A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and...A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and 79% respectively.展开更多
The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)...The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)-based Cu-viologen complex H_(4)[Cu_(2)~ⅠCl_(2)(Hbcbpy)_(4)] [α-Mo_(8)O_(26)] [β-Mo8O_(26)]·H_(2)O(BHU-2,Hbcbpy=1-(4-carboxybenzyl)-4,4'-bipyridinium) was synthesized and characterized by single-crystal X-ray diffraction(XRD),infrared radiation spectra,powder X-ray diffraction(PXRD) and X-ray photoelectron spectroscopy(XPS) spectra.The structural characteristic of BHU-2 is the presence of two types of octamolybdate clusters [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)and a new binuclear Cu~Ⅰ-Hbcbpy complex linked by Cl-bridges[Cu_(2)ⅠCl_(2)(Hbcbpy)_(4)]^(4+).BHU-2 as a heterogeneous catalyst exhibits excellent activities to the oxidation desulfurization and photocatalytic hydrogen production.At room temperature,BHU-2 can catalyze 96% conversion of methyl phenyl sulfide with 98% selectivity,and the process obeys the pseudo-first-order reaction kinetic with the half-life of9.6 min.The notorious 2-chloroethyl ethyl sulfide can achieve 99% conversion with 98% selectivity within only1 min at the presence of BHU-2,and the turnover frequency(TOF) is up to 7400 h^(-1).BHU-2 also exhibits high catalytic activity for the oxidation of other aromatic and aliphatic thioethers within short time at room temperature.Furthermore,BHU-2 shows a high catalytic activity for visible-light-driven hydrogen evolution with an H_(2) evolution rate of 1677.85 μmol·g^(-1)·h^(-1) within 10 h.Moreover,the catalytic activities do not decrease evidently after three cycles,revealing the prominent structural stability and recyclability.展开更多
Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic fram...Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.展开更多
According to the mechanism of sulfur removal easily through oxidation, the process of smelting oxidation desulfurization of copper slags is studied, which supplies a new thinking for obtaining the molten iron of lower...According to the mechanism of sulfur removal easily through oxidation, the process of smelting oxidation desulfurization of copper slags is studied, which supplies a new thinking for obtaining the molten iron of lower sulfur content by smelting reduction of copper slags. Special attention is given to the effects of the holding temperature, the holding time and CaF2, CaO addition amounts on the desulfurization rate of copper slags. The results indicate that the rate of copper slags smelting oxidation desulfurization depends on the matte mass transfer rate through the slag phase. After the oxidation treatment, sulfur of copper slags can be removed as SO2 efficiently. Amount of Ca2+ of copper slags affects the desulfurization rate greatly, and the slag desulfurization rate is reduced by adding a certain amount of CaF2 and CaO. Compared with CaF2, CaO is negative to slags sulfur removal with equal Ca2+ addition. Under the air flow of 0.3 U/min, the sulfur content of copper slags can be reduced to 0. 004 67% in the condition of the holding time of 3 min and the holding temperature of 1 500 ℃. The sulfur content of molten iron is reduced to 0. 000 8 % in the smelting reduction of treated slags, and the problem of high sulfur content of molten iron obtained by smelting reduction with copper slag has been successively solved.展开更多
Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performanc...Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.展开更多
The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an e...The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.展开更多
A C_(9)H_(10)O_(2):0.5ZnCl_(2)/SG catalyst was synthesized using a one-step sol-gel method with silica gel(SG)as the carrier and C_(9)H_(10)O_(2):0.5ZnCl_(2)deep eutectic solvent(DES)as active component.The structure ...A C_(9)H_(10)O_(2):0.5ZnCl_(2)/SG catalyst was synthesized using a one-step sol-gel method with silica gel(SG)as the carrier and C_(9)H_(10)O_(2):0.5ZnCl_(2)deep eutectic solvent(DES)as active component.The structure of the supported catalyst was characterized by FT-IR,XRD,SEM,and N2 adsorption-desorption,and the DES was found to have successfully permeated the SG through its pores.The removal of dibenzothiophene(DBT)in model diesel was studied using C_(9)H_(10)O_(2):0.5ZnCl_(2)/SG as a catalyst and H_(2)O_(2)as an oxidant.The influence of loading dose of DES,reaction temperature,catalyst dosage,O/S molar ratio,and sulfide type on the desulfurization rate was investigated.The removal rates of DBT,4,6-dimethyldibenzothiophene(4,6-DMDBT),and benzothiophene(BT)under optimal reaction conditions were 99.4%,96%,and 78.2%,respectively.C_(9)H_(10)O_(2):0.5ZnCl_(2)/SG catalyst could be recycled five times with a little decrease of oxidative desulfurization activity,and the adsorption-oxidation desulfurization mechanism was examined.展开更多
Heteropoly acid of Keggin structure phosphotungstic(HPW) and phosphomolybdic(HPMo) were chemically anchored to the modified SBA-15 channel. The materials were used as catalyst for oxidative desulfurization of orga...Heteropoly acid of Keggin structure phosphotungstic(HPW) and phosphomolybdic(HPMo) were chemically anchored to the modified SBA-15 channel. The materials were used as catalyst for oxidative desulfurization of organic sulfur compounds including benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethydibenzothiophene (4,6-DMDBT). The experimental results show that the catalysts are efficient and reusable, the catalytic activity is hardly reduced even in the 5th cycle of use.展开更多
12-Tungstophosphoric acid(PW) supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization(ODS) of mixed thiophenic compounds in model oil and crude oil under mild conditions u...12-Tungstophosphoric acid(PW) supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization(ODS) of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide(H2O2) as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-tosulfur compounds(S-compounds) molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene(DBT) and mixed thiophenic model oil under atmospheric pressure at 75 ℃ in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.展开更多
Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot m...Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.展开更多
High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we...High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.展开更多
A series of mesoporous phosphotungstic acid/alumina composites (HPW/Al_2O_3) with various HPW contents were synthesized by evaporation-induced self-assembly method. These composites were characterized by nitrogen ad...A series of mesoporous phosphotungstic acid/alumina composites (HPW/Al_2O_3) with various HPW contents were synthesized by evaporation-induced self-assembly method. These composites were characterized by nitrogen adsorption-desorption, TEM, FTIR, and UV-vis, and were tested as catalysts in oxidation desulfurization of model fuel composed of dibenzothiophene (DBT) and hydrocarbon, using H202 as the oxidant. These composites exhibited high activity in catalytic oxidation of DBT in model fuel and good reusing ability. The best performance was achieved by using the mesoporous HPW/Al_2O_3 with 15wt% HPW content, which resulted in a DBT conversion of 98% after 2 h reaction at 343 K, and it did not show significant activity degradation after 3 recycles. Characterization results showed that the mesoporous structure of alumina and the Keggin structure of HPW were preserved in the formed composite. These results suggested that HPW/ Al_2O_3 could be a promising catalyst in oxidative desulfurization process.展开更多
An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;the...An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;then the generated SO2-containing flue gas was managed using manganese oxide ore and anolyte(MOOA)desulfurization;at last,the desulfurized slurry was introduced to the electrolytic manganese production(EMP).Results showed that 4.0 wt%coke addition reduced the sulfur of calcined EMR to 0.9%,thereby satisfying the cement-buffer requirement.Pilot-scale desulfurization showed that about 7.5 vol%of high SO2 containing flue gas can be cleaned to less than 0.1 vol%through a five-stage countercurrent MOOA desulfurization.The desulfurized slurry had 42.44 g·L-Mn2+and 1.92 g·L-1 S2 O62-,which was suitable for electrowinning after purification,and the purity of manganese product was 99.93%,satisfy the National Standard of China YB/T051-2015.This new integrated technology fulfilled 99.7%of sulfur reutilization from the EMR and 94.1%was effectively used to the EMP.The MOOA desulfurization linked the EMP a closed cycle without any pollutant discharge,which promoted the cleaner production of EMP industry.展开更多
With the aim of deep desulfurization, silica-supported polyoxometalate-based ionic liquids were successfully prepared by a one-pot hydrothermal process and employed in heterogeneous oxidative desulfurization of variou...With the aim of deep desulfurization, silica-supported polyoxometalate-based ionic liquids were successfully prepared by a one-pot hydrothermal process and employed in heterogeneous oxidative desulfurization of various sulfur compounds. The compositions and structures of the hybrid samples were characterized by various methods such as FT-IR, XPS, Raman,UV–Vis, wide-angle XRD and N2adsorption–desorption. The experimental results indicated that the hybrid materials presented a high dispersion of tungsten species and excellent catalytic activity for the removal of 4,6-dimethyldibenzothiophene without any organic solvent as extractant, and the sulfur removal could reach 100.0% under mild conditions.The catalytic performance on various substrates was also investigated in detail. After cycling seven cycles, the sulfur removal of the heterogeneous system still reached 93.0%. The GC-MS analysis results demonstrated that the sulfur compound was first adsorbed by the catalyst and subsequently oxidized to its corresponding sulfone.展开更多
PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS...PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS)activity.The XRD results proved that UiO-66 retained its structure in the PTA/UiO-66 composites.The SEM results showed that the PTA/UiO-66 catalysts exhibited regular octahedral shape.The Raman spectra revealed that PTA in the composites retained the Keggin structure.The XPS results showed that the electron transfer occurred from Zr-MOF to PTA.The ODS reaction mechanism was discussed.Electrons transfer from Zr-MOF to PTA can promote the generation of active species(·OH)and thus enhance the ODS activity.This explanation can be confirmed by the formation of oxygen vacancy and W0 as revealed by the XPS analysis.展开更多
In recent years, transition-metal oxides(TMOs) have been long employed for aerobic oxidative desulfurization. However, the inherent bottlenecks, such as the low explosion of active sites, limit the application of bulk...In recent years, transition-metal oxides(TMOs) have been long employed for aerobic oxidative desulfurization. However, the inherent bottlenecks, such as the low explosion of active sites, limit the application of bulk TMOs catalyst. In this study, V_(2)O_(5) nanoparticles with oxygen vacancies were prepared in large-scale via facile ball milling strategy with adding oxalic acid as a reducing agent. The as-prepared catalysts exhibit remarkable sulfur removal for oils with different initial S-concentrations and different substrates. Sulfur removal could reach up to 99.7%(< 2 ppm) under the optimized reaction conditions. This work provides a feasible desulfurization strategy for fuel oils.展开更多
Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR...Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, Nadsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [Cmim]PMoO/Am TiOonly dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.展开更多
VO2(M) doped with different metals(Ti, Ce, Nb, Zr, W, and Mo) was successfully synthesized by the hydrothermal reduction process using oxalic acid as the reductant. The results showed that doping metals in the VO2(M) ...VO2(M) doped with different metals(Ti, Ce, Nb, Zr, W, and Mo) was successfully synthesized by the hydrothermal reduction process using oxalic acid as the reductant. The results showed that doping metals in the VO2(M) lattice could enhance the oxidative desulfurization(ODS) activity. The DSC and Raman spectra revealed that VO2(M) retained its monoclinic structure after doping. Mechanism for the improvement of ODS activity by doping was investigated. Electron transfer to V(V) atom occurs upon doping, and then V(V) changes into V(IV), which can promote the ODS reaction. This explanation can be confirmed by the fact that doping can promote the proportion of V(Ⅳ) after doping as revealed by the XPS analysis.展开更多
In this paper, the oxidative desulfurization (ODS) system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge (DBD) plasma in...In this paper, the oxidative desulfurization (ODS) system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge (DBD) plasma in the presence of air plus an extraction step with the oxidation-treated fuel put over ionic liquid [BMIM]FeC14 (1-butyl-3-methylimidazolium tetrachloroferrate). This new system exhibited an excellent desulfurization effect. The sulfur content of DBT in diesel oil decreased from 200 ppm to 4.92 ppm (S removal rate up to 97.5%) under the following optimal reaction conditions: air flow rate (v) of 60 mL/min, amplitude of applied voltage (U) on DBD of 16 kV, input frequency (f) of 79 kHz, catalyst amount (w) of 1.25 wt%, reaction time (t) of 10 min. Moreover, a high desulfurization rate was obtained during oxidation of benzothiophene (BT) or 4,6-DMDBT (4,6-dimethyl-dibenzothiophene) under the aforementioned conditions. The oxidation reactivity of different S compounds was decreased in the order of DBT, 4,6-DMDBT and BT. The remarkable advantage of the novel ODS system is that the desulfurization condition applies in the presence of air at ambient conditions without peroxides, aqueous solvent or biphasic oil-aqueous solution system.展开更多
A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loa...A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loading NHPI on h-BN not only benefits to the dispersion and utilization of NHPI,but also can significantly promote the catalytic performance.By employing NHPI/h-BN as the catalyst,azodiisobutyronitrile(AIBN)as the metal-free initiator,a 95%conversion of dibenzothiophene(DBT)can be acquired under the reaction conditions of 120°C and atmospheric pressure with molecular oxygen(O_(2))as oxidant.Moreover,the heterogenization is convenient for the regeneration of the catalyst with>94%DBT conversion after being recycled seven times.Characterizations illustrate that the promoted catalytic activity along with the regenerability originate from the interactions between NHPI and h-BN.The catalytic mechanism study shows that molecular oxygen is readily activated by the NHPI/h-BN to form a superoxide radical(O_(2)^(·-)),which oxidize DBT to DBTO2 for desulfurization.展开更多
基金The project was supported by National Natural Science Foundation of China
文摘A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and 79% respectively.
基金financially supported by the National Natural Science Foundation of China (Nos.22271021,21901018 and 21971024)the Natural Science Foundation of Liaoning Province (No.2022-MS-373)Liaoning Revitalization Talents Program (No.XLYC1902011)。
文摘The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)-based Cu-viologen complex H_(4)[Cu_(2)~ⅠCl_(2)(Hbcbpy)_(4)] [α-Mo_(8)O_(26)] [β-Mo8O_(26)]·H_(2)O(BHU-2,Hbcbpy=1-(4-carboxybenzyl)-4,4'-bipyridinium) was synthesized and characterized by single-crystal X-ray diffraction(XRD),infrared radiation spectra,powder X-ray diffraction(PXRD) and X-ray photoelectron spectroscopy(XPS) spectra.The structural characteristic of BHU-2 is the presence of two types of octamolybdate clusters [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)and a new binuclear Cu~Ⅰ-Hbcbpy complex linked by Cl-bridges[Cu_(2)ⅠCl_(2)(Hbcbpy)_(4)]^(4+).BHU-2 as a heterogeneous catalyst exhibits excellent activities to the oxidation desulfurization and photocatalytic hydrogen production.At room temperature,BHU-2 can catalyze 96% conversion of methyl phenyl sulfide with 98% selectivity,and the process obeys the pseudo-first-order reaction kinetic with the half-life of9.6 min.The notorious 2-chloroethyl ethyl sulfide can achieve 99% conversion with 98% selectivity within only1 min at the presence of BHU-2,and the turnover frequency(TOF) is up to 7400 h^(-1).BHU-2 also exhibits high catalytic activity for the oxidation of other aromatic and aliphatic thioethers within short time at room temperature.Furthermore,BHU-2 shows a high catalytic activity for visible-light-driven hydrogen evolution with an H_(2) evolution rate of 1677.85 μmol·g^(-1)·h^(-1) within 10 h.Moreover,the catalytic activities do not decrease evidently after three cycles,revealing the prominent structural stability and recyclability.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21978119,22202088)Key Research and Development Plan of Hainan Province(ZDYF2022SHFZ285)Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB636)。
文摘Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.
基金Sponsored by National Natural Science Foundation of China ( 50906035 , 51204082 )
文摘According to the mechanism of sulfur removal easily through oxidation, the process of smelting oxidation desulfurization of copper slags is studied, which supplies a new thinking for obtaining the molten iron of lower sulfur content by smelting reduction of copper slags. Special attention is given to the effects of the holding temperature, the holding time and CaF2, CaO addition amounts on the desulfurization rate of copper slags. The results indicate that the rate of copper slags smelting oxidation desulfurization depends on the matte mass transfer rate through the slag phase. After the oxidation treatment, sulfur of copper slags can be removed as SO2 efficiently. Amount of Ca2+ of copper slags affects the desulfurization rate greatly, and the slag desulfurization rate is reduced by adding a certain amount of CaF2 and CaO. Compared with CaF2, CaO is negative to slags sulfur removal with equal Ca2+ addition. Under the air flow of 0.3 U/min, the sulfur content of copper slags can be reduced to 0. 004 67% in the condition of the holding time of 3 min and the holding temperature of 1 500 ℃. The sulfur content of molten iron is reduced to 0. 000 8 % in the smelting reduction of treated slags, and the problem of high sulfur content of molten iron obtained by smelting reduction with copper slag has been successively solved.
文摘Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.
基金the National Natural Science Foundation of China, China (Grant 21920102005, 22288101, and 21835002)the 111 Project, China (B17020)+2 种基金the European Union through the European Research Council, European Union (grant ERC-AdG-2014-671093, SynCatMatch)the Spanish Government through “Severo Ochoa”, Spain (SEV2016-0683, MINECO) for supporting this workthe financial support from China Scholarship Council, China
文摘The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.
基金the financial support of the Natural Science Foundation of Liaoning Province(2019-ZD-0064)the Doctoral Fund of Liaoning Province(201501105).
文摘A C_(9)H_(10)O_(2):0.5ZnCl_(2)/SG catalyst was synthesized using a one-step sol-gel method with silica gel(SG)as the carrier and C_(9)H_(10)O_(2):0.5ZnCl_(2)deep eutectic solvent(DES)as active component.The structure of the supported catalyst was characterized by FT-IR,XRD,SEM,and N2 adsorption-desorption,and the DES was found to have successfully permeated the SG through its pores.The removal of dibenzothiophene(DBT)in model diesel was studied using C_(9)H_(10)O_(2):0.5ZnCl_(2)/SG as a catalyst and H_(2)O_(2)as an oxidant.The influence of loading dose of DES,reaction temperature,catalyst dosage,O/S molar ratio,and sulfide type on the desulfurization rate was investigated.The removal rates of DBT,4,6-dimethyldibenzothiophene(4,6-DMDBT),and benzothiophene(BT)under optimal reaction conditions were 99.4%,96%,and 78.2%,respectively.C_(9)H_(10)O_(2):0.5ZnCl_(2)/SG catalyst could be recycled five times with a little decrease of oxidative desulfurization activity,and the adsorption-oxidation desulfurization mechanism was examined.
基金the National Natural Science Foundation of China (No.50272048)
文摘Heteropoly acid of Keggin structure phosphotungstic(HPW) and phosphomolybdic(HPMo) were chemically anchored to the modified SBA-15 channel. The materials were used as catalyst for oxidative desulfurization of organic sulfur compounds including benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethydibenzothiophene (4,6-DMDBT). The experimental results show that the catalysts are efficient and reusable, the catalytic activity is hardly reduced even in the 5th cycle of use.
基金Razi University Research Council for support of this work
文摘12-Tungstophosphoric acid(PW) supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization(ODS) of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide(H2O2) as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-tosulfur compounds(S-compounds) molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene(DBT) and mixed thiophenic model oil under atmospheric pressure at 75 ℃ in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.
基金financially supported by the National Natural Science Foundation of China (Nos. 21506080 and 21766007)Natural Science Foundation of Jiangsu Province (No. BK20150485)+1 种基金Advanced Talents of Jiangsu University (No. 15JDG053)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.
基金This work was financially supported by the National Natural Science Foundation of China(No.21722604)the Postdoctoral Foundation of China(Nos.2019M651743 and 2020M671365)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20190852)the National Youth Natural Science Foundation(No.8111310009).
文摘High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.
基金Funded by the National Natural Science Foundation of China(21106008)the PetroChina Innovation Foundation(2013D-5006-0405)the Natural Science Foundation of Hubei Province(2011CDB007)
文摘A series of mesoporous phosphotungstic acid/alumina composites (HPW/Al_2O_3) with various HPW contents were synthesized by evaporation-induced self-assembly method. These composites were characterized by nitrogen adsorption-desorption, TEM, FTIR, and UV-vis, and were tested as catalysts in oxidation desulfurization of model fuel composed of dibenzothiophene (DBT) and hydrocarbon, using H202 as the oxidant. These composites exhibited high activity in catalytic oxidation of DBT in model fuel and good reusing ability. The best performance was achieved by using the mesoporous HPW/Al_2O_3 with 15wt% HPW content, which resulted in a DBT conversion of 98% after 2 h reaction at 343 K, and it did not show significant activity degradation after 3 recycles. Characterization results showed that the mesoporous structure of alumina and the Keggin structure of HPW were preserved in the formed composite. These results suggested that HPW/ Al_2O_3 could be a promising catalyst in oxidative desulfurization process.
基金supported by the National Key R&D Program of China(No.2018YFC0213405)。
文摘An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;then the generated SO2-containing flue gas was managed using manganese oxide ore and anolyte(MOOA)desulfurization;at last,the desulfurized slurry was introduced to the electrolytic manganese production(EMP).Results showed that 4.0 wt%coke addition reduced the sulfur of calcined EMR to 0.9%,thereby satisfying the cement-buffer requirement.Pilot-scale desulfurization showed that about 7.5 vol%of high SO2 containing flue gas can be cleaned to less than 0.1 vol%through a five-stage countercurrent MOOA desulfurization.The desulfurized slurry had 42.44 g·L-Mn2+and 1.92 g·L-1 S2 O62-,which was suitable for electrowinning after purification,and the purity of manganese product was 99.93%,satisfy the National Standard of China YB/T051-2015.This new integrated technology fulfilled 99.7%of sulfur reutilization from the EMR and 94.1%was effectively used to the EMP.The MOOA desulfurization linked the EMP a closed cycle without any pollutant discharge,which promoted the cleaner production of EMP industry.
基金financially supported by the National Nature Science Foundation of China (Nos. 21776116, 21576122, 21722604)Postdoctoral Foundation of China (No. 2017M621646)+1 种基金Postdoctoral Foundation of Jiangsu Province (No. 2018K083C)the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘With the aim of deep desulfurization, silica-supported polyoxometalate-based ionic liquids were successfully prepared by a one-pot hydrothermal process and employed in heterogeneous oxidative desulfurization of various sulfur compounds. The compositions and structures of the hybrid samples were characterized by various methods such as FT-IR, XPS, Raman,UV–Vis, wide-angle XRD and N2adsorption–desorption. The experimental results indicated that the hybrid materials presented a high dispersion of tungsten species and excellent catalytic activity for the removal of 4,6-dimethyldibenzothiophene without any organic solvent as extractant, and the sulfur removal could reach 100.0% under mild conditions.The catalytic performance on various substrates was also investigated in detail. After cycling seven cycles, the sulfur removal of the heterogeneous system still reached 93.0%. The GC-MS analysis results demonstrated that the sulfur compound was first adsorbed by the catalyst and subsequently oxidized to its corresponding sulfone.
基金This work was supported by the Natural Science Foundation of Tianjin(19JCTPJC46300).
文摘PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS)activity.The XRD results proved that UiO-66 retained its structure in the PTA/UiO-66 composites.The SEM results showed that the PTA/UiO-66 catalysts exhibited regular octahedral shape.The Raman spectra revealed that PTA in the composites retained the Keggin structure.The XPS results showed that the electron transfer occurred from Zr-MOF to PTA.The ODS reaction mechanism was discussed.Electrons transfer from Zr-MOF to PTA can promote the generation of active species(·OH)and thus enhance the ODS activity.This explanation can be confirmed by the formation of oxygen vacancy and W0 as revealed by the XPS analysis.
基金financial support from the National Natural Science Foundation of China(21722604)China Postdoctoral Science Foundation(2020M671364,2020M671365)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20190243)the Qinglan Project of Jiangsu Province,and the Society Development Fund of Zhenjiang(SH2020020)。
文摘In recent years, transition-metal oxides(TMOs) have been long employed for aerobic oxidative desulfurization. However, the inherent bottlenecks, such as the low explosion of active sites, limit the application of bulk TMOs catalyst. In this study, V_(2)O_(5) nanoparticles with oxygen vacancies were prepared in large-scale via facile ball milling strategy with adding oxalic acid as a reducing agent. The as-prepared catalysts exhibit remarkable sulfur removal for oils with different initial S-concentrations and different substrates. Sulfur removal could reach up to 99.7%(< 2 ppm) under the optimized reaction conditions. This work provides a feasible desulfurization strategy for fuel oils.
基金financially supported by the National Natural Science Foundation of China (Nos. 21576122, 21646001, 21506080)Natural Science Foundation of Jiangsu Province (Nos. BK20150485, BK20170528)+2 种基金China Postdoctoral Science Foundation (2017M611727)Jiangsu Planned Projects for Postdoctoral Research Funds (1701104B)supported by the Student Innovation and Entrepreneurship Training Program (201810299332 W)
文摘Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, Nadsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [Cmim]PMoO/Am TiOonly dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.
基金supported by the Natural Science Foundation of Tianjin(17JCYBJC20000)
文摘VO2(M) doped with different metals(Ti, Ce, Nb, Zr, W, and Mo) was successfully synthesized by the hydrothermal reduction process using oxalic acid as the reductant. The results showed that doping metals in the VO2(M) lattice could enhance the oxidative desulfurization(ODS) activity. The DSC and Raman spectra revealed that VO2(M) retained its monoclinic structure after doping. Mechanism for the improvement of ODS activity by doping was investigated. Electron transfer to V(V) atom occurs upon doping, and then V(V) changes into V(IV), which can promote the ODS reaction. This explanation can be confirmed by the fact that doping can promote the proportion of V(Ⅳ) after doping as revealed by the XPS analysis.
基金supported by National Natural Science Foundation of China(No.21063012)the Ministry of Education Innovation Team of China(No.IRT1161)
文摘In this paper, the oxidative desulfurization (ODS) system is directly applied to deal with the catalytic oxidation of sulfur compounds of sulfur-containing model oil by dielectric barrier discharge (DBD) plasma in the presence of air plus an extraction step with the oxidation-treated fuel put over ionic liquid [BMIM]FeC14 (1-butyl-3-methylimidazolium tetrachloroferrate). This new system exhibited an excellent desulfurization effect. The sulfur content of DBT in diesel oil decreased from 200 ppm to 4.92 ppm (S removal rate up to 97.5%) under the following optimal reaction conditions: air flow rate (v) of 60 mL/min, amplitude of applied voltage (U) on DBD of 16 kV, input frequency (f) of 79 kHz, catalyst amount (w) of 1.25 wt%, reaction time (t) of 10 min. Moreover, a high desulfurization rate was obtained during oxidation of benzothiophene (BT) or 4,6-DMDBT (4,6-dimethyl-dibenzothiophene) under the aforementioned conditions. The oxidation reactivity of different S compounds was decreased in the order of DBT, 4,6-DMDBT and BT. The remarkable advantage of the novel ODS system is that the desulfurization condition applies in the presence of air at ambient conditions without peroxides, aqueous solvent or biphasic oil-aqueous solution system.
基金the financial support from the National Key R&D Program of China(No.2017YFB0306504)National Natural Science Foundation of China(No.22008094,22178154 and 21878133)+2 种基金Chinese Postdoctoral Science Foundation(No.2019M651743,2020M671364 and 2020M673039)Natural Science Foundation of Jiangsu Province(No.BK20190852)Natural Science Foundation for Jiangsu Colleges and Universities(No.19KJB530005)
文摘A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loading NHPI on h-BN not only benefits to the dispersion and utilization of NHPI,but also can significantly promote the catalytic performance.By employing NHPI/h-BN as the catalyst,azodiisobutyronitrile(AIBN)as the metal-free initiator,a 95%conversion of dibenzothiophene(DBT)can be acquired under the reaction conditions of 120°C and atmospheric pressure with molecular oxygen(O_(2))as oxidant.Moreover,the heterogenization is convenient for the regeneration of the catalyst with>94%DBT conversion after being recycled seven times.Characterizations illustrate that the promoted catalytic activity along with the regenerability originate from the interactions between NHPI and h-BN.The catalytic mechanism study shows that molecular oxygen is readily activated by the NHPI/h-BN to form a superoxide radical(O_(2)^(·-)),which oxidize DBT to DBTO2 for desulfurization.