Application of particle image velocity (PIV) techniques for measuringparticle size distribution and total number in an activation chamber of desulfurization system isintroduced. Watersheld algorithm is used to choose ...Application of particle image velocity (PIV) techniques for measuringparticle size distribution and total number in an activation chamber of desulfurization system isintroduced. Watersheld algorithm is used to choose the suitable initial gray level threshold whichis used to change the gray level images taken by PIV to black and white ones, then every particle inan image is isolated totally. For every isolating particle, its contour is tracked by the edgeenhancement filter function and kept by Freeman s chain code. Based on a set of particle s chincode, its size and size distribution are calculated and sorted. Finally, the experimental data ofcalcium particles and water drops, separately injected into the activation chamber, and the erroranalysis of data are given out.展开更多
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
Selective catalytic reduction(SCR) denitration may increase the emission of NH4+and NH3.The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurizat...Selective catalytic reduction(SCR) denitration may increase the emission of NH4+and NH3.The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization(WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system.The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH4+will generate new ammoniumcontaining particles and gaseous ammonia.The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation.Therefore,even if the concentration of NH4+in the desulfurization slurry is quite low, a high level of NH4+was still contained in the fine particles at the outlet of the scrubber.When the accumulated NH4+in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH3 to NH4+and increased the additional emission of primary NH4+aerosols.With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH4+emitted from entrainment and evaporation of the desulfurization slurry decreased.In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH4+concentration and p H values of the slurry.展开更多
Fe-based ionic liquid （Fe-IL） was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigate...Fe-based ionic liquid （Fe-IL） was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigated to construct a ternary desulfurization solution for wet flue gas desulfurization. The effects of flow rate and concentration of SO2, reaction temperature, pH and Fe-IL fraction in aqueous desulfurization solution on the desulfiariza- tion efficiency were investigated. The results shows that the best composition of ternary desulfurization solution of Fe-IL, ethanol and water is 1 ： 1.5 ： 3 by volume ratio, and pH should be controlled at 2.0. Under such conditions, a desulfurization rate greater than 90% could be obtained. The product of sulfuric acid had inhibition effect on the wet desulfurization process. With applying this new ternary desulfurization solution, not only the catalyst Fe-IL can be recycled and reused, but also the product sulfuric acid can be separated directly from the ternary desulfurization system.展开更多
The effects of operating parameters on desulfurization efficiency of a dual-alkali FGD process in a rotating-stream-tray(RST)scrubber are investigated.A dimensionless factor,ε,is proposed in this study to predict des...The effects of operating parameters on desulfurization efficiency of a dual-alkali FGD process in a rotating-stream-tray(RST)scrubber are investigated.A dimensionless factor,ε,is proposed in this study to predict desulfurization efficiency of this dual-alkali FGD system.ε represents the desulfurization ability of a dual alkali FGD system,determined by five main operating parameters such as sodium ion concentration,ratio of absorbent flow rate to flue gas flow rate,pH value of absorbent solution,ratio of sulfate ion to total sulfur ion in absorbent solution,and sulfur dioxide concentration of inlet flue gas.The empirical expression for predicting desulfurization efficiency at different temperatures is obtained through the experimental study and theoretical calculation.It provides useful guide for engineering design.展开更多
Aiming at deep desulfurization of gasoline,three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,or 3) were prepared and characterized.The amphiphilic vanadium(V)-substituted polyoxometalates were dissol...Aiming at deep desulfurization of gasoline,three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,or 3) were prepared and characterized.The amphiphilic vanadium(V)-substituted polyoxometalates were dissolved in water-immiscible ionic liquid([Bmim]PF6),forming a H2O2-in-[Bmim]PF6 emulsion desulfurization system with 30 m% H2O2 serving as the oxidant.The catalytic oxidation of sulfur-containing model oil has been studied in detail under various reaction conditions using this system.The ionic liquid emulsion system showed high catalytic oxidative activity in the treatment of commodity gasoline.Furthermore,the mechanism of catalytic oxidative desulfurization was also elaborated.展开更多
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
This paper combined with the actual case of flue gas desulfurization (FGD) system in cement Plant, analyzes the corrosion environment in each area of the FGD system, and selects appropriate anticorrosive materials for...This paper combined with the actual case of flue gas desulfurization (FGD) system in cement Plant, analyzes the corrosion environment in each area of the FGD system, and selects appropriate anticorrosive materials for different corrosion environment, so as to provide operating experience and reference for the safe, stable and efficient operation of the FGD system.展开更多
In this paper,acetic acid IL is selected as the solvent and mixed with citric acid ionic liquid.Using the formed binary system as a desulfurizer,explore the ability of the ionic liquid of the binary system to remove S...In this paper,acetic acid IL is selected as the solvent and mixed with citric acid ionic liquid.Using the formed binary system as a desulfurizer,explore the ability of the ionic liquid of the binary system to remove SO2 and explore the conditions that affect desulfurization.The results show that temperature is an important factor affecting the desulfurization effect of the desulfurizer,and the desulfurization efficiency decreases with the increase of temperature.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
基金The Special Funds for State Key Projects for Fun- damental Research (G1999022201-04).
文摘Application of particle image velocity (PIV) techniques for measuringparticle size distribution and total number in an activation chamber of desulfurization system isintroduced. Watersheld algorithm is used to choose the suitable initial gray level threshold whichis used to change the gray level images taken by PIV to black and white ones, then every particle inan image is isolated totally. For every isolating particle, its contour is tracked by the edgeenhancement filter function and kept by Freeman s chain code. Based on a set of particle s chincode, its size and size distribution are calculated and sorted. Finally, the experimental data ofcalcium particles and water drops, separately injected into the activation chamber, and the erroranalysis of data are given out.
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supported by the National Natural Science Foundation of China(Nos.51576039 and 51576039).
文摘Selective catalytic reduction(SCR) denitration may increase the emission of NH4+and NH3.The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization(WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system.The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH4+will generate new ammoniumcontaining particles and gaseous ammonia.The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation.Therefore,even if the concentration of NH4+in the desulfurization slurry is quite low, a high level of NH4+was still contained in the fine particles at the outlet of the scrubber.When the accumulated NH4+in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH3 to NH4+and increased the additional emission of primary NH4+aerosols.With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH4+emitted from entrainment and evaporation of the desulfurization slurry decreased.In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH4+concentration and p H values of the slurry.
基金Supported by the National Natural Science Foundation of China (21076019,90610007)the National High Technology Research and Development Program of China (2007AA06Z115)+1 种基金the Ph.D. Programs Foundation of Ministry of Education of China (20090010110003)the Fundamental Research Funds for the Central Universities (ZD1001)
文摘Fe-based ionic liquid （Fe-IL） was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigated to construct a ternary desulfurization solution for wet flue gas desulfurization. The effects of flow rate and concentration of SO2, reaction temperature, pH and Fe-IL fraction in aqueous desulfurization solution on the desulfiariza- tion efficiency were investigated. The results shows that the best composition of ternary desulfurization solution of Fe-IL, ethanol and water is 1 ： 1.5 ： 3 by volume ratio, and pH should be controlled at 2.0. Under such conditions, a desulfurization rate greater than 90% could be obtained. The product of sulfuric acid had inhibition effect on the wet desulfurization process. With applying this new ternary desulfurization solution, not only the catalyst Fe-IL can be recycled and reused, but also the product sulfuric acid can be separated directly from the ternary desulfurization system.
基金Supported by the National Hi-tech Researchand Development Program(863program)of China(No.2001AA642030-1)Key Research Project of Zhejiang Province(No.2004C23028)New Century Excellent Scholar Program of Ministry of Education of the People's Republic of China(No.NCET-04-0549)
文摘The effects of operating parameters on desulfurization efficiency of a dual-alkali FGD process in a rotating-stream-tray(RST)scrubber are investigated.A dimensionless factor,ε,is proposed in this study to predict desulfurization efficiency of this dual-alkali FGD system.ε represents the desulfurization ability of a dual alkali FGD system,determined by five main operating parameters such as sodium ion concentration,ratio of absorbent flow rate to flue gas flow rate,pH value of absorbent solution,ratio of sulfate ion to total sulfur ion in absorbent solution,and sulfur dioxide concentration of inlet flue gas.The empirical expression for predicting desulfurization efficiency at different temperatures is obtained through the experimental study and theoretical calculation.It provides useful guide for engineering design.
基金the National Nature Science Foundation of China(No.51077013,50873026)Production and Research Prospective Joint Project of Jiangsu Province of China(BY2009153)+2 种基金the Key Program for the Scientific Research Guiding Fund of Basic Scientific Research Operation Expenditure,Southeast University(3207040103)333 High-level Talent Training Project,Jiangsu Province of China (BRA2010033)Student Research Training Program of Southeast University(No.091028644) for financial support
文摘Aiming at deep desulfurization of gasoline,three amphiphilic catalysts [C18H37N(CH3)3]3+x [PMo12-xVxO40](x=1,2,or 3) were prepared and characterized.The amphiphilic vanadium(V)-substituted polyoxometalates were dissolved in water-immiscible ionic liquid([Bmim]PF6),forming a H2O2-in-[Bmim]PF6 emulsion desulfurization system with 30 m% H2O2 serving as the oxidant.The catalytic oxidation of sulfur-containing model oil has been studied in detail under various reaction conditions using this system.The ionic liquid emulsion system showed high catalytic oxidative activity in the treatment of commodity gasoline.Furthermore,the mechanism of catalytic oxidative desulfurization was also elaborated.
基金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.
文摘This paper combined with the actual case of flue gas desulfurization (FGD) system in cement Plant, analyzes the corrosion environment in each area of the FGD system, and selects appropriate anticorrosive materials for different corrosion environment, so as to provide operating experience and reference for the safe, stable and efficient operation of the FGD system.
文摘In this paper,acetic acid IL is selected as the solvent and mixed with citric acid ionic liquid.Using the formed binary system as a desulfurizer,explore the ability of the ionic liquid of the binary system to remove SO2 and explore the conditions that affect desulfurization.The results show that temperature is an important factor affecting the desulfurization effect of the desulfurizer,and the desulfurization efficiency decreases with the increase of temperature.
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.
