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
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
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
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
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
Blast furnace gas(BFG)is an important by-product energy for the iron and steel industry and has been widely used for heating or electricity generation.However,the undesirable contaminants in BFG(especially H_(2)S)gene...Blast furnace gas(BFG)is an important by-product energy for the iron and steel industry and has been widely used for heating or electricity generation.However,the undesirable contaminants in BFG(especially H_(2)S)generate harmful environmental emissions.The desulfurization of BFG is urgent for integrated steel plants due to the stringent ultra-low emission standards.Compared with other desulfurization materials,zeolite-based adsorbents represent a viable option with low costs and long service life.In this study,an ammonia-induced CuO modified 13X adsorbent(NH_(3)–CuO/13X)was prepared for H_(2)S removal from simulated BFG at low temperature.The XRD,H_(2)-TPR and TEM analysis proved that smaller CuO particles were formed and the dispersion of Cu on the surface of 13X zeolite was improved via the induction of ammonia.Evaluation on H_(2)S adsorption performance of the adsorbent was carried out using simulated BFG,and the results showed that NH_(3)–CuO/13X-3 has better breakthrough sulfur capacity,which was more than twice the sulfur capacity of CuO/13X.It is proposed that the enhanced desulfurization performance of NH_(3)–CuO/13X is attributed to an abundant pore of 13X,and combined action of 13X and CuO.This work provided an effective way to improve the sulfur capacity of zeolite-based adsorbents via impregnation method by ammonia induction.展开更多
In this paper,the effect of vibration intensity on the spatial distribution of sulfur content in bed particles was studied.The effects of vibration and airflow on the mechanical characteristics of particles were studi...In this paper,the effect of vibration intensity on the spatial distribution of sulfur content in bed particles was studied.The effects of vibration and airflow on the mechanical characteristics of particles were studied,the collision behavior mode of particles was determined,the spatial saltation law of particles was investigated,the spatial functional axis of beds was determined,and the saltation separation period of particles was determined.The test results show that:When separation bed provides inlet airflow velocity(U_(in)) is 2.55 m/s,the airflow distribution interval of I,II and III areas were U_(I)=2.55-2.57 m/s,U_(II)=1.33-1.35 m/s,U_(III)=0.35-0.38 m/s,respectively;when separation bed vibration amplitude (A)A=2.4-2.5 mm,separation bed vibration frequency (f) f=23-24 Hz,the desulfurization effect is the best.When vibration intensity (Γ)Γ=1.22,U_(in)=1.05 m/s,the particles have disordered contact and collision behavior.WhenΓ=14.89,U_(in)=3.18 m/s,the particles have a transition cataclastic collision.WhenΓ=5.80,U_(in)=2.55 m/s,the particles have directional collision behavior.It is determined that the OX axis is the transverse stable diffusion axis of the material,the OY axis is the longitudinal gradient transport axis of the material,and the OZ axis is the vertical density cascade distribution axis of the material.When separation time (T) T=0-10 s was the period of disorderly diffusion and mixing of particles,T=10-20 s was the period of directional migration and stratification of particles,and T=20-30 s was the period of cascade distribution and separation of particles.Finally,separation experiments conducted under optimal operating parameters demonstrated that the clean coal yield was 72.02%with a sulfur content of 0.98%.展开更多
The extractive desulfurization of a model gaso- line containing several alkyl thiols and aromatic thiophenic compounds was investigated using two imidazolium-based ionic liquids （ILs）, 1-butyl-3-methylimidazolium te...The extractive desulfurization of a model gaso- line containing several alkyl thiols and aromatic thiophenic compounds was investigated using two imidazolium-based ionic liquids （ILs）, 1-butyl-3-methylimidazolium tetrachloroaluminate, and 1-octyl-3-methylimidazolium te- trafluoroborate, as extractants. A fractional factorial design of experiments was employed to evaluate the effects and possible interactions of several process variables. Analysis of variance tests indicated that the number of extraction steps and the IL/gasoline volume ratio were of statistically highly significant, but none of the interactions were significant. The results showed that the desulfurization efficiency of the model gasoline by the ILs could reach 95.2 % under the optimal conditions. The optimized conditions were applied to study the extraction of thiophenic compounds in model gasoline and several real gasoline samples; the following order was observed in their separation： benzothio- phenc 〉 thiophcne 〉 3-methylthiophene 〉 2-methylthiophene, with 96.1% removal efficiency for benzothiophene. The IL extraction was successfully applied as a complementary process to the adsorptive desulfurization with acti- vated Raney nickel and acetonitrile solvent. The results indicated that the adsorptive process combined with IL extraction could provide high efficiency and selectivity, which can be regarded as a promising energy efficient desulfurization strategy for production of low-sulfur gasoline.展开更多
In this paper,a novel copper-based catalyst for FCC gasoline improving the ability of removal the sulfur and avoiding the loss of the octane number from olefin saturation by reactive adsorption desulfurization(RADS) w...In this paper,a novel copper-based catalyst for FCC gasoline improving the ability of removal the sulfur and avoiding the loss of the octane number from olefin saturation by reactive adsorption desulfurization(RADS) was investigated.The series of Cu/Zn O-Al_2 O_3 catalysts were characterized by X-ray powder diffraction(XRD),N_2 adsorption analysis and temperature-programmed reduction(TPR) studies,X-ray photoelectron spectroscopy(XPS),scanning electron microscope(SEM) and transmission electron microscopy(TEM).The experiment results showed that the catalysts had an optimum desulfurization ability with copper loading 6 wt%,which the sulfur contents of product decreased less than 10 μg/g and olefin contents decreased from 16.19% to 14.14% for the long period operation.The appropriate Cu loading content could lead to the high active and low apparent activation energy(E_a).Therefore,the Cu-based catalyst may become a novel catalyst for second-generation for reactive adsorption desulfurization,which achieves the high desulfurization active and low olefins saturation to satisfy the upgrading the product.展开更多
Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution. The effects of treatment temperature on crystallinity, textural properties and chemical composi...Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution. The effects of treatment temperature on crystallinity, textural properties and chemical composites were studied by XRD, N2 sorption, FT-IR and XRF techniques. The desulfurization performance of parent and alkaline-treated beta zeolites was investigated by static absorption in four model fuels, containing four sulfur compounds of different molecular sizes like thiophene （TP）, 3-methylthiophene （3-MT）, benzothiophene （BT） and dibenzothiophene （DBT）, respectively. The crystallinity was observed to be successfully maintained when the treatment temperature was below 50 ℃. Mesoporosity of beta zeolite was evidently developed with alkaline treatment. The formation of mesopore remarkably improved the desulfurization performance for TP, 3-MT, BT and DBT, especially for DBT with larger molecular diameter. Though the addition of toluene in the model fuels resulted in a significant drop of the desulfurization performance of mesoporous beta zeolite, the introduction of cerium ions to some extent mitigated the effect of toluene, which means that both the adsorbent’s porous structure and the adsorption mode are responsible for the desulfurization performance. The adsorbent of cerium ion-exchanged mesoporous beta showed about 80% recovery of desulfurization after the first regeneration.展开更多
To investigate the effect of texture structure on the desulfurization performance in the Ni/ZnO reactive adsorption desulfurization（RADS） system,two kinds of ZnO porous materials with rod-shaped morphology were synt...To investigate the effect of texture structure on the desulfurization performance in the Ni/ZnO reactive adsorption desulfurization（RADS） system,two kinds of ZnO porous materials with rod-shaped morphology were synthesized and their structure was characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,and N2 adsorption/desorption.The formation mechanisms of hierarchical porous ZnO（ZnO with meso and macro pores） were also studied.Their application performance was evaluated in the RADS process over Ni/ZnO absorbent.Due to the difference in structure between the two kinds of ZnO,the two ZnO based adsorbents showed different desulfurization activity.展开更多
High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we...High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.展开更多
The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scann...The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scanning electron microscopy(SEM), infrared spectrometry(IR) and the Brunner-Emmet-Teller(BET) techniques. The WO_3/C composite, in comparison with the WO_3 and C_3N_4, features smaller particle size, bigger surface area and higher desulphurization performance. The influence of the reaction temperature, the catalyst dosage, the reaction time, the oxidant dosage, the sulfide type and the extractant dose on desulfurization reaction was studied. The results showed that the WO_3/C composite revealed a higher desulfurization activity than the WO_3. The desulfurization rate could reach up to 95.8% under optimal conditions covering a catalyst dosage of 0.02 g, a H_2O_2 amount of 0.2 mL, a 1-ethyl-3-methylimidazolium ethyl sulfate(EMIES) amount of 1.0 mL, a reaction temperature of 70 ℃ and a reaction time of 180 min. After five recycles, the desulfurization activity of catalyst did not significantly decline.展开更多
Zn-based sorbent （Z20SC） prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearl...Zn-based sorbent （Z20SC） prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp（-8.270×103/RgT） and Dep=1.262×10-4exp（1.522×104/RgT）.It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.展开更多
High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke （SC） and ZnO is selected as the support and active component of sorbent, resp...High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke （SC） and ZnO is selected as the support and active component of sorbent, respectively. The sorbent preparation process includes high-pressure impregnation, filtration, ovendry and calcination. The aim of this research is to primarily study the effects of the impregnation pressure on physical properties and desulfurization ability of the sorbent. The desulfurization experiment was carried out in a fixed-bed reactor at 500 ~C and a simulated coal gas used in this work was composed of CO （33 vol%）, H2 （39 vol%）, H2S （300 ppm in volume）, and N2 （balance）. Experimental results show that the pore structure of the SC support can be improved effectively and ZnO active component can be uniformly dispersed on the support, with the small particle size of 10-500 nm. Sorbents prepared using high-pressure impregnation have better desulfurization capacity and their active components have higher utilization rate. P20-ZnSC sorbent, obtained by high-pressure impregnation at 20 atm, has the best desulfurization ability with a sulfur capacity of 7.54 g S/100g sorbent and a breakthrough time of 44 h. Its desulfurization precision and efficiency of removing H2S from the middle temperature gases can reach 〈 1 ppm and 〉99.7%, respectively, before sorbent breakthrough.展开更多
12-Tungstophosphoric acid（PW） supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization（ODS） of mixed thiophenic compounds in model oil and crude oil under mild conditions u...12-Tungstophosphoric acid（PW） supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization（ODS） of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide（H2O2） as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-tosulfur compounds（S-compounds） molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene（DBT） and mixed thiophenic model oil under atmospheric pressure at 75 ℃ in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.展开更多
The reactive adsorption behavior of thiophene on the reduced Ni/ZnO sample was investigated by a combination of theoretical and experimental study.It is widely accepted that Ni is responsible for the sulfur-removal of...The reactive adsorption behavior of thiophene on the reduced Ni/ZnO sample was investigated by a combination of theoretical and experimental study.It is widely accepted that Ni is responsible for the sulfur-removal of thiophene to release S-free hydrocarbons.Such surface reaction was simulated by DFT method.It is demonstrated that thiophene is mainly adsorbed as p-complexation mode over metallic Ni.During desulfurization,the Se Ni bond is formed and the Ce S bond is thus split without pre-hydrogenation,resulting in the formation of Ni_(3)S_(2)phase and S-free C4 olefin which can be further saturated in the presence of H_(2).The S-transfer between Ni_(3)S_(2)and ZnO was monitored by in-situ XRD and STEM with EDS mapping.Two essential features were identified for efficient S-transfer,namely,1)the H_(2)atmosphere,and 2)the two phases are presented with close contact.Based on the acquired information,a general scenario of sulfur trail has been proposed for the desulfurization of thiophene on Ni/ZnO.展开更多
Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot m...Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.展开更多
With the bimodal mesoporous silica(BMMS)acting as the support and the composite of TiO2 with phosphotungstic acid(PTA)functioning as the active constituent,TiO_(2)-PTA/BMMS was synthesized by the two-step impregnation...With the bimodal mesoporous silica(BMMS)acting as the support and the composite of TiO2 with phosphotungstic acid(PTA)functioning as the active constituent,TiO_(2)-PTA/BMMS was synthesized by the two-step impregnation route.This catalyst was applied in the photocatalytic oxidative desulfurization(PODS)process,with dibenzothiophene serving as the model sulfur compound.PODS proceeds in one pot,in which H_(2)O_(2) acts as the oxidant and methanol plays the role of the solvent.TiO_(2)-PTA/BMMS was characterized by XRD,N_(2) adsorption and desorption,XRF,FTIR,UV-vis,SEM,EDS and TEM techniques.It showed that the introduction of PTA contributes higher order,higher surface area and pore volume to the bimodal mesoporous support.With TiO_(2)-PTA/BMMS used as the catalyst under the UV irradiation,the desulfurization rate can reach 99.6%.This result is obviously higher than that achieved by TiO_(2)/BMMS.The catalyst also has no significant drop in catalytic activity after eight runs of reusing.In such catalytic system,the synergistic effects of this photocatalytic oxidation and the extraction with the methanol serving as the solvent played an indispensable role.展开更多
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.
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.
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financially supported by National Natural Science Foundation of China(Grant.22076189)National Key Research and Development Program of China(No.2023YFC3707003)the Joint Fund of Yulin University and Dalian National Laboratory for Clean Energy(Grant.YLU-DNL Fund 2022003).
文摘Blast furnace gas(BFG)is an important by-product energy for the iron and steel industry and has been widely used for heating or electricity generation.However,the undesirable contaminants in BFG(especially H_(2)S)generate harmful environmental emissions.The desulfurization of BFG is urgent for integrated steel plants due to the stringent ultra-low emission standards.Compared with other desulfurization materials,zeolite-based adsorbents represent a viable option with low costs and long service life.In this study,an ammonia-induced CuO modified 13X adsorbent(NH_(3)–CuO/13X)was prepared for H_(2)S removal from simulated BFG at low temperature.The XRD,H_(2)-TPR and TEM analysis proved that smaller CuO particles were formed and the dispersion of Cu on the surface of 13X zeolite was improved via the induction of ammonia.Evaluation on H_(2)S adsorption performance of the adsorbent was carried out using simulated BFG,and the results showed that NH_(3)–CuO/13X-3 has better breakthrough sulfur capacity,which was more than twice the sulfur capacity of CuO/13X.It is proposed that the enhanced desulfurization performance of NH_(3)–CuO/13X is attributed to an abundant pore of 13X,and combined action of 13X and CuO.This work provided an effective way to improve the sulfur capacity of zeolite-based adsorbents via impregnation method by ammonia induction.
基金supported by Science and Technology Project of Hebei Education Department (No. ZD2022128)Tangshan Science and Technology Plan Project (No. 22130226H)。
文摘In this paper,the effect of vibration intensity on the spatial distribution of sulfur content in bed particles was studied.The effects of vibration and airflow on the mechanical characteristics of particles were studied,the collision behavior mode of particles was determined,the spatial saltation law of particles was investigated,the spatial functional axis of beds was determined,and the saltation separation period of particles was determined.The test results show that:When separation bed provides inlet airflow velocity(U_(in)) is 2.55 m/s,the airflow distribution interval of I,II and III areas were U_(I)=2.55-2.57 m/s,U_(II)=1.33-1.35 m/s,U_(III)=0.35-0.38 m/s,respectively;when separation bed vibration amplitude (A)A=2.4-2.5 mm,separation bed vibration frequency (f) f=23-24 Hz,the desulfurization effect is the best.When vibration intensity (Γ)Γ=1.22,U_(in)=1.05 m/s,the particles have disordered contact and collision behavior.WhenΓ=14.89,U_(in)=3.18 m/s,the particles have a transition cataclastic collision.WhenΓ=5.80,U_(in)=2.55 m/s,the particles have directional collision behavior.It is determined that the OX axis is the transverse stable diffusion axis of the material,the OY axis is the longitudinal gradient transport axis of the material,and the OZ axis is the vertical density cascade distribution axis of the material.When separation time (T) T=0-10 s was the period of disorderly diffusion and mixing of particles,T=10-20 s was the period of directional migration and stratification of particles,and T=20-30 s was the period of cascade distribution and separation of particles.Finally,separation experiments conducted under optimal operating parameters demonstrated that the clean coal yield was 72.02%with a sulfur content of 0.98%.
基金National Iranian Oil Refining & Distribution Company(NIORDC) and Research & Development (R&D) center of this company for their financial support during the completion of this work
文摘The extractive desulfurization of a model gaso- line containing several alkyl thiols and aromatic thiophenic compounds was investigated using two imidazolium-based ionic liquids （ILs）, 1-butyl-3-methylimidazolium tetrachloroaluminate, and 1-octyl-3-methylimidazolium te- trafluoroborate, as extractants. A fractional factorial design of experiments was employed to evaluate the effects and possible interactions of several process variables. Analysis of variance tests indicated that the number of extraction steps and the IL/gasoline volume ratio were of statistically highly significant, but none of the interactions were significant. The results showed that the desulfurization efficiency of the model gasoline by the ILs could reach 95.2 % under the optimal conditions. The optimized conditions were applied to study the extraction of thiophenic compounds in model gasoline and several real gasoline samples; the following order was observed in their separation： benzothio- phenc 〉 thiophcne 〉 3-methylthiophene 〉 2-methylthiophene, with 96.1% removal efficiency for benzothiophene. The IL extraction was successfully applied as a complementary process to the adsorptive desulfurization with acti- vated Raney nickel and acetonitrile solvent. The results indicated that the adsorptive process combined with IL extraction could provide high efficiency and selectivity, which can be regarded as a promising energy efficient desulfurization strategy for production of low-sulfur gasoline.
基金financially support by the National Natural Science Foundation (Grants No.2117625821676300)the Fundamental Research Funds for the Central Universities (Grants No.15CX06051A)
文摘In this paper,a novel copper-based catalyst for FCC gasoline improving the ability of removal the sulfur and avoiding the loss of the octane number from olefin saturation by reactive adsorption desulfurization(RADS) was investigated.The series of Cu/Zn O-Al_2 O_3 catalysts were characterized by X-ray powder diffraction(XRD),N_2 adsorption analysis and temperature-programmed reduction(TPR) studies,X-ray photoelectron spectroscopy(XPS),scanning electron microscope(SEM) and transmission electron microscopy(TEM).The experiment results showed that the catalysts had an optimum desulfurization ability with copper loading 6 wt%,which the sulfur contents of product decreased less than 10 μg/g and olefin contents decreased from 16.19% to 14.14% for the long period operation.The appropriate Cu loading content could lead to the high active and low apparent activation energy(E_a).Therefore,the Cu-based catalyst may become a novel catalyst for second-generation for reactive adsorption desulfurization,which achieves the high desulfurization active and low olefins saturation to satisfy the upgrading the product.
基金supported by the Fundamental Research Funds for the Central Universities(No.DUT10LK25)the Natural Science Foundation of China(No.21106014)
文摘Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution. The effects of treatment temperature on crystallinity, textural properties and chemical composites were studied by XRD, N2 sorption, FT-IR and XRF techniques. The desulfurization performance of parent and alkaline-treated beta zeolites was investigated by static absorption in four model fuels, containing four sulfur compounds of different molecular sizes like thiophene （TP）, 3-methylthiophene （3-MT）, benzothiophene （BT） and dibenzothiophene （DBT）, respectively. The crystallinity was observed to be successfully maintained when the treatment temperature was below 50 ℃. Mesoporosity of beta zeolite was evidently developed with alkaline treatment. The formation of mesopore remarkably improved the desulfurization performance for TP, 3-MT, BT and DBT, especially for DBT with larger molecular diameter. Though the addition of toluene in the model fuels resulted in a significant drop of the desulfurization performance of mesoporous beta zeolite, the introduction of cerium ions to some extent mitigated the effect of toluene, which means that both the adsorbent’s porous structure and the adsorption mode are responsible for the desulfurization performance. The adsorbent of cerium ion-exchanged mesoporous beta showed about 80% recovery of desulfurization after the first regeneration.
基金Financial support from the National Basic Research Program of China (No. 2010CB226905)the National Natural Science Foundation of China (Nos. 21176258, U1162203)the Specialized Research Fund for the Doctoral Program of Higher Education (20110133110002)
文摘To investigate the effect of texture structure on the desulfurization performance in the Ni/ZnO reactive adsorption desulfurization（RADS） system,two kinds of ZnO porous materials with rod-shaped morphology were synthesized and their structure was characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,and N2 adsorption/desorption.The formation mechanisms of hierarchical porous ZnO（ZnO with meso and macro pores） were also studied.Their application performance was evaluated in the RADS process over Ni/ZnO absorbent.Due to the difference in structure between the two kinds of ZnO,the two ZnO based adsorbents showed different desulfurization activity.
基金This work was financially supported by the National Natural Science Foundation of China(No.21722604)the Postdoctoral Foundation of China(Nos.2019M651743 and 2020M671365)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20190852)the National Youth Natural Science Foundation(No.8111310009).
文摘High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.
基金the financial support of the Natural Science Foundation of China (Project No. 21003069)the Liaoning Province Doctoral Fund (Project No.201501105)
文摘The WO_3/C composite was successfully prepared by calcination of a mixture of WO_3 and g-C_3N_4 at 520 ℃. The as-synthesized samples were analyzed by X-ray diffraction(XRD), electronic differential system(EDS), scanning electron microscopy(SEM), infrared spectrometry(IR) and the Brunner-Emmet-Teller(BET) techniques. The WO_3/C composite, in comparison with the WO_3 and C_3N_4, features smaller particle size, bigger surface area and higher desulphurization performance. The influence of the reaction temperature, the catalyst dosage, the reaction time, the oxidant dosage, the sulfide type and the extractant dose on desulfurization reaction was studied. The results showed that the WO_3/C composite revealed a higher desulfurization activity than the WO_3. The desulfurization rate could reach up to 95.8% under optimal conditions covering a catalyst dosage of 0.02 g, a H_2O_2 amount of 0.2 mL, a 1-ethyl-3-methylimidazolium ethyl sulfate(EMIES) amount of 1.0 mL, a reaction temperature of 70 ℃ and a reaction time of 180 min. After five recycles, the desulfurization activity of catalyst did not significantly decline.
基金supported by the National Basic Research Program of China (2012CB723105)the National Natural Science Foundation of China(20976117)+1 种基金Shanxi Province Natural Science Foundation (2010011014-3)Shanxi Province Basic Conditions Platform for Science and Technology Project(2010091015)
文摘Zn-based sorbent （Z20SC） prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp（-8.270×103/RgT） and Dep=1.262×10-4exp（1.522×104/RgT）.It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.
基金supported by the financial support of National Basic Research Program of China (2012CB723105)National Natural Science Foundation of China (20976117)+1 种基金Shanxi Province Natural Science Foundation(2010011014-3)Shanxi Province Basic Conditions Platform for Science and Technology Project (2010091015)
文摘High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke （SC） and ZnO is selected as the support and active component of sorbent, respectively. The sorbent preparation process includes high-pressure impregnation, filtration, ovendry and calcination. The aim of this research is to primarily study the effects of the impregnation pressure on physical properties and desulfurization ability of the sorbent. The desulfurization experiment was carried out in a fixed-bed reactor at 500 ~C and a simulated coal gas used in this work was composed of CO （33 vol%）, H2 （39 vol%）, H2S （300 ppm in volume）, and N2 （balance）. Experimental results show that the pore structure of the SC support can be improved effectively and ZnO active component can be uniformly dispersed on the support, with the small particle size of 10-500 nm. Sorbents prepared using high-pressure impregnation have better desulfurization capacity and their active components have higher utilization rate. P20-ZnSC sorbent, obtained by high-pressure impregnation at 20 atm, has the best desulfurization ability with a sulfur capacity of 7.54 g S/100g sorbent and a breakthrough time of 44 h. Its desulfurization precision and efficiency of removing H2S from the middle temperature gases can reach 〈 1 ppm and 〉99.7%, respectively, before sorbent breakthrough.
基金Razi University Research Council for support of this work
文摘12-Tungstophosphoric acid（PW） supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization（ODS） of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide（H2O2） as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-tosulfur compounds（S-compounds） molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene（DBT） and mixed thiophenic model oil under atmospheric pressure at 75 ℃ in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.
基金financially supported by research grant from Sinopec(Fund No.118016-8)。
文摘The reactive adsorption behavior of thiophene on the reduced Ni/ZnO sample was investigated by a combination of theoretical and experimental study.It is widely accepted that Ni is responsible for the sulfur-removal of thiophene to release S-free hydrocarbons.Such surface reaction was simulated by DFT method.It is demonstrated that thiophene is mainly adsorbed as p-complexation mode over metallic Ni.During desulfurization,the Se Ni bond is formed and the Ce S bond is thus split without pre-hydrogenation,resulting in the formation of Ni_(3)S_(2)phase and S-free C4 olefin which can be further saturated in the presence of H_(2).The S-transfer between Ni_(3)S_(2)and ZnO was monitored by in-situ XRD and STEM with EDS mapping.Two essential features were identified for efficient S-transfer,namely,1)the H_(2)atmosphere,and 2)the two phases are presented with close contact.Based on the acquired information,a general scenario of sulfur trail has been proposed for the desulfurization of thiophene on Ni/ZnO.
基金financially supported by the National Natural Science Foundation of China (Nos. 21506080 and 21766007)Natural Science Foundation of Jiangsu Province (No. BK20150485)+1 种基金Advanced Talents of Jiangsu University (No. 15JDG053)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Deep eutectic solvents(DESs) are a new class of green solvents analogous to ionic liquids due to their biodegradable capacity and low cost. However, the direct extractive desulfurization of diesel oil by DESs cannot meet the government’s standard. In this work, amphiphilic polyoxometalates were synthesized and characterized by FT-IR and mass spectrometry.The oxidative desulfurization results showed that benzothiophene(BT) could be completely removed by employing a [(CH)P(CH)]PMoO, DES(ChCl/2 Ac) and HOsystem. It was also found that the organic cation of catalysts played a positive role in oxidative desulfurization. The reaction conditions, such as reaction temperature and time, the amount of catalyst and DES and HO/S(O/S) molar ratio, were optimized. Different sulfides were tested to determine the desulfurization selectivity of the optimal reaction system, and it was found that 97.2% of dibenzothiophene(DBT) could be removed followed by 80.7% of 4-MDBT and 76.0% of 4,6-DMDBT. After reaction, the IR spectra showed that the catalyst [(CH)P(CH)]PMoOwas stable during the reaction process and the oxidative product was dibenzothiophene sulfone(DBTO). Furthermore, the catalyst can be regenerated and recycled for four runs with little loss of activity.
基金This work was supported by the Program for Liaoning Excellent Talents in Universities‘LNET’(LJQ2015062)the Program for Science and Technology Agency of Liaoning Province(20170540585)+1 种基金the General Scientific Research Project of Liaoning Provincial Department of Education(L2015296,L2016018)the Science and Technology Planning Project of Fushun(FSKJHT201376).
文摘With the bimodal mesoporous silica(BMMS)acting as the support and the composite of TiO2 with phosphotungstic acid(PTA)functioning as the active constituent,TiO_(2)-PTA/BMMS was synthesized by the two-step impregnation route.This catalyst was applied in the photocatalytic oxidative desulfurization(PODS)process,with dibenzothiophene serving as the model sulfur compound.PODS proceeds in one pot,in which H_(2)O_(2) acts as the oxidant and methanol plays the role of the solvent.TiO_(2)-PTA/BMMS was characterized by XRD,N_(2) adsorption and desorption,XRF,FTIR,UV-vis,SEM,EDS and TEM techniques.It showed that the introduction of PTA contributes higher order,higher surface area and pore volume to the bimodal mesoporous support.With TiO_(2)-PTA/BMMS used as the catalyst under the UV irradiation,the desulfurization rate can reach 99.6%.This result is obviously higher than that achieved by TiO_(2)/BMMS.The catalyst also has no significant drop in catalytic activity after eight runs of reusing.In such catalytic system,the synergistic effects of this photocatalytic oxidation and the extraction with the methanol serving as the solvent played an indispensable role.
