为了丰富过硫化氢分子和过硫化氢一价阳离子的电子基态和激发态的信息,采用量子化学中密度泛函理论的B3LYP方法,使用6-311++g(3df,3pd)基组,对其进行了研究。计算得到了过硫化氢分子HSSH基态和过硫化氢离子HSSH+基态及激发态的平衡构型...为了丰富过硫化氢分子和过硫化氢一价阳离子的电子基态和激发态的信息,采用量子化学中密度泛函理论的B3LYP方法,使用6-311++g(3df,3pd)基组,对其进行了研究。计算得到了过硫化氢分子HSSH基态和过硫化氢离子HSSH+基态及激发态的平衡构型、光谱常数、总能量和零点振动能。计算表明:过硫化氢中性分子是长对称陀螺分子,二面角为90.66°,具有C_2对称性,而过硫化氢离子HSSH+有顺式(二面角为0°)和反式(二面角为180°)两种稳定的异构体,反式结构基态能量比顺式结构基态能量低0.129 e V;此外计算还得到了过硫化氢离子HSSH+两种异构体的基态和激发态的电子结构。展开更多
A bench-scale experiment for control of hydrogen sulfide (H2S) emissions was carried out continuously for nearly four months by using bio-trickling filter packed with ZX01 stuffing. The results suggested that the bi...A bench-scale experiment for control of hydrogen sulfide (H2S) emissions was carried out continuously for nearly four months by using bio-trickling filter packed with ZX01 stuffing. The results suggested that the bio-trickling filter had proven excellent performance over substantial operational periods. Removal efficiency of H2S was nearly 100% when volumetric loading of the bio-trickling filter varied from 0.64 g/(m^3·h) to 38.20 g/(m^3·h) and metabolism products of H2S were mainly composed of SO4^2-. When inlet concentration of H2S was 250 mg/m^3, the optimum gas retention time was 30 s and the optimum spray water flow rate was 0.005 9-0.012 L/(cm^2·h). The bio-trickling filter had good ability to resist shock of high volumetric loading, and was not blocked during experiments for nearly four months during which resistance was maintained at relatively lower value, so that the bio-trickling filter need not carry out back washing frequently and can be operated steadily for long-term.展开更多
Hydrogen peroxide was used as an oxidant to modify the cuprite surface and enhance its sulfidization.Surface-adsorption and infrared spectroscopy measurements indicated that the modification of the cuprite surface wit...Hydrogen peroxide was used as an oxidant to modify the cuprite surface and enhance its sulfidization.Surface-adsorption and infrared spectroscopy measurements indicated that the modification of the cuprite surface with hydrogen peroxide before sulfidization increased the adsorption capacity of xanthate.Zeta potential,scanning electron microscopy-energy dispersive X-ray spectroscopy,X-ray photoelectron spectroscopy,and time-of-flight secondary ion mass spectrometry results showed that the modification with hydrogen peroxide increased the contents of S^(2−)and Sn^(2−)species on the cuprite surface.Microflotation tests showed that the recovery of cuprite increased from 61.74%to 83.30%after the modification of the surface with hydrogen peroxide.These results confirm that the modification of the cuprite surface with hydrogen peroxide enhances the sulfidization of cuprite,which in turn improves its flotation.展开更多
The reaction of laser-ablated vanadium, niobium and tantalum atoms with hydrogen sulfide has been investigated using matrix isolation FTIR and theoretical calculations. The metal atoms inserted into the H-S bond of H2...The reaction of laser-ablated vanadium, niobium and tantalum atoms with hydrogen sulfide has been investigated using matrix isolation FTIR and theoretical calculations. The metal atoms inserted into the H-S bond of H2S to form the HMSH molecules (M=V, Nb, Ta), which rearranged to H2MS molecules on annealing for Nb and Ta. The HMSH molecule can also further react with another H2S to form the H2M(SH)2 molecules. These new molecules were identified on the basis of the D2S and H234S isotopic substitutions. DFT (B3LYP and BPW91) theoretical calculations are used to predict energies, geometries, and vibrational frequencies for these novel metal dihydrido complexes and molecules. Reaction mechanism for formation of group V dihydrido complex was investigated by DFT internal reaction coordinate calculations. The dissociation of HVSH gave VS+H2 on broad band irradiation and reverse reaction happened on annealing. Based on B3LYP calculation releasing hydrogen from HVSH is endothermic only by 13.5 kcal/mol with lower energy barrier of 16.9 kcal/mol.展开更多
Iodine-sulfur (IS) thermochemical water-splitting cycle is the most promising massive hydrogen production process. To avoid the undesirable side reactions between hydriodic acid(HI) and sulfuric acid (H2SO4), it...Iodine-sulfur (IS) thermochemical water-splitting cycle is the most promising massive hydrogen production process. To avoid the undesirable side reactions between hydriodic acid(HI) and sulfuric acid (H2SO4), it is necessary to purify the two phases formed by the Bunsen reaction. The purification process could be achieved by reverse reaction of the Bunsen reaction. In this study, the purification of the H2SO4 and HI Phases was studied. The purification proceeded in both batches and the continuous mode, the influences of operational parameters, including the reaction temperature, the flow rate of nitrogen gas, and the composition of the raw material solutions, on the purification effect, were investigated. Results showed that the purification of the H2SO4 phase was dominantly-affected by the reaction temperature, and iodine ion in the sulfuric acid phase could be removed completely when the temperature was above 130℃; although, the purification effect of the HI phase improved with increasing of both the flow rate of nitrogen gas and temperature.展开更多
Transition metal sulfides(TMSs)-based materials have been extensively investigated as effective non-noble catalysts for various applications.However,the exploration of TMSs-based catalysts for hydrogenation of nitro c...Transition metal sulfides(TMSs)-based materials have been extensively investigated as effective non-noble catalysts for various applications.However,the exploration of TMSs-based catalysts for hydrogenation of nitro compounds is limited.Herein,CoSx/NC catalysts were prepared by solvothermal sulfurization of ZIF-67,followed by high-temperature annealing(300–600℃)under NH3 atmosphere.It was found that the structures and compositions of the as-prepared CoSx/NC can be readily tuned by varying the annealing temperature.Particularly,CoSx/NC-500,which possesses higher degree of S defects and larger specific surface areas,can achieve high conversion,selectivity and stability for catalytic reduction of nitro compounds into amines under mild reaction conditions.展开更多
Because of the highly toxic cyanide in the gold cyanide residues,cyanide must be removed for environmental protection.The process mineralogy of residues was studied firstly,and then cyanide removal was carried out by ...Because of the highly toxic cyanide in the gold cyanide residues,cyanide must be removed for environmental protection.The process mineralogy of residues was studied firstly,and then cyanide removal was carried out by three chemical methods.The results showed that the residue mainly contained Si,S and Fe.Pyrite was the main metallic mineral,and the iron-complex cyanides make cyanide removal difficult.The minerals in residues were in ultrafine particle size with high monomer dissociation degrees.In H_(2)O_(2)oxidation process,the self-decomposition and side reactions resulted in high consumption of H_(2)O_(2).In Na_(2)S_(2)O_(5)-air oxidation process,the time for complete process was long because of the reactions between Na_(2)S_(2)O_(5)and O_(2).Na_(2)SO_(3)oxidation method was found to be a new method for cyanide removal without air inflation device.The cyanide content was reduced to the national standard level in 90 min at pH 9.0 with optimum Na_(2)SO_(3)dose of 2.0 g/L.展开更多
Commercial coke was modified by H2O2 and/or NH3.H2O to obtain an activated coke containing additional oxygen functional groups and/or nitrogen functional groups. The aim of the modification was to enhance the SO2 adso...Commercial coke was modified by H2O2 and/or NH3.H2O to obtain an activated coke containing additional oxygen functional groups and/or nitrogen functional groups. The aim of the modification was to enhance the SO2 adsorption capacity of the activated coke. Several techniques, including total nitrogen content measurements, SO2 adsorption, XPS and FTIR analysis, were used to characterize the coke samples. The XPS and FTIR spectra suggest the existence of -CONH2 groups in the H2O2 plus ammonia modified coke. The SO2 adsorption capacity of an activated coke increases slightly with an increase in H2O2 concentration during the modification process. The desulphurization performance of a modified coke is considerably enhanced by increasing the treatment temperature during ammonia modification. The amount of nitrogen in a coke modified by H2O2 plus NH3.H2O is the highest, and the SO2 adsorption capacity of the coke is also the highest (89.9 mg/gC). The NH3.H2O (only) modified sample has lower nitrogen content and lower desulphurization capacity (79.9 mg/gC). H2O modification gives the lowest SO2 adsorption capacity (28.9 mg/gC). The H2O2 pre-treatment is beneficial for the introduction of nitrogen onto the surface of a sample during the following ammonia treatment process.展开更多
Two-dimensional materials(2D)with unique physicochemical properties have been widely studied for their use in many applications,including as hydrogen evolution catalysts to improve the efficiency of water splitting.Re...Two-dimensional materials(2D)with unique physicochemical properties have been widely studied for their use in many applications,including as hydrogen evolution catalysts to improve the efficiency of water splitting.Recently,typical 2D materials MoS2,graphene,MXenes,and black phosphorus have been widely investigated for their application in the hydrogen evolution reaction(HER).In this review,we summarize three efficient strategies—defect engineering,heterostructure formation,and heteroatom doping—for improving the HER performance of 2D catalysts.The d-band theory,density of states,and Fermi energy level are discussed to provide guidance for the design and construction of novel 2D materials.The challenges and prospects of 2D materials in the HER are also considered.展开更多
Oxidative desulfurization was performed on Na2WO4 catalyst in the presence of hydrogen peroxide and acetic acid under mild reaction conditions (atmospheric pressure and temperature range of 293--343 K). Different or...Oxidative desulfurization was performed on Na2WO4 catalyst in the presence of hydrogen peroxide and acetic acid under mild reaction conditions (atmospheric pressure and temperature range of 293--343 K). Different organic compounds including benzothiophene (BT), dibenzothiophene (DBT), 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) were used to investigate the reactivity of this catalyst, and the effect of various parameters, such as temperature, solvents and the amount of oxidant reagent used in oxidative desulfurization reaction, was also examined. The results showed that the Na2WO4- H202 system was very effective for oxidative desulfurization, and the oxidation of BT, DBT and 4, 6-DMDBT was influenced by different parameters.展开更多
This article describes two kinds of model oil samples made of a benzothiophene/octane mixture and a 2-me- thylthiophene/octane mixture. Furthermore, this paper investigates the oxidative desulfurization selectivity an...This article describes two kinds of model oil samples made of a benzothiophene/octane mixture and a 2-me- thylthiophene/octane mixture. Furthermore, this paper investigates the oxidative desulfurization selectivity and reaction efficiency when Ce4+ compound and H2O2 having identical electron equivalent weight were used as oxidants. The test re- sults showed that the two kinds of oxidants were more effective to remove benzothiophene in the model oil samples. For oxidative desulfurization of 2-methylthiophene, Ce4+ compound was obviously superior than H2O2. This paper by means of quantum chemistry analyses elaborates the complex formed between Ce4+ species and 2-methylthiophene and FT-IR spec- trograms of model oil samples before and after oxidation by Ce4+ compound and H2O2, respectively. The results demonstrat- ed that Ce4+ compound could remove sulfur compounds not only through oxidation reaction but also through complexation reaction.展开更多
Aiming at deep desulfurization of gasoline,three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,or 3) were prepared and characterized.The amphiphilic vanadium(V)-substituted polyoxometalates were dissol...Aiming at deep desulfurization of gasoline,three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,or 3) were prepared and characterized.The amphiphilic vanadium(V)-substituted polyoxometalates were dissolved in water-immiscible ionic liquid([Bmim]PF6),forming a H2O2-in-[Bmim]PF6 emulsion desulfurization system with 30 m% H2O2 serving as the oxidant.The catalytic oxidation of sulfur-containing model oil has been studied in detail under various reaction conditions using this system.The ionic liquid emulsion system showed high catalytic oxidative activity in the treatment of commodity gasoline.Furthermore,the mechanism of catalytic oxidative desulfurization was also elaborated.展开更多
Deep desulfurization of liquid fuels is an important and challenging issue in worldwide petroleum refining industry.Extraction and catalytic oxidative desulfurization(ECODS)of liquid fuels using a series of ionic liqu...Deep desulfurization of liquid fuels is an important and challenging issue in worldwide petroleum refining industry.Extraction and catalytic oxidative desulfurization(ECODS)of liquid fuels using a series of ionic liquids(ILs)with two functionalized groups,such as[(CH2)2COOHmim]Cl/n Fe Cl3,[(CH2)2COOHmim]Cl/n Zn Cl2,and[Amim]Cl/n Fe Cl3,was studied.In the ECODS,the ILs were used as both extractant and catalyst and 30 wt%hydrogen peroxide(H2O2)solution as oxidant.The effects of molar ratios of[(CH2)2COOHmim]Cl(or[Amim]Cl)to Fe Cl3(or Zn Cl2)in ILs,H2O2/sulfur(O/S)molar ratio,reaction temperature,and the nature of sulfur compounds on sulfur removal were investigated.The natures of the functional groups(–COOH,–CH2–CH=CH2)in cations and the acid strength of anions play important roles in the ECODS and affect the reaction time,temperature,and desulfurization efficiency of different substrates.Also,nitrogen-containing compounds(pyridine,pyrrole,and quinoline)could be removed simultaneously in the ECODS and had different effects on dibenzothiophene removal.展开更多
In the industrial operation of biotrickling filters for hydrogen sulfide(H2S) removal,shock loads or starvation was common due to process variations or equipment malfunctions.In this study,effects of starvation and sh...In the industrial operation of biotrickling filters for hydrogen sulfide(H2S) removal,shock loads or starvation was common due to process variations or equipment malfunctions.In this study,effects of starvation and shock loads on the performance of biotrickling filters for H2S removal were investigated.Four experiments were conducted to evaluate the changes of biomass and viable bacteria numbers in the biotrickling filters during a 24-d starvation.Compared to biomass,viable bacteria numbers decreased significantly during the starvation,especially when airflow was maintained in the absence of spray liquid.During the subsequent re-acclimation,all the bioreactors could resume high removal efficiencies within 4 d regardless of the previous starvation conditions.The results show that the re-acclimation time,in the case of biotrickling filters for H2S removal,is mainly controlled by viable H2S oxidizing bacteria numbers.On the other hand,the biotrickling filters can protect against shock loads in inlet fluctuating H2S concentration after resuming normal operation.When the biotrickling filters were supplied with H2S at an input of lower than 1700 mg/m3,their removal efficiencies were nearly 98% regardless of previous H2S input.展开更多
Reaction mechanisms of SO2 with O3 and H2O2 were investigated using quantum chemistry ab initio methods. Structures of all reactants, products, and transition states were optimized at the B3LYP/6-311G+(3df,2p) leve...Reaction mechanisms of SO2 with O3 and H2O2 were investigated using quantum chemistry ab initio methods. Structures of all reactants, products, and transition states were optimized at the B3LYP/6-311G+(3df,2p) level, and energy calculations were made at the G2M level. SO2 reactions with O3 and H2O2 occurred by O-abstraction and OH-abstraction by SO2, respectively, at length forming SO3+O2 (3Eg) and H2SO4. For SO2+O3 reactions the barrier height was predicted to be 9.68 kcal/mol with a rate constant of 3.61 × 10^-23 cm^3/(molecule.s) at 300 K, which is below the experimental upper limit. The rate constant predicted for this reaction accords well with the one provided by National Institute for Standards and Technology (NIST) in 250-500 K. For SO2+H2O2 reactions the barrier height was predicted to be 62.39 kcal/mol with a rate constant of 2.48× 10^-61 cm^3/(molecule.s) at 300 K.展开更多
Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chro- matography (HPLC) and mass spectrometry (MS) at 25 ~C. By controlling the slow reaction rate...Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chro- matography (HPLC) and mass spectrometry (MS) at 25 ~C. By controlling the slow reaction rate and choosing appropriate mobile phase, HPLC provides the unique advantages over other methods (UV-Vis, chemical separation) in species tracking and kinetic study. In addition to thiourea and formamidine sulfinic acid, two unreported products were also detected in the hy- drolysis reaction. Mass spectrometry measurement indicates these two products to be formamidine sulfenic acid and thiocyan- ogen with mass weights of 92.28 and 116,36, respectively. In the oxidation of formamidine disulfide by hydrogen peroxide, besides thiourea, formamidine sulfenic acid, formamidine sulfinic acid, thiocyanogen and urea, formamidine sulfonic acid and sulfate could be detected. The oxidation reaction was found to be first order in both forrnamidine disulfide and hydrogen per- oxide. The rate constants of hydrolysis and oxidation reactions were determined in the pH range of 1.5-3.0. It was found both rate constants are increased with the increasing of pH. Experimental curves of different species can be effectively simulated via a mechanism scheme for formamidine disulfide oxidation, including hydrolysis equilibrium of formamidine disulfide and irre- versible hydrolysis of formamidine sulfenic acid.展开更多
文摘为了丰富过硫化氢分子和过硫化氢一价阳离子的电子基态和激发态的信息,采用量子化学中密度泛函理论的B3LYP方法,使用6-311++g(3df,3pd)基组,对其进行了研究。计算得到了过硫化氢分子HSSH基态和过硫化氢离子HSSH+基态及激发态的平衡构型、光谱常数、总能量和零点振动能。计算表明:过硫化氢中性分子是长对称陀螺分子,二面角为90.66°,具有C_2对称性,而过硫化氢离子HSSH+有顺式(二面角为0°)和反式(二面角为180°)两种稳定的异构体,反式结构基态能量比顺式结构基态能量低0.129 e V;此外计算还得到了过硫化氢离子HSSH+两种异构体的基态和激发态的电子结构。
基金Project supported by the Foundation for Scientific Research Col-laborating with Overseas Scholar of Heilongjiang Province, China (No. WC03305)the Foundation for Science and Technology of Harbin City, China (No. 2002AA4CS087)
文摘A bench-scale experiment for control of hydrogen sulfide (H2S) emissions was carried out continuously for nearly four months by using bio-trickling filter packed with ZX01 stuffing. The results suggested that the bio-trickling filter had proven excellent performance over substantial operational periods. Removal efficiency of H2S was nearly 100% when volumetric loading of the bio-trickling filter varied from 0.64 g/(m^3·h) to 38.20 g/(m^3·h) and metabolism products of H2S were mainly composed of SO4^2-. When inlet concentration of H2S was 250 mg/m^3, the optimum gas retention time was 30 s and the optimum spray water flow rate was 0.005 9-0.012 L/(cm^2·h). The bio-trickling filter had good ability to resist shock of high volumetric loading, and was not blocked during experiments for nearly four months during which resistance was maintained at relatively lower value, so that the bio-trickling filter need not carry out back washing frequently and can be operated steadily for long-term.
基金Project funded by Ten Thousand Talent Plans for Young Top-notch Talents of Yunnan Province, China (No. YNWR-QNBJ-2018-051)。
文摘Hydrogen peroxide was used as an oxidant to modify the cuprite surface and enhance its sulfidization.Surface-adsorption and infrared spectroscopy measurements indicated that the modification of the cuprite surface with hydrogen peroxide before sulfidization increased the adsorption capacity of xanthate.Zeta potential,scanning electron microscopy-energy dispersive X-ray spectroscopy,X-ray photoelectron spectroscopy,and time-of-flight secondary ion mass spectrometry results showed that the modification with hydrogen peroxide increased the contents of S^(2−)and Sn^(2−)species on the cuprite surface.Microflotation tests showed that the recovery of cuprite increased from 61.74%to 83.30%after the modification of the surface with hydrogen peroxide.These results confirm that the modification of the cuprite surface with hydrogen peroxide enhances the sulfidization of cuprite,which in turn improves its flotation.
基金This work was supported by the National Natural Science Foundation of China (No.21173158 and No.21373152) and the Ministry of Science and Tech- nology of China (No.2012YQ220113-7).
文摘The reaction of laser-ablated vanadium, niobium and tantalum atoms with hydrogen sulfide has been investigated using matrix isolation FTIR and theoretical calculations. The metal atoms inserted into the H-S bond of H2S to form the HMSH molecules (M=V, Nb, Ta), which rearranged to H2MS molecules on annealing for Nb and Ta. The HMSH molecule can also further react with another H2S to form the H2M(SH)2 molecules. These new molecules were identified on the basis of the D2S and H234S isotopic substitutions. DFT (B3LYP and BPW91) theoretical calculations are used to predict energies, geometries, and vibrational frequencies for these novel metal dihydrido complexes and molecules. Reaction mechanism for formation of group V dihydrido complex was investigated by DFT internal reaction coordinate calculations. The dissociation of HVSH gave VS+H2 on broad band irradiation and reverse reaction happened on annealing. Based on B3LYP calculation releasing hydrogen from HVSH is endothermic only by 13.5 kcal/mol with lower energy barrier of 16.9 kcal/mol.
基金Supported by the National Defense Fundamental Research Fund (A1420080145)
文摘Iodine-sulfur (IS) thermochemical water-splitting cycle is the most promising massive hydrogen production process. To avoid the undesirable side reactions between hydriodic acid(HI) and sulfuric acid (H2SO4), it is necessary to purify the two phases formed by the Bunsen reaction. The purification process could be achieved by reverse reaction of the Bunsen reaction. In this study, the purification of the H2SO4 and HI Phases was studied. The purification proceeded in both batches and the continuous mode, the influences of operational parameters, including the reaction temperature, the flow rate of nitrogen gas, and the composition of the raw material solutions, on the purification effect, were investigated. Results showed that the purification of the H2SO4 phase was dominantly-affected by the reaction temperature, and iodine ion in the sulfuric acid phase could be removed completely when the temperature was above 130℃; although, the purification effect of the HI phase improved with increasing of both the flow rate of nitrogen gas and temperature.
基金Projects(21636010,21878342)supported by the National Natural Science Foundation of ChinaProject(2019JJ50758)supported by the Hunan Provincial Natural Science Foundation of China+1 种基金Project(2019TP1001)supported by the Hunan Provincial Science and Technology Plan Project of ChinaProject(CX20190097)supported by the Fundamental Research Funds for the Central Universities,China。
文摘Transition metal sulfides(TMSs)-based materials have been extensively investigated as effective non-noble catalysts for various applications.However,the exploration of TMSs-based catalysts for hydrogenation of nitro compounds is limited.Herein,CoSx/NC catalysts were prepared by solvothermal sulfurization of ZIF-67,followed by high-temperature annealing(300–600℃)under NH3 atmosphere.It was found that the structures and compositions of the as-prepared CoSx/NC can be readily tuned by varying the annealing temperature.Particularly,CoSx/NC-500,which possesses higher degree of S defects and larger specific surface areas,can achieve high conversion,selectivity and stability for catalytic reduction of nitro compounds into amines under mild reaction conditions.
基金financially supported by the National Key R&D Program of China(No.2018YFC1902002)the Special Fund for the National Natural Science Foundation of China(No.U1608254)。
文摘Because of the highly toxic cyanide in the gold cyanide residues,cyanide must be removed for environmental protection.The process mineralogy of residues was studied firstly,and then cyanide removal was carried out by three chemical methods.The results showed that the residue mainly contained Si,S and Fe.Pyrite was the main metallic mineral,and the iron-complex cyanides make cyanide removal difficult.The minerals in residues were in ultrafine particle size with high monomer dissociation degrees.In H_(2)O_(2)oxidation process,the self-decomposition and side reactions resulted in high consumption of H_(2)O_(2).In Na_(2)S_(2)O_(5)-air oxidation process,the time for complete process was long because of the reactions between Na_(2)S_(2)O_(5)and O_(2).Na_(2)SO_(3)oxidation method was found to be a new method for cyanide removal without air inflation device.The cyanide content was reduced to the national standard level in 90 min at pH 9.0 with optimum Na_(2)SO_(3)dose of 2.0 g/L.
基金Project 50204011 supported by the National Natural Science Foundation of Chinaa part work of the Inno- vation Program for Undergraduate supported by China University of Mining & Technology,Beijing
文摘Commercial coke was modified by H2O2 and/or NH3.H2O to obtain an activated coke containing additional oxygen functional groups and/or nitrogen functional groups. The aim of the modification was to enhance the SO2 adsorption capacity of the activated coke. Several techniques, including total nitrogen content measurements, SO2 adsorption, XPS and FTIR analysis, were used to characterize the coke samples. The XPS and FTIR spectra suggest the existence of -CONH2 groups in the H2O2 plus ammonia modified coke. The SO2 adsorption capacity of an activated coke increases slightly with an increase in H2O2 concentration during the modification process. The desulphurization performance of a modified coke is considerably enhanced by increasing the treatment temperature during ammonia modification. The amount of nitrogen in a coke modified by H2O2 plus NH3.H2O is the highest, and the SO2 adsorption capacity of the coke is also the highest (89.9 mg/gC). The NH3.H2O (only) modified sample has lower nitrogen content and lower desulphurization capacity (79.9 mg/gC). H2O modification gives the lowest SO2 adsorption capacity (28.9 mg/gC). The H2O2 pre-treatment is beneficial for the introduction of nitrogen onto the surface of a sample during the following ammonia treatment process.
文摘Two-dimensional materials(2D)with unique physicochemical properties have been widely studied for their use in many applications,including as hydrogen evolution catalysts to improve the efficiency of water splitting.Recently,typical 2D materials MoS2,graphene,MXenes,and black phosphorus have been widely investigated for their application in the hydrogen evolution reaction(HER).In this review,we summarize three efficient strategies—defect engineering,heterostructure formation,and heteroatom doping—for improving the HER performance of 2D catalysts.The d-band theory,density of states,and Fermi energy level are discussed to provide guidance for the design and construction of novel 2D materials.The challenges and prospects of 2D materials in the HER are also considered.
文摘Oxidative desulfurization was performed on Na2WO4 catalyst in the presence of hydrogen peroxide and acetic acid under mild reaction conditions (atmospheric pressure and temperature range of 293--343 K). Different organic compounds including benzothiophene (BT), dibenzothiophene (DBT), 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) were used to investigate the reactivity of this catalyst, and the effect of various parameters, such as temperature, solvents and the amount of oxidant reagent used in oxidative desulfurization reaction, was also examined. The results showed that the Na2WO4- H202 system was very effective for oxidative desulfurization, and the oxidation of BT, DBT and 4, 6-DMDBT was influenced by different parameters.
文摘This article describes two kinds of model oil samples made of a benzothiophene/octane mixture and a 2-me- thylthiophene/octane mixture. Furthermore, this paper investigates the oxidative desulfurization selectivity and reaction efficiency when Ce4+ compound and H2O2 having identical electron equivalent weight were used as oxidants. The test re- sults showed that the two kinds of oxidants were more effective to remove benzothiophene in the model oil samples. For oxidative desulfurization of 2-methylthiophene, Ce4+ compound was obviously superior than H2O2. This paper by means of quantum chemistry analyses elaborates the complex formed between Ce4+ species and 2-methylthiophene and FT-IR spec- trograms of model oil samples before and after oxidation by Ce4+ compound and H2O2, respectively. The results demonstrat- ed that Ce4+ compound could remove sulfur compounds not only through oxidation reaction but also through complexation reaction.
基金the National Nature Science Foundation of China(No.51077013,50873026)Production and Research Prospective Joint Project of Jiangsu Province of China(BY2009153)+2 种基金the Key Program for the Scientific Research Guiding Fund of Basic Scientific Research Operation Expenditure,Southeast University(3207040103)333 High-level Talent Training Project,Jiangsu Province of China (BRA2010033)Student Research Training Program of Southeast University(No.091028644) for financial support
文摘Aiming at deep desulfurization of gasoline,three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,or 3) were prepared and characterized.The amphiphilic vanadium(V)-substituted polyoxometalates were dissolved in water-immiscible ionic liquid([Bmim]PF6),forming a H2O2-in-[Bmim]PF6 emulsion desulfurization system with 30 m% H2O2 serving as the oxidant.The catalytic oxidation of sulfur-containing model oil has been studied in detail under various reaction conditions using this system.The ionic liquid emulsion system showed high catalytic oxidative activity in the treatment of commodity gasoline.Furthermore,the mechanism of catalytic oxidative desulfurization was also elaborated.
基金supported by the Special Funds of the National Natural Science Foundation of China(21127011)the National Natural Science Foundation of China(21076113,21206169)National Basic Research Program of China(2013CB733506)
文摘Deep desulfurization of liquid fuels is an important and challenging issue in worldwide petroleum refining industry.Extraction and catalytic oxidative desulfurization(ECODS)of liquid fuels using a series of ionic liquids(ILs)with two functionalized groups,such as[(CH2)2COOHmim]Cl/n Fe Cl3,[(CH2)2COOHmim]Cl/n Zn Cl2,and[Amim]Cl/n Fe Cl3,was studied.In the ECODS,the ILs were used as both extractant and catalyst and 30 wt%hydrogen peroxide(H2O2)solution as oxidant.The effects of molar ratios of[(CH2)2COOHmim]Cl(or[Amim]Cl)to Fe Cl3(or Zn Cl2)in ILs,H2O2/sulfur(O/S)molar ratio,reaction temperature,and the nature of sulfur compounds on sulfur removal were investigated.The natures of the functional groups(–COOH,–CH2–CH=CH2)in cations and the acid strength of anions play important roles in the ECODS and affect the reaction time,temperature,and desulfurization efficiency of different substrates.Also,nitrogen-containing compounds(pyridine,pyrrole,and quinoline)could be removed simultaneously in the ECODS and had different effects on dibenzothiophene removal.
基金supported by the Foundation for Society Development of Jilin Province (No.20080412-1)the Education Research Foundation for Science and Technology Development of Jilin Provincethe Foundation for Doctor Research in Northeast Dianli University of Jilin Province (No.BSJXM-200710),China
文摘In the industrial operation of biotrickling filters for hydrogen sulfide(H2S) removal,shock loads or starvation was common due to process variations or equipment malfunctions.In this study,effects of starvation and shock loads on the performance of biotrickling filters for H2S removal were investigated.Four experiments were conducted to evaluate the changes of biomass and viable bacteria numbers in the biotrickling filters during a 24-d starvation.Compared to biomass,viable bacteria numbers decreased significantly during the starvation,especially when airflow was maintained in the absence of spray liquid.During the subsequent re-acclimation,all the bioreactors could resume high removal efficiencies within 4 d regardless of the previous starvation conditions.The results show that the re-acclimation time,in the case of biotrickling filters for H2S removal,is mainly controlled by viable H2S oxidizing bacteria numbers.On the other hand,the biotrickling filters can protect against shock loads in inlet fluctuating H2S concentration after resuming normal operation.When the biotrickling filters were supplied with H2S at an input of lower than 1700 mg/m3,their removal efficiencies were nearly 98% regardless of previous H2S input.
基金Project supported by the National Basic Research Program (973) of China (No. 2006CB200303)the National Natural Science Foundation for Distinguished Young Scholars (No. 50525620), China
文摘Reaction mechanisms of SO2 with O3 and H2O2 were investigated using quantum chemistry ab initio methods. Structures of all reactants, products, and transition states were optimized at the B3LYP/6-311G+(3df,2p) level, and energy calculations were made at the G2M level. SO2 reactions with O3 and H2O2 occurred by O-abstraction and OH-abstraction by SO2, respectively, at length forming SO3+O2 (3Eg) and H2SO4. For SO2+O3 reactions the barrier height was predicted to be 9.68 kcal/mol with a rate constant of 3.61 × 10^-23 cm^3/(molecule.s) at 300 K, which is below the experimental upper limit. The rate constant predicted for this reaction accords well with the one provided by National Institute for Standards and Technology (NIST) in 250-500 K. For SO2+H2O2 reactions the barrier height was predicted to be 62.39 kcal/mol with a rate constant of 2.48× 10^-61 cm^3/(molecule.s) at 300 K.
基金supported by the National Natural Science Foundation of China (21073232 & 50921002)the Fundamental Research Fund from the Chinese Central University (2010LKHX02)
文摘Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chro- matography (HPLC) and mass spectrometry (MS) at 25 ~C. By controlling the slow reaction rate and choosing appropriate mobile phase, HPLC provides the unique advantages over other methods (UV-Vis, chemical separation) in species tracking and kinetic study. In addition to thiourea and formamidine sulfinic acid, two unreported products were also detected in the hy- drolysis reaction. Mass spectrometry measurement indicates these two products to be formamidine sulfenic acid and thiocyan- ogen with mass weights of 92.28 and 116,36, respectively. In the oxidation of formamidine disulfide by hydrogen peroxide, besides thiourea, formamidine sulfenic acid, formamidine sulfinic acid, thiocyanogen and urea, formamidine sulfonic acid and sulfate could be detected. The oxidation reaction was found to be first order in both forrnamidine disulfide and hydrogen per- oxide. The rate constants of hydrolysis and oxidation reactions were determined in the pH range of 1.5-3.0. It was found both rate constants are increased with the increasing of pH. Experimental curves of different species can be effectively simulated via a mechanism scheme for formamidine disulfide oxidation, including hydrolysis equilibrium of formamidine disulfide and irre- versible hydrolysis of formamidine sulfenic acid.