An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a qu...An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.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
Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration ...Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration of DA as hard segments into the PU molecular chain.The effects of DA content(φ)on the mechanical properties,thermal stability,and hydrophobicity of PU,both before and after the addition of KH550,were thoroughly examined.The results of microscopic mechanism analysis confirmed that KH550 chemically modified the surface of DA,facilitating its incorporation into the polyurethane molecular chain,thereby significantly enhancing the compatibility and dispersion of DA within the PU matrix.When the mass fraction of modified DA(MDA)reached 12%,the mechanical properties,thermal stability,and hydrophobicity of the composites were substantially improved,with the tensile strength reaching 14.9 MPa,and the contact angle measuring 100.6°.展开更多
A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structur...A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.展开更多
Porous ionic liquids have demonstrated excellent performance in the field of separation,attributed to their high specific surface area and efficient mass transfer.Herein,task-specific protic porous ionic liquids(PPILs...Porous ionic liquids have demonstrated excellent performance in the field of separation,attributed to their high specific surface area and efficient mass transfer.Herein,task-specific protic porous ionic liquids(PPILs)were prepared by employing a novel one-step coupling neutralization reaction strategy for extractive desulfurization.The single-extraction efficiency of PPILs reached 75.0%for dibenzothiophene.Moreover,adding aromatic hydrocarbon interferents resulted in a slight decrease in the extraction efficiency of PPILs(from 45.2%to 37.3%,37.9%,and 33.5%),indicating the excellent extraction selectivity of PPILs.The experimental measurements and density functional theory calculations reveal that the surface channels of porous structures can selectively capture dibenzothiophene by the stronger electrophilicity(Eint(HS surface channel/DBT)=-39.8 kcal mol^(-1)),and the multiple extraction sites of ion pairs can effectively enrich and transport dibenzothiophene from the oil phase into PPILs throughπ...π,C-H...πand hydrogen bonds interactions.Furthermore,this straightforward synthetic strategy can be employed in preparing porous liquids,offering new possibilities for synthesizing PPILs with tailored functionalities.展开更多
In order to reduce the sulfur compounds in diesel fuel,boron nitride(BN)has been used as a novel metal-free catalyst in the present research.This nanocatalyst was synthesized via template-free approach followed by hea...In order to reduce the sulfur compounds in diesel fuel,boron nitride(BN)has been used as a novel metal-free catalyst in the present research.This nanocatalyst was synthesized via template-free approach followed by heating treatment at 900℃ in nitrogen atmosphere that the characteristics of the sample were identified by the X-ray diffraction,Fourier-transform infrared spectroscopy,Raman spectroscopy,field emission scanning electron microscopy,transmission electron microscopy,atomic force microscopy,and N2 adsorption-desorption isotherms.The results of structural and morphological analysis represented that BN has been successfully synthesized.The efficacy of the main operating parameters on the process was studied by using response surface methodology based on the Box-Behnken design method.The prepared catalyst showed high efficiency in oxidative desulfurization of diesel fuel with initial sulfur content of 8040 mg·kg^(-1)S.From statistical analysis,a significant quadratic model was obtained to predict the sulfur removal as a function of efficient parameters.The maximum efficiency of 72.4%was achieved under optimized conditions at oxidant/sulfur molar ratio of 10.2,temperature of 71℃,reaction time of 113 min,and catalyst dosage of 0.36 g.Also,the reusability of the BN was studied,and the result showed little reduction in activity of the catalyst after 10 times regeneration.Moreover,a plausible mechanism was proposed for oxidation of sulfur compounds on the surface of the catalyst.The present study shows that BN materials can be selected as promising metal-free catalysts for desulfurization process.展开更多
The synergistic impact of mechanical ball milling and flue gas desulfurization(FGD)gypsum on the dealkalization of bauxite residue was investigated through integrated analyses of solution chemistry,mineralogy,and micr...The synergistic impact of mechanical ball milling and flue gas desulfurization(FGD)gypsum on the dealkalization of bauxite residue was investigated through integrated analyses of solution chemistry,mineralogy,and microtopography.The results showed a significant decrease in Na_(2)O content(>30 wt.%)of FGD gypsum-treated bauxite residue after 30 min of mechanical ball milling.Mechanical ball milling resulted in differentiation of the elemental distribution,modification of the minerals in crystalline structure,and promotion in the dissolution of alkaline minerals,thus enhancing the acid neutralization capacity of bauxite residue.5 wt.%FGD gypsum combined with 30 min mechanical ball milling was optimal for the dealkalization of bauxite residue.展开更多
A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were ch...A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.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
Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this...Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this issue with a double benefit.Herein,the amino-functionalized lotus root-like carbon nanofibers(NH_(2)-PLCNFs)are prepared by the amination of electrospinning carbon nanofibers under dielectric barrier discharge plasma.Selective catalytic oxidation of H_(2)S to elemental sulfur(S)is achieved over the metalfree NH_(2)-PLCNFs catalyst,and the obtained composite S@NH_(2)-PLCNFs is further used as cathode in LSBs.NH_(2)-PLCNFs enable efficient desulfurization(removal capacity as high as 3.46 g H_(2)S g^(−1) catalyst)and strongly covalent stabilization of S on modified carbon nanofibers.LSBs equipped with S@NH_(2)-PLCNFs deliver a high specific capacity of 705.8 mA h g^(−1) at 1 C after 1000 cycles based on the spatial confinement and the covalent stabilization of electroactive materials on amino-functionalized porous carbon matrix.It is revealed that S@NH_(2)-PLCNFs obtained by this kind of chemical vapor deposition leads to a more homogeneous S distribution and superior electrochemical performance to the sample S/NH_(2)-PLCNF-M prepared by the traditional molten infusion.This work opens a new avenue for the combination of environment protection and energy storage.展开更多
The ultra-deep desulfurization of oil needs to be solved urgently due to various problems,including environmental pollution and environmental protection requirements.Oxidative desulfurization(ODS)was considered to be ...The ultra-deep desulfurization of oil needs to be solved urgently due to various problems,including environmental pollution and environmental protection requirements.Oxidative desulfurization(ODS)was considered to be the most promising technology.The facile synthesis of highly efficient and stable HPW-based heterogeneous catalysts for oxidative desulfurization is still a challenging task.In this paper,pentamethylene hexamine(PEHA)and phosphotungstic acid(HPW)were combined by a simple one-step method to prepare a heterogeneous catalyst of PEHA-HPW for the production of ultra-deep desulfurization fuel oil.The composite material exhibited excellent catalytic activity and high recyclability,which could reach a 100% dibenzothiophene(DBT)removal rate in 30 min and be recycled at least 5 times.Experiments and DFT simulations were used to better examine the ODS mechanism of PEHA-HPW.It was proved that the rich amino groups on the surface of PEHA-HPW play a crucial role.This work provides a simple and feasible way for the manufacture of efficient HPW-based catalysts.展开更多
In the reaction process of carbonate desulfurization lead paste,the produced PbCO_(3) is easily wrapped in the outer periphery of PbSO_(4) to form a product layer,hindering the mass transfer process.Therefore,it is ne...In the reaction process of carbonate desulfurization lead paste,the produced PbCO_(3) is easily wrapped in the outer periphery of PbSO_(4) to form a product layer,hindering the mass transfer process.Therefore,it is necessary to break the PbCO_(3) product layer.In this work,the rotor stator-reinforced reactor was selected as the enhanced desulfurization reactor for the purpose of breaking the PbCO_(3) product layer and promoting mass transfer.The breakage process of the PbCO_(3) product layer generated during the PbSO_(4) desulfurization was modeled.Computational fluid dynamics simulation to the rotation conditions was carried out to theoretically analyze the fluid flow characteristics of PbSO_(4) slurry and the wall shear stress affecting the breakage of PbCO_(3) product layer.By optimizing the rotation conditions,the distribution ratio of effective rotor wall shear stress range achieved 96.1%,and the stator wall shear stress range reached 99.15%under a rotation of 2000 r·min^(-1).The research work provides a reference for analysis of the mechanism of product layer breakage in the PbSO_(4) desulfurization process,and gives a clear and intuitive systematic study on the fluid flow characteristics and wall shear stress of the desulfurization reactor.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
As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO ...As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.展开更多
Heavy oil is characterized by high viscosity.High viscosity makes it challenging to recover and transport.HZSM-5,MoO_(3)/HZSM-5,ZrO_(2)/HZSM-5 and MoO_(3)–ZrO_(2)/HZSM-5 catalysts were developed to promote in situ de...Heavy oil is characterized by high viscosity.High viscosity makes it challenging to recover and transport.HZSM-5,MoO_(3)/HZSM-5,ZrO_(2)/HZSM-5 and MoO_(3)–ZrO_(2)/HZSM-5 catalysts were developed to promote in situ desulfurization and viscosity reduction of heavy oil.The physical and chemical properties of catalysts were characterized by XPS,XRD,TEM,NH3-TPD,etc.The effects of temperature,catalyst type and addition amount on viscosity and composition of heavy oil were evaluated.The results showed that the presence of MoO_(3)–ZrO_(2)/HZSM-5 nanoparticles during aquathermolysis could improve the oil quality by reducing the heavy fractions.It reduced viscosity by 82.56%after the reaction at 280℃ and catalyst addition of 1 wt%.The contents of resins and asphaltic in the oil samples were 5.69%lower than that in the crude oil.Sulfur content decreased from 1.45%to 1.03%.The concentration of H2S produced by the reaction was 2225 ppm.The contents of sulfur-containing functional groups sulfoxide and sulfone sulfur in the oil samples decreased by 19.92%after the catalytic reaction.The content of stable thiophene sulfur increased by 5.71%.This study provided a basis for understanding the mechanism of heavy oil desulfurization and viscosity reduction.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
The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-excha...The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-exchange adsorption properties of layered double hydroxides(LDHs).Self-supported porous adsorbent materials loaded with AFm and AFt were prepared from a composite cementitious system consisting of calcium aluminate cement(CAC)and flue gas desulfurization gypsum(FGDG)by chemical foaming technique.The mineral composition of the adsorbent material was characterized by X-ray diffraction(XRD)and Scanning electron microscopy(SEM).Through the static adsorption experiment,the adsorption effect of the mineral composition of the adsorbent on fluoride ions was deeply analyzed,and the adsorption mechanism was revealed.XRD and SEM showed that the main hydration phases of the composite cementitious system consisting of CAC and FGDG are AFm,AFt,AH_(3),and CaSO_(4)·2H_(2)O.FGDG accelerates the hydration process of CAC and inhibits the transformation of AFt to AFm.The AFt content increased,and the AFm content decreased or even disappeared as the amount of FGDG increased.Static adsorption experiment results showed that AFm and AFt in adsorbent materials could significantly enhance the adsorption of fluoride ions.The adsorption of F^(−)in aqueous solution by PAG tends more towards monolayer adsorption with a theoretical maximum capacity of 108.70 mg/g and is similar to the measured value of 112.77 mg/g.展开更多
Electroslag remelting(ESR) gives a combination of liquid metal refining and solidification structure control.One of the typical aspects of liquid metal refining during ESR for the advanced steel and alloy production i...Electroslag remelting(ESR) gives a combination of liquid metal refining and solidification structure control.One of the typical aspects of liquid metal refining during ESR for the advanced steel and alloy production is desulfurization.It involves two patterns, i.e., slag–metal reaction and gas–slag reaction(gasifying desulfurization).In this paper, the advances in desulfurization practices of ESR are reviewed.The effects of processing parameters, including the initial sulfur level of consumable electrode, remelting atmosphere, deoxidation schemes of ESR,slag composition, melting rate, and electrical parameters on the desulfurization in ESR are assessed.The interrelation between desulfurization and sulfide inclusion evolution during ESR is discussed, and advancements in the production of sulfur-bearing steel at a high-sulfur level during ESR are described.The remaining challenges for future work are also proposed.展开更多
A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and m...A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.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
基金the financial supports from National Natural Science Foundation of China(22172066,22378176)supported by State Key Laboratory of Heavy Oil ProcessingSupported by Jiangsu Collaborative Innovation Center of Technology and Material of Water Treatment,Suzhou University of Science and Technology。
文摘An efficient mass transfer process is a critical factor for regulating catalytic activity in a photocatalytic desulfurization system.Herein,a phosphotungstic acid(HPW)active center is successfully composited with a quaternary ammonium phosphotungstate-based hexadecyltrimethylammonium chloride ionic liquid(CTAC-HPW)by the ion exchange method for the photocatalytic oxidative desulfurization of dibenzothiophene sulfide.The keggin structure of HPW and highly mass transfer performance of organic cations synergistically enhanced the photocatalytic activity towards the effective convertion of dibenzothiophene(DBT)with the excitation of visible light.The deep desulfurization(<10 mg·kg^(-1))is attained within 30 min,and well stability is demonstrated within 25 cycles.Moreover,the CTAC-HPW photocatalyst projects well selectivity to interference from coexisting compounds such as olefins and aromatic hydrocarbons and universality of dibenzothiophenes,for example,4-methyldibenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT).Ultimately,a possible photocatalytic desulfurization mechanism is proposed according to the Gaschromatography-mass spectrometry(GC-MS),proving that the final product is the corresponding sulfone.The trapping experiment and electron spin resonance(ESR)analysis confirmed that h^(+)and,COOH played critical roles in the oxidation process.The work offers a practicable strategy for efficiently converting DBT to DBTO_(2) with added value.
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Funded by the National Key Research and Development Project(No.2019YFC1908204)the Guiding Projects in Fujian Province(No.2023H0023)the Fuzhou Science and Technology Plan Project(No.2022-P-012)。
文摘Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration of DA as hard segments into the PU molecular chain.The effects of DA content(φ)on the mechanical properties,thermal stability,and hydrophobicity of PU,both before and after the addition of KH550,were thoroughly examined.The results of microscopic mechanism analysis confirmed that KH550 chemically modified the surface of DA,facilitating its incorporation into the polyurethane molecular chain,thereby significantly enhancing the compatibility and dispersion of DA within the PU matrix.When the mass fraction of modified DA(MDA)reached 12%,the mechanical properties,thermal stability,and hydrophobicity of the composites were substantially improved,with the tensile strength reaching 14.9 MPa,and the contact angle measuring 100.6°.
基金financial support from the National Natural Science Foundation of China(22178154,22008094,21908082,21878133)Natural Science Foundation of Jiangsu Province(BK20190852,BK20190854)Natural Science Foundation for Jiangsu Colleges and Universities(19KJB530005).
文摘A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.
基金financially supported by the National Natural Science Foundation of China (Nos.22078135,21808092,21978119,22202088)。
文摘Porous ionic liquids have demonstrated excellent performance in the field of separation,attributed to their high specific surface area and efficient mass transfer.Herein,task-specific protic porous ionic liquids(PPILs)were prepared by employing a novel one-step coupling neutralization reaction strategy for extractive desulfurization.The single-extraction efficiency of PPILs reached 75.0%for dibenzothiophene.Moreover,adding aromatic hydrocarbon interferents resulted in a slight decrease in the extraction efficiency of PPILs(from 45.2%to 37.3%,37.9%,and 33.5%),indicating the excellent extraction selectivity of PPILs.The experimental measurements and density functional theory calculations reveal that the surface channels of porous structures can selectively capture dibenzothiophene by the stronger electrophilicity(Eint(HS surface channel/DBT)=-39.8 kcal mol^(-1)),and the multiple extraction sites of ion pairs can effectively enrich and transport dibenzothiophene from the oil phase into PPILs throughπ...π,C-H...πand hydrogen bonds interactions.Furthermore,this straightforward synthetic strategy can be employed in preparing porous liquids,offering new possibilities for synthesizing PPILs with tailored functionalities.
文摘In order to reduce the sulfur compounds in diesel fuel,boron nitride(BN)has been used as a novel metal-free catalyst in the present research.This nanocatalyst was synthesized via template-free approach followed by heating treatment at 900℃ in nitrogen atmosphere that the characteristics of the sample were identified by the X-ray diffraction,Fourier-transform infrared spectroscopy,Raman spectroscopy,field emission scanning electron microscopy,transmission electron microscopy,atomic force microscopy,and N2 adsorption-desorption isotherms.The results of structural and morphological analysis represented that BN has been successfully synthesized.The efficacy of the main operating parameters on the process was studied by using response surface methodology based on the Box-Behnken design method.The prepared catalyst showed high efficiency in oxidative desulfurization of diesel fuel with initial sulfur content of 8040 mg·kg^(-1)S.From statistical analysis,a significant quadratic model was obtained to predict the sulfur removal as a function of efficient parameters.The maximum efficiency of 72.4%was achieved under optimized conditions at oxidant/sulfur molar ratio of 10.2,temperature of 71℃,reaction time of 113 min,and catalyst dosage of 0.36 g.Also,the reusability of the BN was studied,and the result showed little reduction in activity of the catalyst after 10 times regeneration.Moreover,a plausible mechanism was proposed for oxidation of sulfur compounds on the surface of the catalyst.The present study shows that BN materials can be selected as promising metal-free catalysts for desulfurization process.
基金the National Natural Science Foundation of China(Nos.42177391,42077379)the Natural Science Foundation of Hunan Province,China(No.2022JJ20060)+1 种基金the Central South University Innovation-driven Research Program,China(No.2023CXQD065)the Fundamental Research Funds for the Central Universities of Central South University,China(No.2023ZZTS0800).
文摘The synergistic impact of mechanical ball milling and flue gas desulfurization(FGD)gypsum on the dealkalization of bauxite residue was investigated through integrated analyses of solution chemistry,mineralogy,and microtopography.The results showed a significant decrease in Na_(2)O content(>30 wt.%)of FGD gypsum-treated bauxite residue after 30 min of mechanical ball milling.Mechanical ball milling resulted in differentiation of the elemental distribution,modification of the minerals in crystalline structure,and promotion in the dissolution of alkaline minerals,thus enhancing the acid neutralization capacity of bauxite residue.5 wt.%FGD gypsum combined with 30 min mechanical ball milling was optimal for the dealkalization of bauxite residue.
基金the College Student Innovation and Entrepreneurship Training Program Project of Liaoning Province(202310148016)Doctoral Fund of Liaoning Province(201501105).
文摘A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.
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financial support from projects funded by the National Natural Science Foundation of China(22179017,52172038).
文摘Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this issue with a double benefit.Herein,the amino-functionalized lotus root-like carbon nanofibers(NH_(2)-PLCNFs)are prepared by the amination of electrospinning carbon nanofibers under dielectric barrier discharge plasma.Selective catalytic oxidation of H_(2)S to elemental sulfur(S)is achieved over the metalfree NH_(2)-PLCNFs catalyst,and the obtained composite S@NH_(2)-PLCNFs is further used as cathode in LSBs.NH_(2)-PLCNFs enable efficient desulfurization(removal capacity as high as 3.46 g H_(2)S g^(−1) catalyst)and strongly covalent stabilization of S on modified carbon nanofibers.LSBs equipped with S@NH_(2)-PLCNFs deliver a high specific capacity of 705.8 mA h g^(−1) at 1 C after 1000 cycles based on the spatial confinement and the covalent stabilization of electroactive materials on amino-functionalized porous carbon matrix.It is revealed that S@NH_(2)-PLCNFs obtained by this kind of chemical vapor deposition leads to a more homogeneous S distribution and superior electrochemical performance to the sample S/NH_(2)-PLCNF-M prepared by the traditional molten infusion.This work opens a new avenue for the combination of environment protection and energy storage.
基金supported by the National Natural Science Foundation of China(22378065,22278077)the Fujian Province Department of Science&Technology,China(2019YZ017001)。
文摘The ultra-deep desulfurization of oil needs to be solved urgently due to various problems,including environmental pollution and environmental protection requirements.Oxidative desulfurization(ODS)was considered to be the most promising technology.The facile synthesis of highly efficient and stable HPW-based heterogeneous catalysts for oxidative desulfurization is still a challenging task.In this paper,pentamethylene hexamine(PEHA)and phosphotungstic acid(HPW)were combined by a simple one-step method to prepare a heterogeneous catalyst of PEHA-HPW for the production of ultra-deep desulfurization fuel oil.The composite material exhibited excellent catalytic activity and high recyclability,which could reach a 100% dibenzothiophene(DBT)removal rate in 30 min and be recycled at least 5 times.Experiments and DFT simulations were used to better examine the ODS mechanism of PEHA-HPW.It was proved that the rich amino groups on the surface of PEHA-HPW play a crucial role.This work provides a simple and feasible way for the manufacture of efficient HPW-based catalysts.
基金financially supported by the National Key Research and Development Program of China (2018YFC1903603)。
文摘In the reaction process of carbonate desulfurization lead paste,the produced PbCO_(3) is easily wrapped in the outer periphery of PbSO_(4) to form a product layer,hindering the mass transfer process.Therefore,it is necessary to break the PbCO_(3) product layer.In this work,the rotor stator-reinforced reactor was selected as the enhanced desulfurization reactor for the purpose of breaking the PbCO_(3) product layer and promoting mass transfer.The breakage process of the PbCO_(3) product layer generated during the PbSO_(4) desulfurization was modeled.Computational fluid dynamics simulation to the rotation conditions was carried out to theoretically analyze the fluid flow characteristics of PbSO_(4) slurry and the wall shear stress affecting the breakage of PbCO_(3) product layer.By optimizing the rotation conditions,the distribution ratio of effective rotor wall shear stress range achieved 96.1%,and the stator wall shear stress range reached 99.15%under a rotation of 2000 r·min^(-1).The research work provides a reference for analysis of the mechanism of product layer breakage in the PbSO_(4) desulfurization process,and gives a clear and intuitive systematic study on the fluid flow characteristics and wall shear stress of the desulfurization reactor.
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supported by the National Natural Science Foundation of China(22178388,21776315)the Taishan Scholars Program of Shandong Province(tsqn201909065)the Fundamental Research Funds for the Central Universities(19CX05001A).
文摘As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.
基金support provided by the National Science and Technology Major Project of the Ministry of Science and Technology of China(2016ZX05012-002-005)Shandong Provincial Natural Science Foundation(Grant no.:ZR2021QE051)+1 种基金National Natural Science Foundation of China(Grant no.:52206291)the Fundamental Research Funds for the Central Universities(Grant no.:22CX06030A).
文摘Heavy oil is characterized by high viscosity.High viscosity makes it challenging to recover and transport.HZSM-5,MoO_(3)/HZSM-5,ZrO_(2)/HZSM-5 and MoO_(3)–ZrO_(2)/HZSM-5 catalysts were developed to promote in situ desulfurization and viscosity reduction of heavy oil.The physical and chemical properties of catalysts were characterized by XPS,XRD,TEM,NH3-TPD,etc.The effects of temperature,catalyst type and addition amount on viscosity and composition of heavy oil were evaluated.The results showed that the presence of MoO_(3)–ZrO_(2)/HZSM-5 nanoparticles during aquathermolysis could improve the oil quality by reducing the heavy fractions.It reduced viscosity by 82.56%after the reaction at 280℃ and catalyst addition of 1 wt%.The contents of resins and asphaltic in the oil samples were 5.69%lower than that in the crude oil.Sulfur content decreased from 1.45%to 1.03%.The concentration of H2S produced by the reaction was 2225 ppm.The contents of sulfur-containing functional groups sulfoxide and sulfone sulfur in the oil samples decreased by 19.92%after the catalytic reaction.The content of stable thiophene sulfur increased by 5.71%.This study provided a basis for understanding the mechanism of heavy oil desulfurization and viscosity reduction.
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supported by the National Natural Science Foundation of China(No.52279138)supported by Scientific Research Project of Shanxi Province(2018SF-367).
文摘The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-exchange adsorption properties of layered double hydroxides(LDHs).Self-supported porous adsorbent materials loaded with AFm and AFt were prepared from a composite cementitious system consisting of calcium aluminate cement(CAC)and flue gas desulfurization gypsum(FGDG)by chemical foaming technique.The mineral composition of the adsorbent material was characterized by X-ray diffraction(XRD)and Scanning electron microscopy(SEM).Through the static adsorption experiment,the adsorption effect of the mineral composition of the adsorbent on fluoride ions was deeply analyzed,and the adsorption mechanism was revealed.XRD and SEM showed that the main hydration phases of the composite cementitious system consisting of CAC and FGDG are AFm,AFt,AH_(3),and CaSO_(4)·2H_(2)O.FGDG accelerates the hydration process of CAC and inhibits the transformation of AFt to AFm.The AFt content increased,and the AFm content decreased or even disappeared as the amount of FGDG increased.Static adsorption experiment results showed that AFm and AFt in adsorbent materials could significantly enhance the adsorption of fluoride ions.The adsorption of F^(−)in aqueous solution by PAG tends more towards monolayer adsorption with a theoretical maximum capacity of 108.70 mg/g and is similar to the measured value of 112.77 mg/g.
基金financially supported by the National Natural Science Foundation of China (Nos.51874026 and 52074027)the Fundamental Research Funds for the Central Universities (No.FRF-TP-18-004A3)the State Key Laboratory of Advanced Metallurgy of China (No.41619019)。
文摘Electroslag remelting(ESR) gives a combination of liquid metal refining and solidification structure control.One of the typical aspects of liquid metal refining during ESR for the advanced steel and alloy production is desulfurization.It involves two patterns, i.e., slag–metal reaction and gas–slag reaction(gasifying desulfurization).In this paper, the advances in desulfurization practices of ESR are reviewed.The effects of processing parameters, including the initial sulfur level of consumable electrode, remelting atmosphere, deoxidation schemes of ESR,slag composition, melting rate, and electrical parameters on the desulfurization in ESR are assessed.The interrelation between desulfurization and sulfide inclusion evolution during ESR is discussed, and advancements in the production of sulfur-bearing steel at a high-sulfur level during ESR are described.The remaining challenges for future work are also proposed.
基金supported by the National Nature Science Foundation of China(21276117,21376111,21406092)~~
文摘A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.
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.
