The thermodynamic properties of 135 polybrominated dibenzothiophenes （PBDTs） in the gaseous state at 298.15 K and 1.013×10^5 Pa, are calculated using the density functional theory （the B3LYP/6-311G^＊＊） wit...The thermodynamic properties of 135 polybrominated dibenzothiophenes （PBDTs） in the gaseous state at 298.15 K and 1.013×10^5 Pa, are calculated using the density functional theory （the B3LYP/6-311G^＊＊） with Gaussian 03. Based on these data, the isodesmic reacflons are designed to calculate the standard enthalpy of formation （△fH^θ） and the standard Gibbs energy of formation （△fG^θ） of PBDTs. The relations of these thermodynamic parameters with the number and positionof bromine subsfituents （NPBS） are discussed, and it is found that there exist good correlations between othermody namic parameters （including heat capacity at constant volume, entropy, enthaipy, free energy, △fH^θ, △fG^θ） and NPBS. Thoe relative stability order of PBDT congeners is proposed theoretically based on the relative magnitude of their △fG^θ. In addition, the values of molar heat capacities at constant pressure （Cp,m） for PBDT c ongelaers are calculated.展开更多
Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes（PCDT/TAs）,sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans（PCDD/Fs）, has been well-documented to occur via ra...Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes（PCDT/TAs）,sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans（PCDD/Fs）, has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol（2-CTP） as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene（1-MCTA）, 1,6-dichlorothianthrene（1,6-DCTA）, 4,6-dichlorodibenzothiophene（4,6-DCDT）and 1,6-dichlorodibenzothiophene（1,6-DCDT）. The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.展开更多
Aromatic fractions of 140 oils and condensates that originated from different types of source rocks （marine shale,terrestrial shale and marine carbonate） were analyzed using gas chromatographymass spectrometry （GC...Aromatic fractions of 140 oils and condensates that originated from different types of source rocks （marine shale,terrestrial shale and marine carbonate） were analyzed using gas chromatographymass spectrometry （GC-MS） to investigate the relative distributions of methylated dibenzothiophenes with respect to thermal maturity.The positions of methyl groups of trimethyldibenzothiophene isomers （TMDBTs） including those used in the definition of maturity indicator TMDBT index in previous studies were firmly identified by co-elution of internal standards in GC-MS analysis and by comparing with reported retention indices.A new maturity ratio related to dimethyldibenzothiophenes （DMDBTs） is proposed on the basis of the differences in thermodynamic stability among different DMDBT isomers.Another maturity index （TMDBT-I2） based on TMDBTs is also suggested on the basis of our empirical observations and presumed thermodynamic stability of TMDBT isomers.These two newly proposed （2,6 ＋ 3,6）-/1,4-DMDBT ratio and TMDBT-I2 correlate well with MDR （4-/1-methyldibenzothiophene）and 2,4-/1,4-DMDBT ratios,suggesting their common chemical reaction mechanisms and similar behavior with increasing maturity.Therefore,they can be effectively applied for maturity assessments.Furthermore,the TMDBTs related maturity parameters are more reliable for over-mature oils and condensates due to the relatively higher concentrations of thermodynamically unstable TMDBT isomers,i.e.1,4,6-,1,4,8-and 3,4,6-TMDBT in this study than those of 1-methyldibenzothiophene （1-MDBT） or 1,4-DMDBT.In contrast with 4,6-/1,4-DMDBT,the newly proposed （2,6 ＋ 3,6）-/1,4-DMDBT ratios for oils that originated from different types of source rocks have approximately same relationship with the oil maturity （Rc %）.This suggests that the lithology and organic facies may have relatively less influence on （2,6 ＋ 3,6）-/1,4-DMDBT ratio compared to 4,6-/1,4-DMDBT.The maturity parameters based on methylated dibenzothiophenes are particularly useful in the maturity assessments of post-and over-mature oils and condensates and can complement maturity indicators based on steranes and terpanes.展开更多
Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations...Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations of electrostatic potentials(ESPs)on molecular surface have been performed for all 135 PCDTs and 135 PCDTO2 congeners at the HF/6-31G*level of theory.A number of statistically-based parameters have been extracted.Linear relationship between gas-chromatographic retention index(RI)and the structural descriptors have been established by multiple linear regression.The result shows that two descriptors derived from positive electrostatic potential on molecular surface,■andπ,together with the molecular volume(Vmc)and the energy of the lowest unoccupied molecular orbital(ELUMO)can be well used to express the quantitative structure-retention relationship(QSRR)of PCDTs and PCDTO2.Predictive capability of the two models has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient(RCV)of 0.996 and 0.997,respectively.Furthermore,the predictive power of the models is further examined for the external test set.Correlation coefficients(R)between the observed and predicted RI values for the external test set are 0.997 and0.998,respectively,validating the robustness and good prediction of our model.The QSRR model established may provide again a powerful method for predicting chromatographic properties of aromatic organosulfur compounds.展开更多
TS-1 zeolites with different grain sizes were prepared under hydrothermal conditions by tuning the amount of template agent,chelating agent,and temperature,which were further used as supports for the NiMo/TS-1 catalys...TS-1 zeolites with different grain sizes were prepared under hydrothermal conditions by tuning the amount of template agent,chelating agent,and temperature,which were further used as supports for the NiMo/TS-1 catalysts.The optimization of synthesis conditions has achieved controllable synthesis of grain sizes from nano-scale to micron-scale.TS-1 with smaller grain sizes possess larger specific surface area,external specific surface area,and pore volume,which can effectively shorten the diffusion path of the sulfide with complex structure.Nanoscale TS-1 has more highly-coordinated Ti species,acting as electronic additives to increase the sulfidation degree of the catalyst.Nano-scale NiMo/TS-1 exhibits higher acidity,which is beneficial for hydrodesulfurization(HDS)reactions.Among the series of NiMo/TS-1 catalysts,NiMo/TS-1(120 nm)catalyst exhibits the highest dibenzothiophene(DBT,88.4%)and 4,6-dimethylbenzothiophene(4,6-DMDBT,62.1%)HDS activities.展开更多
The condensates are generally characterized by high maturity,low concentration of steranes and ter-panes biomarkers and low content of non-hydrocarbon fraction.In this case commonly used steranes,terpanes and carbazol...The condensates are generally characterized by high maturity,low concentration of steranes and ter-panes biomarkers and low content of non-hydrocarbon fraction.In this case commonly used steranes,terpanes and carbazoles parameters cannot be effectively applied in the reservoir-filling tracing.The hydrogen bond formed by sulfur atom in the dibenzothiophenes(DBTs)results in molecule adsorption and fractionation during oil migration in reservoir.Like carbazoles,total DBTs content decreases with the increasing of oil migration distance.Therefore,a new parameter——total DBTs content is proposed to be used to trace the oil migration orientation and filling pathway.In present study,total DBTs con-tents of condensates and light oils are obtained by adding internal standard——eight deuterium atoms substituted DBT during Gas Chromatography-Mass Spectrometry analysis of aromatic fraction.Except for a few samples with much lower content of non-hydrocarbon fraction,the total DBTs content shows a fine positive correlation with that of carbazoles.Large errors can be caused in the process of pyrrolic nitrogen compounds separation.The application of this new parameter in the Fushan Depression of Beibu Gulf Basin,South China Sea indicates that this parameter is a reliable one to trace filling pathway in condensate reservoirs.Combined with other DBTs-related parameters,such as 4-/1-methydibenzo-thiophene and 2,4-/1,4-dimethyldibenzothiophene,oil migration orientation and filling pathway of the Fushan Depression was determined.The accumulations of Huachang oil field in the Fushan Depres-sion are mainly migrated and charged from northeast to southeast along the Huachang uplift.It can be predicated that the light oil and condensates in the Huachang oil field should be sourced from the source kitchen at the Bailian Sag.It shows that total DBTs content is an effective parameter to tracing oil migration orientation and filling pathway.展开更多
A one-step synthesized Ni-Mo-S catalyst supported on SiO2 was prepared and used for hydrodesulphurization （HDS） of dibenzothiophene （DBT）, and 4,6-dimethyl-dibenzothiophene （4,6-DMDBT）, and for hydrogenation of ...A one-step synthesized Ni-Mo-S catalyst supported on SiO2 was prepared and used for hydrodesulphurization （HDS） of dibenzothiophene （DBT）, and 4,6-dimethyl-dibenzothiophene （4,6-DMDBT）, and for hydrogenation of tetralin. The catalyst showed relatively high HDS activity with complete conversion of DBT and 4,6-DMDBT at temperature of 280℃ and a constant pressure of 435 psi. The HDS conversions of DBT and 4,6- DMDBT increased with increasing temperature and pressure, and decreasing liquid hourly space velocity （LHSV）. The HDS of DBT proceeded mostly through the direct desulphurization （DDS） pathway whereas that of 4,6-DMDBT occurred mainly through the hydrogenation- desulphurization （HYD） pathway. Although the catalyst showed up to 24% hydrogenation/dehydrogenation con- version oftetralin, it had low conversion and selectivity for ring opening and contraction due to the competitive adsorption of DBT and 4,6-DMDBT and insufficient acidic sites on the catalyst surface.展开更多
Thiadiamondoids(TDs)have recently attracted increasing attention as molecular proxies for thermochemical sulfate reduction(TSR)reactions in reservoirs.However,their formation mechanisms,as well as the generation and e...Thiadiamondoids(TDs)have recently attracted increasing attention as molecular proxies for thermochemical sulfate reduction(TSR)reactions in reservoirs.However,their formation mechanisms,as well as the generation and evolution processes,remain poorly understood.In this study,simulation experiments with a duration of 160 h were conducted on the model compound 1,3-dimethyladamantane(1,3-DMA)using the CaSO_(4),MgSO_(4),and elemental S systems,with measurements at the 10th,20th,40th,80th and 160th hours during the simulation process being presented.The results indicate that at the end of simulation,the MgSO_(4) system exhibited the lowest residual amounts of 1,3-DMA,suggesting the highest degree of TSR.Four types of non-hydrocarbon compounds with adamantane structures were detected in the liquid products in the three experiment systems:adamantanones,adamantanols,adamantanethiols(ATs),and thiaadamantanes(TAs).Among these,adamantanones exhibited the highest concentrations in the three simulation systems.In addition,TAs were dominated by C_(3)-TAs in the CaSO_(4) and MgSO_(4) systems and by C_(2)-TAs in the elemental S system.The simulation experiments revealed a strong correlation between the concentrations of TAs and adamantanones,suggesting that adamantanones might be the intermediates for TAs.Combined with the synthesis mechanism of TAs from thiaadamamantane-4,8-dione,TDs might have two different genetic mechanisms:(a)low temperature cationic carbon ion rearrangement from diagenesis to early catagenesis stage,and(b)a free sulfur radical mechanism in high-temperature TSR process during middle-late catagenesis.TAs exhibited different generation and evolution processes across different experiment systems.Notably,the MgSO_(4) system revealed that TAs undergo generation,accumulation,and destruction process,corresponding to Easy%Ro values of 0.89%-0.98%,0.98%-1.21%,and>1.21%,respectively.Among these three simulation systems,dibenzothiophenes(DBTs)concentrations consistently trended upwards,indicating TAs have lower thermal stability than DBTs.展开更多
Preparation of highly active hydrodesulfurization catalysts is extremely meaningful for the sulfur removal from thiophene substances.In this work,commercial nano-Al_(2)O_(3)with mesoporous structure supported monometa...Preparation of highly active hydrodesulfurization catalysts is extremely meaningful for the sulfur removal from thiophene substances.In this work,commercial nano-Al_(2)O_(3)with mesoporous structure supported monometallic phosphide(NiP/Al_(2)O_(3)and MoP/Al_(2)O_(3))and bimetallic phosphide(NiMoP/Al_(2)O_(3)with various Ni/Mo molar ratio)catalysts are successfully prepared by temperature-programmed reduction.X-ray diffraction(XRD)result shows the Ni/Mo molar ratio affect the crystal phase in catalysts.Scanning electron microscopy(SEM),transmission electron microscopy(TEM)and X-ray photoelectron spectroscopy(XPS)characterizations co-confirm the interact between Ni and Mo elements in bimetallic phosphide.Catalyst evaluation in hydrodesulfurization of dibenzothiophene shows that bimetallic phosphide samples exhibit better catalytic performance than monometallic phosphide.62.1%conversion and 86.3%biphenyl selectivity with 30 h stability are achieved over NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst at 400℃under 3 MPa H_(2).All characterization results demonstrate that the improved activity of bimetallic phosphide owes to the Ni-Mo synergistic effect in NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst.This finding provides a guide to the design of bimetallic catalyst with synergistic effect.展开更多
In this study,the infl uence of CeO_(2) loading(5-30 wt%)on the structure and hydrodesulfurization(HDS)performance of Ni-based catalysts for dibenzothiophene(DBT)removal was systematically investigated.Catalysts were ...In this study,the infl uence of CeO_(2) loading(5-30 wt%)on the structure and hydrodesulfurization(HDS)performance of Ni-based catalysts for dibenzothiophene(DBT)removal was systematically investigated.Catalysts were synthesized via incipient wetness co-impregnation and characterized by XRD,N2 adsorption-desorption,SEM,TEM,XPS,and H_(2)-TPR.Results showed that CeO_(2) incorporation improved Ni dispersion and reducibility,with the 10%NiO-30%CeO_(2)/Al_(2)Ocatalyst achieving 99.6%DBT conversion and 90%biphenyl(BP)selectivity under optimal conditions(340℃,4 MPa,WHSV=6 h^(-1)).The presence of CeO_(2) promoted the direct desulfurization(DDS)pathway,reducing hydrogen consumption and preserving aromatic structures.Structural analysis revealed that CeO_(2) enhanced metal-support interactions,leading to the formation of interfaces between Ni and CeO_(2) and improved sulfidation efficiency.These findings provide insights into the design of high-performance Ni-CeO_(2) catalysts for ultra-deep HDS applications.展开更多
Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization（HDS） catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation ...Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization（HDS） catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation method,and characterized using N2 physisorption,X-ray diffraction,temperature-programmed NH3 desorption,temperature-programmed reduction（TPR）,ultraviolet-visible diffuse reflectance spectroscopy,and high-resolution transmission electron microscopy（HRTEM）.The results show that the CoMo/ZK-1 catalysts have high surface areas（～700 m^2/g）,large pore volumes,and hierarchical porous structures,which promote the dispersion of Co and Mo oxide phases on the ZK-1 supports.The TPR results show that the interactions between the Co and Mo oxide phases and the ZK-1 support are weaker than those in the CoMo/γ-Al2O3 catalyst.The HRTEM results show that the CoMo/ZK-1 catalysts have better MoS2 dispersion and more active edge sites.The catalysts were tested in HDS of dibenzothiophene.Under mild reaction conditions,the activity of Co and Mo sulfides supported on ZK-1 was higher than those of Co and Mo sulfides supported on ZSM-5,A1KIT-1,and γ-Al2O3.展开更多
A highly active catalyst of phosphomolybdic acid ~HPMo） was prepared and applied in the catalytic oxidative desulfurization （CODS） system. The catalyst was characterized by FT-IR, XRD, XPS and superconducting NMR. ...A highly active catalyst of phosphomolybdic acid ~HPMo） was prepared and applied in the catalytic oxidative desulfurization （CODS） system. The catalyst was characterized by FT-IR, XRD, XPS and superconducting NMR. The influences of rn（catalyst）/m（oil）, V（H202）fV（oil）, reaction temperature and reaction time on the fractional conversion of benzothiophene （BT） and dibenzothiophene （DBT） were investigated. GC-MS and micra-coulometric methods were employed to investigate the reaction. The catalyst has high desulfurization activity in the removal of BT and DBT under mild conditions. The recycling experiments indicated that DBT and BT removal could still reach 95.2% and 95.7% after 10 cycles.展开更多
Polychlorinated dibenzothiophenes（PCDTs） are a group of important persistent organic pollutants.In the present study,geometrical optimization and electrostatic potential calculations have been performed for all 135 ...Polychlorinated dibenzothiophenes（PCDTs） are a group of important persistent organic pollutants.In the present study,geometrical optimization and electrostatic potential calculations have been performed for all 135 PCDTs congeners at the B3LYP/6-31G＊ level of theory.By means of the VSMP（variable selection and modeling based on prediction） program,one optimal descriptor（molecular polarizability,α） was selected to develop a QSRR model for the prediction of gas chromatographic retention indices（GC-RI） of PCDTs.The estimated correlation coefficients（r2） and LOO-validated correlation coefficients（q2）,all more than 0.99,were built by multiple linear regression,which shows a good estimation ability and stability of the models.A prediction power for the external samples was validated by the model built from the training set with 17 polychlorinated dibenzothiophenes.展开更多
Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxi...Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.展开更多
Commercial hydrodesulfurization(HDS)cata-lysts consist of MoS_(2)-type phases supported on γ-Al2O3 and promoted by Co or Ni[1.2].More strin-gent environmental regulations mean that the activity of such catalysts must...Commercial hydrodesulfurization(HDS)cata-lysts consist of MoS_(2)-type phases supported on γ-Al2O3 and promoted by Co or Ni[1.2].More strin-gent environmental regulations mean that the activity of such catalysts must be improved.Thus,there isgrowing interest in developing alternatives,which in-clude transition metal nitrides and carbides[3,4],to the widely used sulfides.Transition metal phosphides have recently been reported as a new class of highly active hydroprocessing catalysts that have substantial promise as the next generation catalysts.They are a group of stable,sulfur-resistant metallic compounds that have exceptional hydroprocessing properties[5,6].In this paper,Ni_(2)P,MoP,NiMoP,Ni_(2)P/SiO_(2),MoP/SiO_(2) and NiMoP/SiO_(2) were prepared from an inexpensive phosphate precursor by the temperature-programmed reduction method.Dibenzothiophene(DBT)HDS activity of these phosphide catalysts was measured and compared with MoS_(2)/SiO_(2),NiS/SiO_(2) and NiMoS/SiO_(2) catalysts.展开更多
A new bacterial strain DMT-7 capable of selectively desulfurizing dibenzothiophene（DBT） was isolated from diesel contaminated soil.The DMT-7 was characterized and identified as Lysinibacillus sphaericus DMT-7（NCBI ...A new bacterial strain DMT-7 capable of selectively desulfurizing dibenzothiophene（DBT） was isolated from diesel contaminated soil.The DMT-7 was characterized and identified as Lysinibacillus sphaericus DMT-7（NCBI GenBank Accession No.GQ496620） using 16S rDNA gene sequence analysis.The desulfurized product of DBT,2-hydroxybiphenyl（2HBP）,was identified and confirmed by high performance liquid chromatography analysis and gas chromatography-mass spectroscopy analysis respectively.The desulfurization kinetics revealed that DMT-7 started desulfurization of DBT into 2HBP after the lag phase of 24 hr,exponentially increasing the accumulation of 2HBP up to 15 days leading to approximately 60% desulfurization of the DBT.However,further growth resulted into DBT degradation.The induced culture of DMT-7 showed shorter lag phase of 6 hr and early onset of stationary phase within 10 days for desulfurization as compared to that of non-induced culture clearly indicating the inducibility of the desulfurization pathway of DMT-7.In addition,Lysinibacillus sphaericus DMT-7 also possess the ability to utilize broad range of substrates as sole source of sulfur such as benzothiophene,3,4-benzo DBT,4,6-dimethyl DBT,and 4,6-dibutyl DBT.Therefore,Lysinibacillus sphaericus DMT-7 could serve as model system for efficient biodesulfurization of diesel and petrol.展开更多
Platinum group metals(PGMs)usually exhibit promising aerobic catalytic abilities,providing a green and feasible oxidative desulfurization method.However,often,the PGM nanoparticles(NPs)get leached,and the catalysts ar...Platinum group metals(PGMs)usually exhibit promising aerobic catalytic abilities,providing a green and feasible oxidative desulfurization method.However,often,the PGM nanoparticles(NPs)get leached,and the catalysts are deactivated.In this work,Pt NPs with particle sizes of approximately 4–5 nm were encapsulated effectively and uniformly on the surface of vanadium pentoxide(V2O5)nanosheets(with thicknesses of approximately six atomic layers)through strong metal-support interactions.The synthesized catalysts promote catalytic aerobic oxidation reactions,realizing deep desulfurization(99.1%,<5μg g^(–1))under atmospheric pressure and 110℃reaction temperature.Remarkable degrees of sulfur removal could be achieved for oils with different initial S-concentrations and substrates.Additionally,the as-prepared catalysts could be recycled for reuse at least seven times.展开更多
By using the bimodal mesoporous silica(BMMS) as the carrier and butyl titanate as the titanium source, the TiO_2/BMMS catalyst was prepared. The samples were characterized by XRD, XRF, N_2 adsorption and desorption, F...By using the bimodal mesoporous silica(BMMS) as the carrier and butyl titanate as the titanium source, the TiO_2/BMMS catalyst was prepared. The samples were characterized by XRD, XRF, N_2 adsorption and desorption, FTIR, UVvis,SEM, EDS, and TEM techniques. The test results showed that TiO_2 was amorphous, the TiO_2/BMMS catalyst had an ordered bimodal mesoporous structure, and the chemical interaction existed between BMMS and TiO_2. Since the TiO_2/BMMS had a lower band gap, its photocatalytic activity was better than TiO_2. Under UV irradiation a one-pot PODS system was set up, using TiO_2/BMMS as the catalyst, H_2O_2 as the oxidant, and methanol as the solvent. The TiO_2/BMMS catalyst showed better photocatalytic activity than the mono-modal mesoporous TiO_2/SBA-15 catalyst, and the desulfurization rate of dibenzothiophene(DBT) over TiO_2/BMMS catalyst could reach 99._2%. The TiO_2/BMMS catalyst also had so good stability that the desulfurization rate of DBT did not drop apparently after 8 cycles of reusing, and could still be close to 90%.展开更多
Dibenzothiophene(DBT) degradation mechanisms and the transformation of pathways during the incubation of three types of coastal sediments with C/N ratios ranging from 1 to 9 were investigated. The DBT degradation effi...Dibenzothiophene(DBT) degradation mechanisms and the transformation of pathways during the incubation of three types of coastal sediments with C/N ratios ranging from 1 to 9 were investigated. The DBT degradation efficiencies were clearly improved with increasing C/N ratio in reed wetland sediments, tidal wetlands sediments and estuary wetland sediments. The quantitative response relationships between DBT degradation rates and related functional genes demonstrate that the Kodama pathway-related gene groups were dominant factors at low C/N ratios, while the 4S-related gene groups mainly determined the degradation rate when the C/N ratio was up to 5. Network analysis also shows that the pathway shifts from the Kodama pathway to the 4S pathway occurred through changes in the connections between functional genomes and rates. Furthermore, there were competition and collaboration between the Kodama and 4S pathways. The 4S pathway-related bacteria were more active in estuary wetland sediments compared with reed wetland sediments and tidal wetland sediments. The higher degradation efficiency in estuary wetland sediments may indicate the greater participation of the 4S pathway in the DBT biodegradation reaction. And the effects of ring cleavage of Kodama pathway caused more complete metabolizing of DBT.展开更多
A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DE...A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DESs) were used as electron-donors for aerobic oxidative desulfurization(AODS) of diesel fuel. Different compositions of DESs were used and the polyethylene glycol 2000(PEG2000)/2.5 BSA system showed the highest desulfurization activity, with the removal of dibenzothiophene(DBT) at 60 ℃ reaching 95% in 60 min. The excellent desulfurization activity of the system is due to the in situ formation of peroxysulfonate via a biomimetic process. By constructing a coupled redox system, Fe-Anderson type POMs as ETMs reduce the activation energy of oxygen-activated sulfonate. The physical characteristics of four different DESs were tested. The results show that the conductivity of DESs is correlated with the composition of BSA-based DESs. However, there is no similar trend in viscosity testing at the same temperature, and the maximum viscosity value is obtained for the PEG2000/2.5 BSA system at 60 ℃, which may be associated with the stronger hydrogen bonds. It is worth noting that the PEG2000/2.5 BSA system also possesses the best desulfurization activity, which suggests that the activity of the desulfurization system is related to the strength of the hydrogen bond in DESs. Finally, the biomimetic desulfurization system exhibits excellent performance and good stability under mild reaction conditions(60 ℃, atmospheric pressure, oxygen as the oxidant).展开更多
基金Supported by the National Natural Science Foundation of China （20737001）.
文摘The thermodynamic properties of 135 polybrominated dibenzothiophenes （PBDTs） in the gaseous state at 298.15 K and 1.013×10^5 Pa, are calculated using the density functional theory （the B3LYP/6-311G^＊＊） with Gaussian 03. Based on these data, the isodesmic reacflons are designed to calculate the standard enthalpy of formation （△fH^θ） and the standard Gibbs energy of formation （△fG^θ） of PBDTs. The relations of these thermodynamic parameters with the number and positionof bromine subsfituents （NPBS） are discussed, and it is found that there exist good correlations between othermody namic parameters （including heat capacity at constant volume, entropy, enthaipy, free energy, △fH^θ, △fG^θ） and NPBS. Thoe relative stability order of PBDT congeners is proposed theoretically based on the relative magnitude of their △fG^θ. In addition, the values of molar heat capacities at constant pressure （Cp,m） for PBDT c ongelaers are calculated.
基金supported by the National Natural Science Foundation (Nos. 21407167, 21621064, and 21607168)the Chinese Academy of Sciences (No. XDB14030500)
文摘Homogeneous formation of polychlorinated dibenzothiophenes/thianthrenes（PCDT/TAs）,sulfurated compounds analogous to polychlorinated dibenzo-p-dioxin/dibenzofurans（PCDD/Fs）, has been well-documented to occur via radical–radical coupling reactions from chlorinated thiophenol precursors. However, the current understanding of the formation mechanism of PCDT/TAs is exclusively limited to the inherent point of view that chlorothiophenoxy radicals act as the only required intermediates for PCDT/TAs. This study investigates reaction pathways for the formation of PCDT/TAs involving two new types of radical species, i.e., substituted phenyl radicals and substituted thiophenoxyl diradicals. Taking 2-chlorothiophenol（2-CTP） as a model compound for chlorothiophenols,we found that apart from the mostly discussed chlorothiophenoxy radicals, substituted phenyl radicals and substituted thiophenoxyl diradicals could also be readily formed via the reaction of 2-CTP with H radicals. Furthermore, direct self-and cross-coupling of these radicals can result in the formation of PCDT/TAs, including 1-monochlorothianthrene（1-MCTA）, 1,6-dichlorothianthrene（1,6-DCTA）, 4,6-dichlorodibenzothiophene（4,6-DCDT）and 1,6-dichlorodibenzothiophene（1,6-DCDT）. The pathways proposed in this work are proven to be both thermodynamically and kinetically favorable. Particularly, comparisons were made between the formation mechanisms of sulfurated and oxygenated dioxin systems from an energetic point view, showing that replacing oxygen with sulfur atoms greatly reduces the activation barriers of the rate-controlling steps involved in the PCDT/TA formation processes compared with those involved for PCDD/Fs. The calculated results in this work may improve our understanding of the formation mechanism of PCDT/TAs from chlorothiophenol precursors and should be informative to environmental scientists.
基金funded by the National Natural Science Foundation of China (Grant No. 41272158)the State Key Laboratory of Petroleum Resources and Prospecting (PRP/indep-2-1302)
文摘Aromatic fractions of 140 oils and condensates that originated from different types of source rocks （marine shale,terrestrial shale and marine carbonate） were analyzed using gas chromatographymass spectrometry （GC-MS） to investigate the relative distributions of methylated dibenzothiophenes with respect to thermal maturity.The positions of methyl groups of trimethyldibenzothiophene isomers （TMDBTs） including those used in the definition of maturity indicator TMDBT index in previous studies were firmly identified by co-elution of internal standards in GC-MS analysis and by comparing with reported retention indices.A new maturity ratio related to dimethyldibenzothiophenes （DMDBTs） is proposed on the basis of the differences in thermodynamic stability among different DMDBT isomers.Another maturity index （TMDBT-I2） based on TMDBTs is also suggested on the basis of our empirical observations and presumed thermodynamic stability of TMDBT isomers.These two newly proposed （2,6 ＋ 3,6）-/1,4-DMDBT ratio and TMDBT-I2 correlate well with MDR （4-/1-methyldibenzothiophene）and 2,4-/1,4-DMDBT ratios,suggesting their common chemical reaction mechanisms and similar behavior with increasing maturity.Therefore,they can be effectively applied for maturity assessments.Furthermore,the TMDBTs related maturity parameters are more reliable for over-mature oils and condensates due to the relatively higher concentrations of thermodynamically unstable TMDBT isomers,i.e.1,4,6-,1,4,8-and 3,4,6-TMDBT in this study than those of 1-methyldibenzothiophene （1-MDBT） or 1,4-DMDBT.In contrast with 4,6-/1,4-DMDBT,the newly proposed （2,6 ＋ 3,6）-/1,4-DMDBT ratios for oils that originated from different types of source rocks have approximately same relationship with the oil maturity （Rc %）.This suggests that the lithology and organic facies may have relatively less influence on （2,6 ＋ 3,6）-/1,4-DMDBT ratio compared to 4,6-/1,4-DMDBT.The maturity parameters based on methylated dibenzothiophenes are particularly useful in the maturity assessments of post-and over-mature oils and condensates and can complement maturity indicators based on steranes and terpanes.
基金supported by the Science and Technology Project of Zhejiang Province(2016C33039)the Public Technology Research Project(Analysis and Measurement)of Zhejiang Province(LGC19B070004)+1 种基金State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences(KF2018-15)Natural Science Foundation of Zhejiang Province(LY18C030003)
文摘Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations of electrostatic potentials(ESPs)on molecular surface have been performed for all 135 PCDTs and 135 PCDTO2 congeners at the HF/6-31G*level of theory.A number of statistically-based parameters have been extracted.Linear relationship between gas-chromatographic retention index(RI)and the structural descriptors have been established by multiple linear regression.The result shows that two descriptors derived from positive electrostatic potential on molecular surface,■andπ,together with the molecular volume(Vmc)and the energy of the lowest unoccupied molecular orbital(ELUMO)can be well used to express the quantitative structure-retention relationship(QSRR)of PCDTs and PCDTO2.Predictive capability of the two models has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient(RCV)of 0.996 and 0.997,respectively.Furthermore,the predictive power of the models is further examined for the external test set.Correlation coefficients(R)between the observed and predicted RI values for the external test set are 0.997 and0.998,respectively,validating the robustness and good prediction of our model.The QSRR model established may provide again a powerful method for predicting chromatographic properties of aromatic organosulfur compounds.
基金sponsored by the National Natural Science Foundation of China(No.22308381 and 22402093)Science Foundation of China University of Petroleum-Beijing(No.2462023QNXZ002 and 2462023QNXZ005)the Special Foundation of Nanyang Normal University(No.2024ZX003).
文摘TS-1 zeolites with different grain sizes were prepared under hydrothermal conditions by tuning the amount of template agent,chelating agent,and temperature,which were further used as supports for the NiMo/TS-1 catalysts.The optimization of synthesis conditions has achieved controllable synthesis of grain sizes from nano-scale to micron-scale.TS-1 with smaller grain sizes possess larger specific surface area,external specific surface area,and pore volume,which can effectively shorten the diffusion path of the sulfide with complex structure.Nanoscale TS-1 has more highly-coordinated Ti species,acting as electronic additives to increase the sulfidation degree of the catalyst.Nano-scale NiMo/TS-1 exhibits higher acidity,which is beneficial for hydrodesulfurization(HDS)reactions.Among the series of NiMo/TS-1 catalysts,NiMo/TS-1(120 nm)catalyst exhibits the highest dibenzothiophene(DBT,88.4%)and 4,6-dimethylbenzothiophene(4,6-DMDBT,62.1%)HDS activities.
基金Supported by the National Natural Science Foundation of China(Grant No.40672093)the CNPC Innovation Fund(Grant No.07E1001)
文摘The condensates are generally characterized by high maturity,low concentration of steranes and ter-panes biomarkers and low content of non-hydrocarbon fraction.In this case commonly used steranes,terpanes and carbazoles parameters cannot be effectively applied in the reservoir-filling tracing.The hydrogen bond formed by sulfur atom in the dibenzothiophenes(DBTs)results in molecule adsorption and fractionation during oil migration in reservoir.Like carbazoles,total DBTs content decreases with the increasing of oil migration distance.Therefore,a new parameter——total DBTs content is proposed to be used to trace the oil migration orientation and filling pathway.In present study,total DBTs con-tents of condensates and light oils are obtained by adding internal standard——eight deuterium atoms substituted DBT during Gas Chromatography-Mass Spectrometry analysis of aromatic fraction.Except for a few samples with much lower content of non-hydrocarbon fraction,the total DBTs content shows a fine positive correlation with that of carbazoles.Large errors can be caused in the process of pyrrolic nitrogen compounds separation.The application of this new parameter in the Fushan Depression of Beibu Gulf Basin,South China Sea indicates that this parameter is a reliable one to trace filling pathway in condensate reservoirs.Combined with other DBTs-related parameters,such as 4-/1-methydibenzo-thiophene and 2,4-/1,4-dimethyldibenzothiophene,oil migration orientation and filling pathway of the Fushan Depression was determined.The accumulations of Huachang oil field in the Fushan Depres-sion are mainly migrated and charged from northeast to southeast along the Huachang uplift.It can be predicated that the light oil and condensates in the Huachang oil field should be sourced from the source kitchen at the Bailian Sag.It shows that total DBTs content is an effective parameter to tracing oil migration orientation and filling pathway.
文摘A one-step synthesized Ni-Mo-S catalyst supported on SiO2 was prepared and used for hydrodesulphurization （HDS） of dibenzothiophene （DBT）, and 4,6-dimethyl-dibenzothiophene （4,6-DMDBT）, and for hydrogenation of tetralin. The catalyst showed relatively high HDS activity with complete conversion of DBT and 4,6-DMDBT at temperature of 280℃ and a constant pressure of 435 psi. The HDS conversions of DBT and 4,6- DMDBT increased with increasing temperature and pressure, and decreasing liquid hourly space velocity （LHSV）. The HDS of DBT proceeded mostly through the direct desulphurization （DDS） pathway whereas that of 4,6-DMDBT occurred mainly through the hydrogenation- desulphurization （HYD） pathway. Although the catalyst showed up to 24% hydrogenation/dehydrogenation con- version oftetralin, it had low conversion and selectivity for ring opening and contraction due to the competitive adsorption of DBT and 4,6-DMDBT and insufficient acidic sites on the catalyst surface.
基金funded by the Natural Science Foundation of China(Grants Nos.42272167,U24B6001,and 41772153)Science&Technology Project of Sinopec(Grant Nos.P23167 and P24173).
文摘Thiadiamondoids(TDs)have recently attracted increasing attention as molecular proxies for thermochemical sulfate reduction(TSR)reactions in reservoirs.However,their formation mechanisms,as well as the generation and evolution processes,remain poorly understood.In this study,simulation experiments with a duration of 160 h were conducted on the model compound 1,3-dimethyladamantane(1,3-DMA)using the CaSO_(4),MgSO_(4),and elemental S systems,with measurements at the 10th,20th,40th,80th and 160th hours during the simulation process being presented.The results indicate that at the end of simulation,the MgSO_(4) system exhibited the lowest residual amounts of 1,3-DMA,suggesting the highest degree of TSR.Four types of non-hydrocarbon compounds with adamantane structures were detected in the liquid products in the three experiment systems:adamantanones,adamantanols,adamantanethiols(ATs),and thiaadamantanes(TAs).Among these,adamantanones exhibited the highest concentrations in the three simulation systems.In addition,TAs were dominated by C_(3)-TAs in the CaSO_(4) and MgSO_(4) systems and by C_(2)-TAs in the elemental S system.The simulation experiments revealed a strong correlation between the concentrations of TAs and adamantanones,suggesting that adamantanones might be the intermediates for TAs.Combined with the synthesis mechanism of TAs from thiaadamamantane-4,8-dione,TDs might have two different genetic mechanisms:(a)low temperature cationic carbon ion rearrangement from diagenesis to early catagenesis stage,and(b)a free sulfur radical mechanism in high-temperature TSR process during middle-late catagenesis.TAs exhibited different generation and evolution processes across different experiment systems.Notably,the MgSO_(4) system revealed that TAs undergo generation,accumulation,and destruction process,corresponding to Easy%Ro values of 0.89%-0.98%,0.98%-1.21%,and>1.21%,respectively.Among these three simulation systems,dibenzothiophenes(DBTs)concentrations consistently trended upwards,indicating TAs have lower thermal stability than DBTs.
基金supported by National Natural Science Foundation of China(22202093)the Scientific and Technological Innovation Youth Talent Team of Shanxi Province(202204051001005)。
文摘Preparation of highly active hydrodesulfurization catalysts is extremely meaningful for the sulfur removal from thiophene substances.In this work,commercial nano-Al_(2)O_(3)with mesoporous structure supported monometallic phosphide(NiP/Al_(2)O_(3)and MoP/Al_(2)O_(3))and bimetallic phosphide(NiMoP/Al_(2)O_(3)with various Ni/Mo molar ratio)catalysts are successfully prepared by temperature-programmed reduction.X-ray diffraction(XRD)result shows the Ni/Mo molar ratio affect the crystal phase in catalysts.Scanning electron microscopy(SEM),transmission electron microscopy(TEM)and X-ray photoelectron spectroscopy(XPS)characterizations co-confirm the interact between Ni and Mo elements in bimetallic phosphide.Catalyst evaluation in hydrodesulfurization of dibenzothiophene shows that bimetallic phosphide samples exhibit better catalytic performance than monometallic phosphide.62.1%conversion and 86.3%biphenyl selectivity with 30 h stability are achieved over NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst at 400℃under 3 MPa H_(2).All characterization results demonstrate that the improved activity of bimetallic phosphide owes to the Ni-Mo synergistic effect in NiMoP/Al_(2)O_(3)(Ni/Mo=1∶1)catalyst.This finding provides a guide to the design of bimetallic catalyst with synergistic effect.
基金supported financially by the project of Tianchi Talent(BT-2025-TCYC-0059)the Science and Technology Commission of Shanghai Municipality(10dz2220500).
文摘In this study,the infl uence of CeO_(2) loading(5-30 wt%)on the structure and hydrodesulfurization(HDS)performance of Ni-based catalysts for dibenzothiophene(DBT)removal was systematically investigated.Catalysts were synthesized via incipient wetness co-impregnation and characterized by XRD,N2 adsorption-desorption,SEM,TEM,XPS,and H_(2)-TPR.Results showed that CeO_(2) incorporation improved Ni dispersion and reducibility,with the 10%NiO-30%CeO_(2)/Al_(2)Ocatalyst achieving 99.6%DBT conversion and 90%biphenyl(BP)selectivity under optimal conditions(340℃,4 MPa,WHSV=6 h^(-1)).The presence of CeO_(2) promoted the direct desulfurization(DDS)pathway,reducing hydrogen consumption and preserving aromatic structures.Structural analysis revealed that CeO_(2) enhanced metal-support interactions,leading to the formation of interfaces between Ni and CeO_(2) and improved sulfidation efficiency.These findings provide insights into the design of high-performance Ni-CeO_(2) catalysts for ultra-deep HDS applications.
基金financially supported by the National Natural Science Foundation of China (NNSFC,21206017)~~
文摘Micro-mesoporous ZK-1 molecular sieves with different Si/Al ratios were used as supports for binary Co-Mo hydrodesulfurization（HDS） catalysts.The CoMo/ZK-1 catalysts were prepared using an over-loading impregnation method,and characterized using N2 physisorption,X-ray diffraction,temperature-programmed NH3 desorption,temperature-programmed reduction（TPR）,ultraviolet-visible diffuse reflectance spectroscopy,and high-resolution transmission electron microscopy（HRTEM）.The results show that the CoMo/ZK-1 catalysts have high surface areas（～700 m^2/g）,large pore volumes,and hierarchical porous structures,which promote the dispersion of Co and Mo oxide phases on the ZK-1 supports.The TPR results show that the interactions between the Co and Mo oxide phases and the ZK-1 support are weaker than those in the CoMo/γ-Al2O3 catalyst.The HRTEM results show that the CoMo/ZK-1 catalysts have better MoS2 dispersion and more active edge sites.The catalysts were tested in HDS of dibenzothiophene.Under mild reaction conditions,the activity of Co and Mo sulfides supported on ZK-1 was higher than those of Co and Mo sulfides supported on ZSM-5,A1KIT-1,and γ-Al2O3.
基金supported by the National Natural Science Foundation of China (21473126)~~
文摘A highly active catalyst of phosphomolybdic acid ~HPMo） was prepared and applied in the catalytic oxidative desulfurization （CODS） system. The catalyst was characterized by FT-IR, XRD, XPS and superconducting NMR. The influences of rn（catalyst）/m（oil）, V（H202）fV（oil）, reaction temperature and reaction time on the fractional conversion of benzothiophene （BT） and dibenzothiophene （DBT） were investigated. GC-MS and micra-coulometric methods were employed to investigate the reaction. The catalyst has high desulfurization activity in the removal of BT and DBT under mild conditions. The recycling experiments indicated that DBT and BT removal could still reach 95.2% and 95.7% after 10 cycles.
基金Sponsored by the NSF of Guangxi Province (No. 2011XNSFA018059)Guangxi Key Laboratory Research Fund of Environmental Engineering and Protection Assessment (No. 0801Z026)+1 种基金Major Science of Water Pollution Control and Management (No. 2008ZX07317-02)the Guangxi Zhuang Autonomous Region Department of Education Research (No. 201010LX174) Funding
文摘Polychlorinated dibenzothiophenes（PCDTs） are a group of important persistent organic pollutants.In the present study,geometrical optimization and electrostatic potential calculations have been performed for all 135 PCDTs congeners at the B3LYP/6-31G＊ level of theory.By means of the VSMP（variable selection and modeling based on prediction） program,one optimal descriptor（molecular polarizability,α） was selected to develop a QSRR model for the prediction of gas chromatographic retention indices（GC-RI） of PCDTs.The estimated correlation coefficients（r2） and LOO-validated correlation coefficients（q2）,all more than 0.99,were built by multiple linear regression,which shows a good estimation ability and stability of the models.A prediction power for the external samples was validated by the model built from the training set with 17 polychlorinated dibenzothiophenes.
基金supported by the National Natural Science Foundation of China(21676230,21373177)~~
文摘Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.
基金Supported by the National Basic Researeh Program of China(G2000048003)the National Natural Science Foundationof China(20303018).
文摘Commercial hydrodesulfurization(HDS)cata-lysts consist of MoS_(2)-type phases supported on γ-Al2O3 and promoted by Co or Ni[1.2].More strin-gent environmental regulations mean that the activity of such catalysts must be improved.Thus,there isgrowing interest in developing alternatives,which in-clude transition metal nitrides and carbides[3,4],to the widely used sulfides.Transition metal phosphides have recently been reported as a new class of highly active hydroprocessing catalysts that have substantial promise as the next generation catalysts.They are a group of stable,sulfur-resistant metallic compounds that have exceptional hydroprocessing properties[5,6].In this paper,Ni_(2)P,MoP,NiMoP,Ni_(2)P/SiO_(2),MoP/SiO_(2) and NiMoP/SiO_(2) were prepared from an inexpensive phosphate precursor by the temperature-programmed reduction method.Dibenzothiophene(DBT)HDS activity of these phosphide catalysts was measured and compared with MoS_(2)/SiO_(2),NiS/SiO_(2) and NiMoS/SiO_(2) catalysts.
文摘A new bacterial strain DMT-7 capable of selectively desulfurizing dibenzothiophene（DBT） was isolated from diesel contaminated soil.The DMT-7 was characterized and identified as Lysinibacillus sphaericus DMT-7（NCBI GenBank Accession No.GQ496620） using 16S rDNA gene sequence analysis.The desulfurized product of DBT,2-hydroxybiphenyl（2HBP）,was identified and confirmed by high performance liquid chromatography analysis and gas chromatography-mass spectroscopy analysis respectively.The desulfurization kinetics revealed that DMT-7 started desulfurization of DBT into 2HBP after the lag phase of 24 hr,exponentially increasing the accumulation of 2HBP up to 15 days leading to approximately 60% desulfurization of the DBT.However,further growth resulted into DBT degradation.The induced culture of DMT-7 showed shorter lag phase of 6 hr and early onset of stationary phase within 10 days for desulfurization as compared to that of non-induced culture clearly indicating the inducibility of the desulfurization pathway of DMT-7.In addition,Lysinibacillus sphaericus DMT-7 also possess the ability to utilize broad range of substrates as sole source of sulfur such as benzothiophene,3,4-benzo DBT,4,6-dimethyl DBT,and 4,6-dibutyl DBT.Therefore,Lysinibacillus sphaericus DMT-7 could serve as model system for efficient biodesulfurization of diesel and petrol.
文摘Platinum group metals(PGMs)usually exhibit promising aerobic catalytic abilities,providing a green and feasible oxidative desulfurization method.However,often,the PGM nanoparticles(NPs)get leached,and the catalysts are deactivated.In this work,Pt NPs with particle sizes of approximately 4–5 nm were encapsulated effectively and uniformly on the surface of vanadium pentoxide(V2O5)nanosheets(with thicknesses of approximately six atomic layers)through strong metal-support interactions.The synthesized catalysts promote catalytic aerobic oxidation reactions,realizing deep desulfurization(99.1%,<5μg g^(–1))under atmospheric pressure and 110℃reaction temperature.Remarkable degrees of sulfur removal could be achieved for oils with different initial S-concentrations and substrates.Additionally,the as-prepared catalysts could be recycled for reuse at least seven times.
基金financially supported by the Program for Liaoning Excellent Talents in University,abbreviated as“LNET”(LJQ2015062)Program for Science and Technology Agency of Liaoning Province(20170540585)+1 种基金General Scientific Research Project of Liaoning Provincial Department of Education(L2015296,L2016018)Science and Technology Planning project of Fushun(FSKJHT201376)
文摘By using the bimodal mesoporous silica(BMMS) as the carrier and butyl titanate as the titanium source, the TiO_2/BMMS catalyst was prepared. The samples were characterized by XRD, XRF, N_2 adsorption and desorption, FTIR, UVvis,SEM, EDS, and TEM techniques. The test results showed that TiO_2 was amorphous, the TiO_2/BMMS catalyst had an ordered bimodal mesoporous structure, and the chemical interaction existed between BMMS and TiO_2. Since the TiO_2/BMMS had a lower band gap, its photocatalytic activity was better than TiO_2. Under UV irradiation a one-pot PODS system was set up, using TiO_2/BMMS as the catalyst, H_2O_2 as the oxidant, and methanol as the solvent. The TiO_2/BMMS catalyst showed better photocatalytic activity than the mono-modal mesoporous TiO_2/SBA-15 catalyst, and the desulfurization rate of dibenzothiophene(DBT) over TiO_2/BMMS catalyst could reach 99._2%. The TiO_2/BMMS catalyst also had so good stability that the desulfurization rate of DBT did not drop apparently after 8 cycles of reusing, and could still be close to 90%.
基金Foundation for Innovative Research Groups of the National Natural Science Foundation of China (No.51721006)the National Natural Science Foundation of China (No.51679001) provided support for this study
文摘Dibenzothiophene(DBT) degradation mechanisms and the transformation of pathways during the incubation of three types of coastal sediments with C/N ratios ranging from 1 to 9 were investigated. The DBT degradation efficiencies were clearly improved with increasing C/N ratio in reed wetland sediments, tidal wetlands sediments and estuary wetland sediments. The quantitative response relationships between DBT degradation rates and related functional genes demonstrate that the Kodama pathway-related gene groups were dominant factors at low C/N ratios, while the 4S-related gene groups mainly determined the degradation rate when the C/N ratio was up to 5. Network analysis also shows that the pathway shifts from the Kodama pathway to the 4S pathway occurred through changes in the connections between functional genomes and rates. Furthermore, there were competition and collaboration between the Kodama and 4S pathways. The 4S pathway-related bacteria were more active in estuary wetland sediments compared with reed wetland sediments and tidal wetland sediments. The higher degradation efficiency in estuary wetland sediments may indicate the greater participation of the 4S pathway in the DBT biodegradation reaction. And the effects of ring cleavage of Kodama pathway caused more complete metabolizing of DBT.
文摘A unique redox-coupled biomimetic system was developed, in which Fe-Anderson type polyoxometalates(POMs) were employed as electron transfer mediators(ETMs) and benzenesulfonic acid(BSA)-based deep eutectic solvents(DESs) were used as electron-donors for aerobic oxidative desulfurization(AODS) of diesel fuel. Different compositions of DESs were used and the polyethylene glycol 2000(PEG2000)/2.5 BSA system showed the highest desulfurization activity, with the removal of dibenzothiophene(DBT) at 60 ℃ reaching 95% in 60 min. The excellent desulfurization activity of the system is due to the in situ formation of peroxysulfonate via a biomimetic process. By constructing a coupled redox system, Fe-Anderson type POMs as ETMs reduce the activation energy of oxygen-activated sulfonate. The physical characteristics of four different DESs were tested. The results show that the conductivity of DESs is correlated with the composition of BSA-based DESs. However, there is no similar trend in viscosity testing at the same temperature, and the maximum viscosity value is obtained for the PEG2000/2.5 BSA system at 60 ℃, which may be associated with the stronger hydrogen bonds. It is worth noting that the PEG2000/2.5 BSA system also possesses the best desulfurization activity, which suggests that the activity of the desulfurization system is related to the strength of the hydrogen bond in DESs. Finally, the biomimetic desulfurization system exhibits excellent performance and good stability under mild reaction conditions(60 ℃, atmospheric pressure, oxygen as the oxidant).
