the clean utilization of low-grade coal.

Assessment of the Influence of Sulfuric Acid/Hydrogen Peroxide Mixture on Organic Sulfur Reduction of High Sulfur Coals and Their Chemical Composition

One of the contaminants in coal is sulphur. The adverse impact of sulfur on coal, such as environmental pollution, degradation of steel quality, and reduction of coal’s thermal value, has led to the attention of sulfur separation methods in recent decades. Leaching (chemical dissolution) is one of the best methods for desulfurising coal, reducing sulfur in coal. In this study, hydrogen peroxide as an oxidising agent on sulfuric acid yield in reducing sulfur types of coal and chemical structure and the organic texture of high sulfur coal was investigated. The experiments were designed using a three-level response surface methodology with four duplicate points and 27 experiments. The independent variables studied were temperature, time, stirring speed and ratio of sulfuric acid to hydrogen peroxide. Dependent variables included reduction percentage of total, pyritic and organic sulfur. This study showed that 99.99% of total sulfur, 30.11% of pyritic sulfur and 69.08% of organic sulfur were reduced. These values were obtained at a temperature of 60°C, time 120 min, stirring speed 200 rpm and 3:1 ratio of sulfuric acid to hydrogen peroxide. Significant changes were observed by infrared spectroscopy (FTIR) of the coal structure before and after desulphurisation. On the other hand, the studies showed no specific changes in the bonds related to the organic coal matrix. The results showed that this method could be used as a secure process for removing inorganic and organic sulfur without destroying the organic coal matrix.

Sulfur-containing amino acid methionine as the precursor of volatile organic sulfur compounds in algea-induced black bloom

After the application of methionine, a progressive and significant increase occurred in five volatile organic sulfur compounds （VOSCs）： methanethiol （MESH）, dimethyl sulfide （DMS）, dime^yl disulfide （DMDS）, dimethyl trisulfide （DMTS） and dimethyl tetrasulfide （DMTeS）. Even in the untreated control without a methionine addition, methionine and its catabolites （VOSCs, mainly DMDS） were found in considerable amounts that were high enough to account for the water＇s offensive odor. However, blackening only occurred in two methionine-amended treatments. The VOSCs production was observed to precede black color development, and the reaching of a peak value for total VOSCs was often followed by water blackening. The presence of glucose stimulated the degradation of methionine while postponing the occurrence of the black color and inhibiting the production of VOSCs. In addition, DMDS was found to be the most abundant species produced after the addition of methionine alone, and DMTeS appeared to be the most important compound produced after the addition of methionine＋glucose. These results suggest that methionine acted as an important precursor of the VOSCs in lakes suffering from algea-induced black bloom. The existence of glucose may change the transformation pathway of methionine into VOSCs to form larger molecular weight compounds, such as DMTS and DMTeS.

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur(DOS)by electrospray ionizationFourier transform ion cyclotron resonance mass spectrometry(ESI-FTICR MS)is necessary for further understanding of the role of DOS in the environment.Here,ESI spray solvent,a key parameter for ion production during ESI process,was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS.100%MeOH as spray solvent was found for the first time to remarkably enhance the ionization efficiency of the majority of CHOS-molecules in NOM,which facilitated a total of 1473 CHOS-molecular formulas with one sulfur atom to be detected.The number of CHOS-molecular formulas obtained using 100%MeOH as spray solvent increased notably over 740 in comparison with those using 50%MeOH aqueous solution(731)or 50%ACN aqueous solution(653).Moreover,due to the enhancement of ionization efficiency of DOS during ESI processes,the tandem mass spectra of the NOM CHOS-molecules could be easily obtained using 100%MeOH as spray solvent,which were hardly obtained using 50%MeOH aqueous solution as spray solvent.The results of the tandem mass spectra suggested the first discovery of organosulfates or sulfonic acids in Suwannee River NOM sample.A simple method based on 100%MeOH as ESI spray solvent for advanced molecular characterization of DOS by ESI-FTICR MS was proposed and applied,and the results revealed more molecular information of DOS in sea DOM samples.

Dissolved organic sulfur in streams draining forested catchments in southern China

Dissolved organic sulfur （DOS） is an important fraction for sulfur mobilization in ecosystem. In this work stream waters were sampled in 25 forested sites in southern China to study the dissolved sulfur fractions. Dissolved sulfur was fractionated into dissolved organic sulfur （DOS） and inorganic sulfate （SO]-） for 95 stream water samples. The results showed that the concentration of DOS ranged from 0 to 13.1 mg/L （average 1,3 mg/L） in all the streams, High concentrations of DOS in stream waters were found in the sites with high concentrations of sulfate. DOS constituted less than 60.1% of dissolved sulfur （average 17.9%）. Statistical analysis showed that DOS concentration was correlated with SO42- in streams waters and total sulfur in surface layer soils. The results also showed that DOS concentration in stream waters had a seasonal variation, but no trends were found with it. The implication was that the long term sulfur deposition had led the increase of the concentration and fraction of DOS in stream waters in acid rain prevailing regions

STUDY ON REGULATIONS OF SULFUR OCCURRENCE AND PYRITE MAGNETISM OF LATE PERMIAN COALS IN SOUTHWEST CHINA

The Permian coal in southwest China contains highest sulfur among the Chinese coal .Compositional variations of sumir in coal are mainly controlled by palaogeographital environmentsduring peat accumulation. High organic sulfur coal is formed in peat swamp developing in tidal flat of limited carbonate platform, and it is provided with especial petrologital and geochemical characteristics, and its organoschr-containing compounds are mainly thiophene series. The macroscopitaland microscopical shapes or types of pyrites in Late Permisn coal are diversined. Bituminous coal and anthracite are diamagnetic, but the pyrites are paramagnetic. The magnetic susceptibility oftbe pyrites is depended on the content of paramagnatic elements associnted with pyrites.

Chemical, carbon and sulfur isotopic compositions constrain the origin of Upper Carboniferous-Lower Triassic gases in eastern Sichuan Basin, SW China

Methane dominated gas is one of the cleanest energy resources;however, there is no direct method to determine its source rock. Natural gases produced from the eastern Sichuan Basin together with seismic data were studied for their sources and secondary alteration by thermochemical sulfate reduction(TSR). Our results demonstrate that Upper Permian to Lower Triassic(P_(3)ch-T_(1)f) gases in the surrounding of the Kaijiang-Liangping area show volatile organic sulfur compounds(VOSCs) δ^(34)S values close to those of the associated H_(2)S, and may have been altered by methane-dominated TSR, resulting in positive shift in methane δ^(13)C_(1)values with increasing TSR extents. Other(or group 2) gases produced from the P_(3)ch-T_(1)f reservoirs from the southern area and the Upper Carboniferous to Middle Permian(C_(2)h-P_(2)q) from the eastern Sichuan Basin are not significantly changed by TSR, show similar δ^(34)S values between the kerogens and some VOSCs, and may have been derived from the Lower Silurian and Middle Permian source rocks. This study demonstrates a case for the first time showing the δ^(34)S values of VOSCs can be used as a tool for direct correlation between non-TSR altered gas and source rocks. Methane-dominated gas pools can be found using gas and source rock geochemistry combined with seismic data.

Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion(SPICE) in the Jiangnan Basin, South China

Global occurrences of Steptoean Positive Carbon Isotope Excursion（SPICE） during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon（δ^（13）C） and organic carbon（δ^（13）C_（org）） isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate（CAS, δ^（34）S_（CAS）） and pyrite（δ^（34）S_（pyrite））, unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰ increase in δ^（13）C_（carb） of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions in δ^（34）S_（CAS） and δ^（34）S_（pyrite） have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound（VOSC, such as methanethiol and dimethyl sulfide） formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of ^（32）S from continental margins to open oceans, elevating δ^（34）S of seawater sulfate in continental margins. A simple box model indicates that about 35% to 75% of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

Molecular characterization of sulfur compounds in some special sulfur-rich Chinese crude oils by FT-ICR MS

Routine GC/MS analysis may apply to the volatilized Low-Molecular-Weight compounds in saturate and aromatic hydrocarbon fractions;thus,relative studies using this technique inevitably bring about some limitations on distribution of miscellaneous sulfur atom.In this article,Fourier Transform Ion Cyclotron Resonance Mass Spectrometry(FT-ICR MS)with high resolution is employed to investigate the distribution of organic sulfur compounds(OSCs)in the crude oil typically derived from the Eogene carbonate-evaporite sediments with further chemical compositional characterization in molecular level by miscellaneous atomic type,carbon number,and double bond equivalent(DBE).A variety of miscellaneous atomic types with S1,S2,S3,OS,OS2,O2S,O2S2,NS,and NOS etc.(S1 means those OSCs with one sulfur atom in a molecule)were identified in OSCs in these oil samples.High levels of alkyl thioether series compounds with one ring structure were presented mainly in the crude oil in the Jianghan Basin whereas high amounts of benzothiophene,dibenzothiophene etc.compounds with higher values in DBE and carbon number range occurred in the sulfur-rich heavy oil in the Jinxian Sag.Although carbonate-evaporite sediments deposited in the saline lacustrine facies in the Eogene basin both occurred in the Jinxian Sag and Jianghan Basin,obviously,they possess different chemical diagenetic pathway of sulfur under various microbial reactions,leading to diverse distributional characteristics on biomarkers,OSCs,and even different hydrocarbon generation mechanism of immature crude oil.

Beyond hypoxia: Occurrence and characteristics of black blooms due to the decomposition of the submerged plant Potamogeton crispus in a shallow lake

Organic matter-induced black blooms （hypoxia and an offensive odor） are a serious ecosystem disasters that have occurred in some large eutrophic shallow lakes in China. In this study, we investigated two separate black blooms that were induced by Potamogeton crispus in Lake Taihu, China. The main physical and chemical characteristics, including color- and odor-related substances, of the black blooms were analyzed. The black blooms were characterized by low dissolved oxygen concentration （close to 0 mg/L）, low oxidation-reduction potential, and relatively low pH of overlying water. Notably higher Fe^2＋ and ∑S2- were found in the black-bloom waters than in waters not affected by black blooms. The black color of the water may be attributable to the high concentration of these elements, as black FeS was considered to be the main substance causing the black color of blooms in freshwater lakes. Volatile organic sulfur compounds, including dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, were very abundant in the black-bloom waters. The massive anoxic degradation of dead Potamogeton crispus plants released dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, which were the main odor-causing compounds in the black blooms. The black blooms also induced an increase in ammonium nitrogen and soluble reactive phosphorus levels in the overlying waters. This extreme phenomenon not only heavily influenced the original lake ecosystem but also greatly changed the cycling of Fe, S, and nutrients in the water column.

Deciphering the effect of sodium dodecylbenzene sulfonate on up-flow anaerobic sludge blanket treatment of synthetic sulfate-containing wastewater

In this study,the effects of organic sulfur on anaerobic biological processes were investigated by operating two up-flow anaerobic sludge blanket(UASB)reactors with sodium dodecylbenzene sulfonate(SDBS)as a representative of organic sulfur.The results indicated that the specific methanogenic activity(SMA)and chemical oxygen demand(COD)removal efficiency of R2(with SDBS added)were higher than those of R1(without SDBS)when the COD/SO_(4)^(2−)ratio was above 5.0.However,when the COD/SO_(4)^(2−)ratio was lower than 5.0,the sulfate reduction efficiency of R2 was higher than that of R1.These results and the observed SDBS transformation efficiency in anaerobic reactors indicate that low concentrations of SDBS accelerate methane production and the continuous accumulation of SDBS does not weaken the reduction of sulfate.Similarly,the calculated electron flux for a COD/SO_(4)^(2−)ratio of 1.0 indicates that the utilization intensity of electrons by sulfate-reducing bacteria(SRB)in R2 was 36.48%higher than that of SRB in R1 and exceeded that of methane-producing archaea(MPA)under identical working conditions.Moreover,the addition of SDBS in R2 made sulfidogenesis the dominant reaction at low COD/SO_(4)^(2−),and Methanobacterium and Methanobrevibacter with H_(2)/CO_(2)as the substrate and Desulfomicrobium were the dominant MPA and SRB,respectively.However,methanogenesis was still the dominant reaction in R1,and Methanosaeta with acetic acid as the substrate and Desulfovibrio were the dominant MPA and SRB,respectively.

Isolation and Characterization of Methanethiol-Producing Bacteria from Agricultural Soils

Methanethiol(MT) produced from terrestrial soils can have important effects on atmospheric chemistry and ecosystem-level processes, and it originates mainly from the metabolism of sulfur-containing amino acids by microorganisms.Methanethiol producing bacteria(MPB) were enriched and isolated from agricultural soils in a modified basal medium containing methionine(Met) as the sole carbon source.The isolates were identified as Bacillus sp.WH-R1, WH-R2, and WH-R3; Arthrobacter sp.SZLB-W3; and Delftia sp.CHZG-R4 based on cell morphology, physiological and biochemical characteristics, and 16 S r RNA sequence analysis.Delftia sp.CHZG-R4 was identified as a novel strain producing MT using Met as a precursor, and it had the most active MT-producing potential, with the production of MT being 21.8 μg at 30℃ and pH 7.0.Optimal MT production was observed at 35℃ and pH6.0, with 51.3% of sulfur content in Met being converted into MT.Under these conditions, MT production changed according to the supply of both carbon and nitrogen sources.The addition of 2 g L^(-1) each of starch, sucrose, urea, and potassium nitrate promoted MT production by more than 10%, whereas addition of 2 g L^(-1) each of ammonia sulfate and peptone decreased MT production by16% and 87%, respectively.This is the first study to report MT production by Delftia sp.CHZG-R4, providing useful information for the microbial mechanism of MT production from agricultural soils.Our findings also contribute to improving our knowledge of the function of Delftia sp.CHZG-R4.

Voltammetric determination of stability constants of lead complexes with diallyl disulfide, dimethyl disulfide, and diallyl sulfide

The complexation of Pb^（2＋）by diallyl disulfide（DADS）, dimethyl disulfide（DMDS） and diallyl sulfide（DAS）has been studied by differential pulse voltammetry. Stability constants,（log b）, of the 1：1（PbL） and 1：2（PbL_2） complexes, where L = ligand, were found to be in the range of ca. 3.8-4.2 and 9.4-10.2,respectively. Complex formation is accompanied with a significant decrease in the peak current and the shift of the Pb2＋/Pb half-wave potential to a higher one upon the addition of the sulfur containing ligands（L）. The formation of 1：1 and 1：2 complexes, i.e., PbL^（2＋）and PbL_2^（2＋）was observed in the case of the three ligands. The consecutive formation constants of labile lead complexes with DADS, DMDS, and DAS were determined at 298 K by the method of De Ford and Hume. Apparently due to the large size of the lead ion,steric hindrance caused by the greater steric bulk of DADS compared to that of DMDS have little or no effects on the formation constants, so that very similar values were obtained in the case of the two ligands. Also, the possible participation of C=C double bonds in coordination with the metal center in the case of DADS appears to compensate for the steric effects caused by the larger size of this ligand. In agreement with the Jorgensen principle of symbiosis, the second formation constants were found to be approximately six orders of magnitude greater than the first ones.

Role of secondary aerosols in haze formation in summer in the Megacity Beijing

A field experiment from 18 August to 8 September 2006 in Beijing, China, was carried out. A hazy day was defined as visibility 〈 10 km and RH（relative humidity） 〈 90%. Four haze episodes, which accounted for ～ 60% of the time during the whole campaign, were characterized by increases of SNA（sulfate, nitrate, and ammonium） and SOA（secondary organic aerosol） concentrations. The average values with standard deviation of SO2-＋4, NO-3, NH4 and SOA were 49.8（± 31.6）, 31.4（±22.3）, 25.8（±16.6） and 8.9（±4.1） μg/m3, respectively, during the haze episodes, which were 4.3, 3.4, 4.1, and 1.7 times those in the non-haze days. The SO2-4,NO-3, NH＋4, and SOA accounted for 15.8%, 8.8%, 7.3%, and 6.0% of the total mass concentration of PM10 during the non-haze days. The respective contributions of SNA species to PM10 rose to about27.2%, 15.9%, and 13.9% during the haze days, while the contributions of SOA maintained the same level with a slight decrease to about 4.9%. The observed mass concentrations of SNA and SOA increased with the increase of PM10 mass concentration, however, the rate of increase of SNA was much faster than that of the SOA. The SOR（sulfur oxidation ratio） and NOR（nitrogen oxidation ratio） increased from non-haze days to hazy days, and increased with the increase of RH. High concentrations of aerosols and water vapor favored the conversion of SO2 to SO2-4and NO2 to NO-3, which accelerated the accumulation of the aerosols and resulted in the formation of haze in Beijing.