The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a...The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a higher isobutene selectivity.However,the catalyst stability remains a key problem for the long-running acetone conversion and the reasons for catalyst deactivation are poorly understood up to now.Herein,the deactivation mechanism of Lewis acidic Y/Beta catalyst during the acetone to isobutene conversion was investigated by various characterization techniques,including acetone-temperature-programmed surface reaction,gas chromatography-mass spectrometry,in situ ultraviolet-visible,and ^(13)C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy.A successive aldol condensation and cyclization were observed as the main side-reactions during the acetone conversion at Lewis acidic Y sites.In comparison with the low reaction temperature,a rapid formation and accumulation of the larger cyclic unsaturated aldehydes/ketones and aromatics could be observed,and which could strongly adsorb on the Lewis acidic sites,and thus cause the catalyst deactivation eventually.After a simple calcination,the coke deposits could be easily removed and the catalytic activity could be well restored.展开更多
A shaped binderless and two binder‐containing ZSM‐11 zeolite catalysts were prepared and characterized by powder X‐ray diffraction, N2 adsorption‐desorption, and pyridine adsorption‐infrared measurements. The bin...A shaped binderless and two binder‐containing ZSM‐11 zeolite catalysts were prepared and characterized by powder X‐ray diffraction, N2 adsorption‐desorption, and pyridine adsorption‐infrared measurements. The binderless catalyst was synthesized using a dry‐gel conversion technique, inwhich 1,6‐hexanediamine and tetrabutylammonium bromide were used as structure‐directingagents and no other alkaline materials were added. The catalytic performance of the zeolites in the direct amination of isobutene to tert‐butylamine was evaluated in a fixed‐bed reactor. By virtue of its high crystallinity as well as its good mechanical strength, the shaped binderless ZSM‐11 catalyst showed a higher rate of formation of tert‐butylamine than did the binder‐containing catalysts.展开更多
The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with...The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas.ZrO_(2) with small crystalline size showed higher CO conversion and isobutene selectivity,while samples with large crystalline size preferred to form dimethyl ether(DME)instead of hydrocarbons,much less to isobutene.Oxygen defects(ODefects)analyzed by X-ray photoelectron spectroscopy(XPS)provided evidence that more ODefectsoccupied on the surface of ZrO_(2) catalysts with smaller crystalline size.Electron paramagnetic resonance(EPR)and ultraviolet–visible diffuse reflectance(UV–vis DRS)confirmed the presence of high concentration of surface defects and Zr3+on mZrO_(2)-5.9 sample,respectively.In situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS)analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased.These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species,and thus the products distribution changed.This study provides an in-depth insight for active sites regulation of ZrO_(2) catalyst in CO hydrogenation reaction.展开更多
The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane s...The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.展开更多
The catalytic property of AICl(3) catalyst immobilized on gamma -Al2O3 for isobutene polymerization has been studied. It was found that the activity, selectivity and stability of the catalyst are dependent greatly on ...The catalytic property of AICl(3) catalyst immobilized on gamma -Al2O3 for isobutene polymerization has been studied. It was found that the activity, selectivity and stability of the catalyst are dependent greatly on geometric characteristic pf the pore structure and size of catalyst. Although the activity and selectivity of the catalysts with micro- and meso-pore structure are all high in initial stage, but their stability is low, while those with bimodal meso- and macro-pore structure are excellent. Increasing granularity of the catalyst(particle become fine) brings about an increase in isobutene conversion, but a decrease in selectivity, resulting in lower average molecular weight and iis broader distribution.展开更多
Isooctane attracts great interest in recent years because of its promising potential as friendlyenvironmental gasoline,which is obtained by dimerization of isobutene with a hydrogenation step.Herein,a solid acid catal...Isooctane attracts great interest in recent years because of its promising potential as friendlyenvironmental gasoline,which is obtained by dimerization of isobutene with a hydrogenation step.Herein,a solid acid catalyst sulfated zirconia modified by ZnO was prepared.The oligomerization of isobutene had been investigated over ZrO_(2)-SO_(4) and ZnO(X)/ZrO_(2)-SO_(4) catalyst in order to find efficient catalysts for the production of isobutene oligomers.The presence of ZnO obviously enhanced the dimerization of isobutene and ZnO(X)/ZrO_(2)-SO_(4) exhibited the highest di-isobutene yield of 60%.Kinetic studies showed the higher trimerization-to-dimerization activation energy ratios of ZnO(X)/ZrO_(2)-SO_(4) than those of ZrO_(2)-SO_(4) from 353 to 393 K.In addition,reaction rate of dimerization was higher than trimerization over ZnO(X)/ZrO_(2)-SO_(4).The high L/B ratio manifested the capability to enhance the selectivity of C8 in isobutene dimerization.Furthermore,ZnO(X)/ZrO_(2)-SO_(4) exhibited stable conversion for the dimerization of isobutene.展开更多
Mixed oxide catalyst Cs0.1Fe2Co6BiMnMo12Ox was prepared by the coprecipitation method. Selective oxidation of isobutene was carried out in a fixed-bed reactor over Cs0.1Fe2Co6BiMnMo12Ox. The results showed that the ca...Mixed oxide catalyst Cs0.1Fe2Co6BiMnMo12Ox was prepared by the coprecipitation method. Selective oxidation of isobutene was carried out in a fixed-bed reactor over Cs0.1Fe2Co6BiMnMo12Ox. The results showed that the catalyst had high catalytic activity. Under the optimum reaction conditions (n(i-C4=):n(O2)=1:2-1:4, space velocity=180 h-1, T=360℃), the yields of methacrolein and methacrylic acid can reach 80% and 8%, respectively. The total yield of liquid products (methacrolein, methacrylic acid and acetic acid) can reach about 90%.展开更多
Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a tempe...Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a temperature range of 338-383 K in the presence of laboratory prepared Ni/Al_2O_3 as a catalyst and n-pentane as solvent.The influence of various parameters such as temperature,catalyst loading and initial concentration of IB was examined.A Langmuir-Hinshelwood kinetic model of IB dimerization was established and the parameters were estimated on the basis of the measured data.The feasibility of oligomerization of IB based on the reactive distillation was simulated in ASPEN PLUS using the kinetics developed.The simulation results showed that the catalyst of Ni/Al_2O_3 had higher selectivity to diisobutene(DIB) and slightly lower conversion of IB than ion exchange resin in the absence of polar substances.展开更多
The oxidative dehydrogenation of isobutane to isobutene was examined for the use in the preparation of FSM-16 and related compounds doped by chromium with expectations that a yield of isobutene of greater than 8% coul...The oxidative dehydrogenation of isobutane to isobutene was examined for the use in the preparation of FSM-16 and related compounds doped by chromium with expectations that a yield of isobutene of greater than 8% could be achieved. The activity depended on the molding procedure of the catalyst and the doping method of the chromium species. In the present study, 8.8% and 8.3% of the yield of isobutene were obtained at 0.75 h and 6 h on-stream for the catalyst （Cr-loading; 6.2 wt.%） molded using wet treatment hut not pressurization treatment, in which the chromium species were directly added into the aqueous solution containing raw FSM-16 （hydrated sodium silicate powder） at an initial stage of the catalyst preparation. The structure information was based on XRD （X-ray diffraction）, the specific surface area was determined using a conventional BET （Brunauer-Emmett-Teller） nitrogen adsorption and the loading of chromium was estimated using ICP （inductively coupled plasma）. All those parameters combined with the molding method indicated that the catalytic activity was more influenced by the loading of chromium into bulk but not on surface of the catalyst rather than by the hexagonal structure of FSM-16 and the surface area.展开更多
Ternary multifunctional A<sub>1</sub>Zn<sub>y</sub>Zr<sub>z</sub>O<sub>n</sub> catalysts are prepared by introducing A-site transition metals with the redox capability i...Ternary multifunctional A<sub>1</sub>Zn<sub>y</sub>Zr<sub>z</sub>O<sub>n</sub> catalysts are prepared by introducing A-site transition metals with the redox capability into binary Zn<sub>1</sub>Zr<sub>8</sub>O<sub>n</sub>. Structure and morphology were investigated by means of XRD, BET and FESEM, respectively. Activity data showed that Cr addition exhibited obvious beneficial effect to promote isobutene production from direct conversion of bio-ethanol compared to other A-site metal dopants. A significant higher yield of isobutene over Cr-promoted Zn<sub>1</sub>Zr<sub>8</sub>O<sub>n</sub> catalyst was also observed with respect to its binary Zn<sub>1</sub>Zr<sub>8</sub>O<sub>n</sub> counterpart. The choice of A-site metal is of prime importance in the isobutene production, catalyzing mainly the ethanol dehydrogenation, meanwhile the appropriate addition of zinc on the catalyst surface is also essential for good isobutene yield.展开更多
The further improvement of methacrolein(MAL)selectivity from isobutene(IB)oxidation is crucial and challenging.In this study,based on the typical Mo-Bi-Fe-Co-K-O mixed metal oxide,the rare earth element Gd-doped,Ce-do...The further improvement of methacrolein(MAL)selectivity from isobutene(IB)oxidation is crucial and challenging.In this study,based on the typical Mo-Bi-Fe-Co-K-O mixed metal oxide,the rare earth element Gd-doped,Ce-doped and CeGd co-doped catalysts were prepared by co-precipitation strategy to increase the selectivity of MAL from 47.9%to 49.8%,64.2% and 68.6%,respectively.In order to elucidate in-depth the promoting effect of Ce and/or Gd,various characterizations were utilized including X-ray diffraction patterns(XRD),Raman,X-ray fluorescence spectrometry(XRF),X-ray photoelectron spectroscopy(XPS),O_(2)-temperature programmed desorption(O_(2)-TPD),H2-temperature programmed reduction(H2-TPR),CO_(2)-temperature programmed desorption(CO_(2)-TPD),IB-temperature programmed desorption(i-C4-TPD)and in-situ IB-Fourier transform infrared spectroscopy(IB-FTIR).Both Ce and Gd finely regulate the bulk and surface structure of the catalyst,thus altering the redox ability,oxygen mobility and storage ability and basicity.Compared with Ce,Gd addition slightly regulates the variation of Co^(2+)/Co^(3+)redox couples,greatly enhances the interaction among the components on the catalyst,thus only increases the content of surface oxygen species and has little effect on their mobility.While Cecontaining catalyst performs stronger oxygen storage and migration ability,thus leading to the overproduction of surface Odefectspecies,which are proposed to be the active sites for the production of MAL and COx.The CeGd co-doped catalyst possesses the proper content of surface Odefectspecies,thus exhibits much higher MAL selectivity.Moreover,the promoting mechanism of Ce and/or Gd over IB oxidation is proposed.Therefore,this work is helpful for understanding the influence of rare earth elements on the structure of mixed metal oxides and the olefin selective oxidation reaction.展开更多
Frameworks of NanZSM-5 type zeolites with various Si/A1 ratios have been constructed and optimized with molecular dynamic quench simulation. The results show that the structure parameters of NanZSM-5 type zeolite, inc...Frameworks of NanZSM-5 type zeolites with various Si/A1 ratios have been constructed and optimized with molecular dynamic quench simulation. The results show that the structure parameters of NanZSM-5 type zeolite, including the bond length and atomic charges, are consistent with those predicted by ab initio cluster calculations. It was also observed that atomic charges of Si atoms were shifted to higher field in NanZSM-5 type zeolite with lower Si/Al ratio. Then, the adsorption of isobutene on NanZSM-5 with various Si/Al ratios has been investigated using grand canonical ensemble Monte Carlo simulation and Cvff-300-1.01 forcefield. The simulated adsorption amount was in good agreement with the experimental data. Based on these facts, the effects of Si/Al ratio on the adsorption amount and adsorption isotherms of isobutene on NanZSM-5 were predicted. The results indicated that Si/Al ratio was important for the adsorption of isobutene and the adsorption amount was decreased as the Si/Al ratio was increased, which can be explained that the atomic charge of Na^＋ cation would influence greatly the π electrons of the isobutene double bond due to the Coulomb force. In addition, the adsorption sites of isobutene and interaction energy of isobutene with NanZSM-5 were also discussed.展开更多
Dimerization of isobutene in liquid state to form high octane value gasoline components was investigated over a homemade novel ion exchange resin, SPPESK, which shows high activity and selectivity in isobutene dimeri...Dimerization of isobutene in liquid state to form high octane value gasoline components was investigated over a homemade novel ion exchange resin, SPPESK, which shows high activity and selectivity in isobutene dimerization under mild conditions.展开更多
Efficient separation of C4 olefins is of critical importance and a challenging task in petrochemical industry. Covalent organic frameworks(COFs) could be used as promising candidates for membrane-based isobutene/1,3-b...Efficient separation of C4 olefins is of critical importance and a challenging task in petrochemical industry. Covalent organic frameworks(COFs) could be used as promising candidates for membrane-based isobutene/1,3-butadiene(i-C4H8/C4H6) separation. Owing to large amounts of COFs appearing, however, the rapid prediction of optimal COFs is imperative before experimental efforts. In this work, we combine molecular simulation and machine learning to study COF membranes for efficient isolation of i-C4H8 over C4H6. Using molecular simulation, four potential COF membranes, which possess both high membrane performance score (MPS) value and moderate membrane selectivity were screened out and the mechanism of membrane separation further revealed is an adsorption dominated process. Further, random forest(RF) model with high prediction accuracy(R2>0.84) was obtained and used for elucidating key factors in controlling the membrane selectivity and i-C4H8 permeability. Ultimately, the optimal COF features were obtained through structure-performance relationship study. Our results may trigger experimental efforts to accelerate the design of novel COFs with better i-C4H8/C4H6separation performance.展开更多
The spectral structures of acetamide-AlCl_(3)-based ionic liquid(IL)analogs were determined in detail through IR,NMR,and Raman spectroscopy.IR spectroscopy showed that 0.65AA-1.0AlCl_(3) was the coordination structure...The spectral structures of acetamide-AlCl_(3)-based ionic liquid(IL)analogs were determined in detail through IR,NMR,and Raman spectroscopy.IR spectroscopy showed that 0.65AA-1.0AlCl_(3) was the coordination structure of Al and O atoms because of the resonance structure of acetamide.The mutual verification of the results of ^(27)Al NMR and ^(1)H NMR indicated that acetamide coexisted mainly in the form of cationic Al species and molecular Al species in xAA-1.0AlCl_(3),and AA/AlCl_(3) molar ratio affected the transformation of cationic Al species to molecular Al species.xAA-1.0AlCl_(3) was used as a green acidic catalyst for isobutene oligomerization,and the effects of AA/AlCl_(3) molar ratio,reaction temperature,reaction time,and volumetric ratio between IL analog and isobutene on product distribution were investigated.Optimal reaction conditions were AA/AlCl_(3) molar ratio of 0.75,reaction temperature of 60 C,reaction time of 30 min,and catalyst/i-C4¼volumetric ratio of 1.4 v/v.Under optimal conditions,isobutene conversion,(C8^(-)+C12^(-))selectivity,(C16^(-)+C20^(-))selectivity,and by-product selectivity were 85.26,80.20,6.80,and 13.00 wt%,respectively。展开更多
The dehydrogenation of isobutane （IB） to produce isobutene coupled with reverse water gas shift in the presence of carbon dioxide was investigated over the catalyst Cr2O3 supported on active carbon （Cr2O3/AC）. The...The dehydrogenation of isobutane （IB） to produce isobutene coupled with reverse water gas shift in the presence of carbon dioxide was investigated over the catalyst Cr2O3 supported on active carbon （Cr2O3/AC）. The results illustrated that isobutane conversion and isobutene yield can be enhanced through the reaction coupling in the presence of carbon dioxide. Moreover, carbon dioxide can partially eliminate carbonaceous deposition on the catalyst and keep the active phase （Cr2O3）, which are then helpful to alleviate the catalyst deactivation.展开更多
The effects of Bi on the catalytic performance of selective oxidation of isobutane to methacrolein over MoVO/AlPO4 catalyst were investigated by XRD, FT-Raman, XPS, UV-vis DRS techniques. The results show that the add...The effects of Bi on the catalytic performance of selective oxidation of isobutane to methacrolein over MoVO/AlPO4 catalyst were investigated by XRD, FT-Raman, XPS, UV-vis DRS techniques. The results show that the addition of Bi component into the MoVO/AlPO4 catalyst obviously improves the catalytic performance, and the selectivity to methacrolein can increase from 14.2% to 45.1% with the increase of Bi/V molar ratio from 0 to 1. Combining the characterization results with the reaction evaluation, it is concluded that the catalytic activities of the MoV0.3Bix/AlPO4 catalysts are related to the crystalline phase composition and the dispersion of molybdenum and vanadium oxides species in general, and also to the V5＋/V4＋ molar ratio on the surface in particular.展开更多
This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–g...This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–gel method. The effects of calcinating temperature and the addition of CaCO_3 as a pore-enlarging agent on texture structure and catalytic performance in isobutane dehydrogenation to isobutene were investigated. Characterization of N_2 sorption,mechanical strength tests,and optical photographs confirmed that the obtained carbon materials had high mechanical strength,a good degree of sphericity,and a large surface area. Introducing CaCO_3 as a pore-enlarging agent during the preparation process promoted the formation of a mesoporous structure of carbon spheres and evidently increased the surface area and oxygen content,which can improve isobutane conversion and isobutene selectivity of these carbon spheres. The conversion of isobutane reached up to 28% for this spherical activated carbon,and the selectivity of isobutene reached up to 96%. Isobutane conversion increased with an increase in calcination temperature due to an increase in the oxygen content,whereas the selectivity of isobutene decreased due to the slight decrease in the specific surface area.展开更多
Molybdenum based oxide catalysts Mo-H,Mo-Fe,Mo-Ce,and Mo-Sn were prepared by calcining H3PMo12O40,Fe1.5 PMo 12O40,Ce1.5PMo12O40,and Sn1.5 PMo12O40 heteropolyanion precursors at700℃,respectively.The prepared oxides ha...Molybdenum based oxide catalysts Mo-H,Mo-Fe,Mo-Ce,and Mo-Sn were prepared by calcining H3PMo12O40,Fe1.5 PMo 12O40,Ce1.5PMo12O40,and Sn1.5 PMo12O40 heteropolyanion precursors at700℃,respectively.The prepared oxides have been characterized and tested for the dehydrogenation of isobutane(IB)to isobutene in the presence of CO2.The effects of temperature,time on stream,and CO2 /IB ratio were investigated.It was found that α-and-MoO3 phases were present in all catalysts.Catalytic tests showed that increasing the reaction temperature increased both the conversion and isobutene selectivity,whereas increasing the CO2 /IB molar ratio increased the conversion but decreased the selectivity for isobutene.Iron was found to be an effective additive element for the enhancement of catalytic activity compared with Ce and Sn.展开更多
In this study, a series of novel Pt-Ni bimetallic catalysts supported on LaFeO_3/SiO_2 with different amounts of Ni were prepared by the lattice atomic-confined reduction of LaFe_(1-x)(Ni, Pt)_xO_3/SiO_2 perovskite pr...In this study, a series of novel Pt-Ni bimetallic catalysts supported on LaFeO_3/SiO_2 with different amounts of Ni were prepared by the lattice atomic-confined reduction of LaFe_(1-x)(Ni, Pt)_xO_3/SiO_2 perovskite precursors and applied in isobutane dehydrogenation to isobutene reaction. The catalysts were characterized by X-ray diffraction, H_2-temperature-programmed reduction, Brunauer-Emmett-Teller analysis, transmission electron microscopy, energy dispersive X-ray, CO chemisorption, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The as-synthesized Pt-Ni bimetallic catalysts possessed smaller most probable particle size with tunable Pt-Ni interaction, depending on the Ni content. The catalyst with Ni content of 3.0 wt% showed excellent activity and stability(the isobutane conversion and isobutene selectivity remained at about 38% and 92%, respectively, after 310 min) for the isobutane dehydrogenation reaction. It also provided approximately six times turnover frequency of the catalyst without Ni. The excellent activity and stability of the 3.0 wt% Ni-containing catalyst can be attributed to its small metal nanoparticles with high dispersion and suitable Pt-Ni interaction. Moreover, the Pt(Ni)-LaFeO_3/SiO_2 catalyst with Ni content of 3.0 wt% had been run for more than 35 h without obvious loss of activity,indicating its long-term stability, and the decrease in the Pt-Ni interaction that accompanied the formation of the FeNi alloy phase was thought to be responsible for the slight decrease in activity.展开更多
文摘The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a higher isobutene selectivity.However,the catalyst stability remains a key problem for the long-running acetone conversion and the reasons for catalyst deactivation are poorly understood up to now.Herein,the deactivation mechanism of Lewis acidic Y/Beta catalyst during the acetone to isobutene conversion was investigated by various characterization techniques,including acetone-temperature-programmed surface reaction,gas chromatography-mass spectrometry,in situ ultraviolet-visible,and ^(13)C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy.A successive aldol condensation and cyclization were observed as the main side-reactions during the acetone conversion at Lewis acidic Y sites.In comparison with the low reaction temperature,a rapid formation and accumulation of the larger cyclic unsaturated aldehydes/ketones and aromatics could be observed,and which could strongly adsorb on the Lewis acidic sites,and thus cause the catalyst deactivation eventually.After a simple calcination,the coke deposits could be easily removed and the catalytic activity could be well restored.
基金supported by K.C.Wong Education Foundation, Hong Kong (201611)Youth Innovation Promotion Association, CAS (20120155)~~
文摘A shaped binderless and two binder‐containing ZSM‐11 zeolite catalysts were prepared and characterized by powder X‐ray diffraction, N2 adsorption‐desorption, and pyridine adsorption‐infrared measurements. The binderless catalyst was synthesized using a dry‐gel conversion technique, inwhich 1,6‐hexanediamine and tetrabutylammonium bromide were used as structure‐directingagents and no other alkaline materials were added. The catalytic performance of the zeolites in the direct amination of isobutene to tert‐butylamine was evaluated in a fixed‐bed reactor. By virtue of its high crystallinity as well as its good mechanical strength, the shaped binderless ZSM‐11 catalyst showed a higher rate of formation of tert‐butylamine than did the binder‐containing catalysts.
基金financially supported by the Natural Science Foundation of China(21978312,21908235 and 21802155)the Key Research Program of Frontier Sciences,CAS(QYZDB–SSW–JS C043)+1 种基金Foundation of State Key Laboratory of Highefficiency Utilization of Coal and Green Chemical Engineering(2019-KF-05 and 2018-K22)Supported by Shanxi Scholarship Council of China and Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province are also greatly appreciated。
文摘The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas.ZrO_(2) with small crystalline size showed higher CO conversion and isobutene selectivity,while samples with large crystalline size preferred to form dimethyl ether(DME)instead of hydrocarbons,much less to isobutene.Oxygen defects(ODefects)analyzed by X-ray photoelectron spectroscopy(XPS)provided evidence that more ODefectsoccupied on the surface of ZrO_(2) catalysts with smaller crystalline size.Electron paramagnetic resonance(EPR)and ultraviolet–visible diffuse reflectance(UV–vis DRS)confirmed the presence of high concentration of surface defects and Zr3+on mZrO_(2)-5.9 sample,respectively.In situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS)analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased.These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species,and thus the products distribution changed.This study provides an in-depth insight for active sites regulation of ZrO_(2) catalyst in CO hydrogenation reaction.
基金supported by the National Natural Science Foundation of China (21476120)the Shandong Province Prioritized Development Plan (2017GGX40107)the Taishan Scholar Project of Shandong Province in China (ts201511033)
文摘The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.
文摘The catalytic property of AICl(3) catalyst immobilized on gamma -Al2O3 for isobutene polymerization has been studied. It was found that the activity, selectivity and stability of the catalyst are dependent greatly on geometric characteristic pf the pore structure and size of catalyst. Although the activity and selectivity of the catalysts with micro- and meso-pore structure are all high in initial stage, but their stability is low, while those with bimodal meso- and macro-pore structure are excellent. Increasing granularity of the catalyst(particle become fine) brings about an increase in isobutene conversion, but a decrease in selectivity, resulting in lower average molecular weight and iis broader distribution.
基金supported by the National Natural Science Foundation of China(21676141,21808104)the National Key Research and Development Program of China(2017YFB0307304)+3 种基金the Natural Science Foundation of Jiangsu Province(BK20170989)the Natural Science Foundation of Jiangsu Higher Education Institutions of China(17KJB530005)the Project"333"of Jiangsu Province(BRA2016418)the Six Major Talent Peak Project of Jiangsu Province(XCL-017)。
文摘Isooctane attracts great interest in recent years because of its promising potential as friendlyenvironmental gasoline,which is obtained by dimerization of isobutene with a hydrogenation step.Herein,a solid acid catalyst sulfated zirconia modified by ZnO was prepared.The oligomerization of isobutene had been investigated over ZrO_(2)-SO_(4) and ZnO(X)/ZrO_(2)-SO_(4) catalyst in order to find efficient catalysts for the production of isobutene oligomers.The presence of ZnO obviously enhanced the dimerization of isobutene and ZnO(X)/ZrO_(2)-SO_(4) exhibited the highest di-isobutene yield of 60%.Kinetic studies showed the higher trimerization-to-dimerization activation energy ratios of ZnO(X)/ZrO_(2)-SO_(4) than those of ZrO_(2)-SO_(4) from 353 to 393 K.In addition,reaction rate of dimerization was higher than trimerization over ZnO(X)/ZrO_(2)-SO_(4).The high L/B ratio manifested the capability to enhance the selectivity of C8 in isobutene dimerization.Furthermore,ZnO(X)/ZrO_(2)-SO_(4) exhibited stable conversion for the dimerization of isobutene.
基金Foundation item: Supported by Scientific Research Fund of Hunan Provincial Education Department (02C463 and 03C515)Hunan Provincial Natural Science Foundation of China (04JJ6003).
文摘Mixed oxide catalyst Cs0.1Fe2Co6BiMnMo12Ox was prepared by the coprecipitation method. Selective oxidation of isobutene was carried out in a fixed-bed reactor over Cs0.1Fe2Co6BiMnMo12Ox. The results showed that the catalyst had high catalytic activity. Under the optimum reaction conditions (n(i-C4=):n(O2)=1:2-1:4, space velocity=180 h-1, T=360℃), the yields of methacrolein and methacrylic acid can reach 80% and 8%, respectively. The total yield of liquid products (methacrolein, methacrylic acid and acetic acid) can reach about 90%.
基金Supported by the State key Development Program for Basic Research of China(2012CB720502)the National High Technology Research and Development(2012AA040306)+1 种基金the National Natural Science Foundation of China(21076074)the Shanghai Pujiang Talents Program(10PJ1402400)
文摘Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a temperature range of 338-383 K in the presence of laboratory prepared Ni/Al_2O_3 as a catalyst and n-pentane as solvent.The influence of various parameters such as temperature,catalyst loading and initial concentration of IB was examined.A Langmuir-Hinshelwood kinetic model of IB dimerization was established and the parameters were estimated on the basis of the measured data.The feasibility of oligomerization of IB based on the reactive distillation was simulated in ASPEN PLUS using the kinetics developed.The simulation results showed that the catalyst of Ni/Al_2O_3 had higher selectivity to diisobutene(DIB) and slightly lower conversion of IB than ion exchange resin in the absence of polar substances.
文摘The oxidative dehydrogenation of isobutane to isobutene was examined for the use in the preparation of FSM-16 and related compounds doped by chromium with expectations that a yield of isobutene of greater than 8% could be achieved. The activity depended on the molding procedure of the catalyst and the doping method of the chromium species. In the present study, 8.8% and 8.3% of the yield of isobutene were obtained at 0.75 h and 6 h on-stream for the catalyst （Cr-loading; 6.2 wt.%） molded using wet treatment hut not pressurization treatment, in which the chromium species were directly added into the aqueous solution containing raw FSM-16 （hydrated sodium silicate powder） at an initial stage of the catalyst preparation. The structure information was based on XRD （X-ray diffraction）, the specific surface area was determined using a conventional BET （Brunauer-Emmett-Teller） nitrogen adsorption and the loading of chromium was estimated using ICP （inductively coupled plasma）. All those parameters combined with the molding method indicated that the catalytic activity was more influenced by the loading of chromium into bulk but not on surface of the catalyst rather than by the hexagonal structure of FSM-16 and the surface area.
文摘Ternary multifunctional A<sub>1</sub>Zn<sub>y</sub>Zr<sub>z</sub>O<sub>n</sub> catalysts are prepared by introducing A-site transition metals with the redox capability into binary Zn<sub>1</sub>Zr<sub>8</sub>O<sub>n</sub>. Structure and morphology were investigated by means of XRD, BET and FESEM, respectively. Activity data showed that Cr addition exhibited obvious beneficial effect to promote isobutene production from direct conversion of bio-ethanol compared to other A-site metal dopants. A significant higher yield of isobutene over Cr-promoted Zn<sub>1</sub>Zr<sub>8</sub>O<sub>n</sub> catalyst was also observed with respect to its binary Zn<sub>1</sub>Zr<sub>8</sub>O<sub>n</sub> counterpart. The choice of A-site metal is of prime importance in the isobutene production, catalyzing mainly the ethanol dehydrogenation, meanwhile the appropriate addition of zinc on the catalyst surface is also essential for good isobutene yield.
基金supported by Petro China Innovation Foundation(2019D-5007-0404)。
文摘The further improvement of methacrolein(MAL)selectivity from isobutene(IB)oxidation is crucial and challenging.In this study,based on the typical Mo-Bi-Fe-Co-K-O mixed metal oxide,the rare earth element Gd-doped,Ce-doped and CeGd co-doped catalysts were prepared by co-precipitation strategy to increase the selectivity of MAL from 47.9%to 49.8%,64.2% and 68.6%,respectively.In order to elucidate in-depth the promoting effect of Ce and/or Gd,various characterizations were utilized including X-ray diffraction patterns(XRD),Raman,X-ray fluorescence spectrometry(XRF),X-ray photoelectron spectroscopy(XPS),O_(2)-temperature programmed desorption(O_(2)-TPD),H2-temperature programmed reduction(H2-TPR),CO_(2)-temperature programmed desorption(CO_(2)-TPD),IB-temperature programmed desorption(i-C4-TPD)and in-situ IB-Fourier transform infrared spectroscopy(IB-FTIR).Both Ce and Gd finely regulate the bulk and surface structure of the catalyst,thus altering the redox ability,oxygen mobility and storage ability and basicity.Compared with Ce,Gd addition slightly regulates the variation of Co^(2+)/Co^(3+)redox couples,greatly enhances the interaction among the components on the catalyst,thus only increases the content of surface oxygen species and has little effect on their mobility.While Cecontaining catalyst performs stronger oxygen storage and migration ability,thus leading to the overproduction of surface Odefectspecies,which are proposed to be the active sites for the production of MAL and COx.The CeGd co-doped catalyst possesses the proper content of surface Odefectspecies,thus exhibits much higher MAL selectivity.Moreover,the promoting mechanism of Ce and/or Gd over IB oxidation is proposed.Therefore,this work is helpful for understanding the influence of rare earth elements on the structure of mixed metal oxides and the olefin selective oxidation reaction.
基金Project supported by the National Basic Research Program of China （No. G2003CB615807）, the National Natural Science Foundation of China （No. 20476004） and the Research Program of China Petroleum ＆ Chemical Corporation （No. X504023）.
文摘Frameworks of NanZSM-5 type zeolites with various Si/A1 ratios have been constructed and optimized with molecular dynamic quench simulation. The results show that the structure parameters of NanZSM-5 type zeolite, including the bond length and atomic charges, are consistent with those predicted by ab initio cluster calculations. It was also observed that atomic charges of Si atoms were shifted to higher field in NanZSM-5 type zeolite with lower Si/Al ratio. Then, the adsorption of isobutene on NanZSM-5 with various Si/Al ratios has been investigated using grand canonical ensemble Monte Carlo simulation and Cvff-300-1.01 forcefield. The simulated adsorption amount was in good agreement with the experimental data. Based on these facts, the effects of Si/Al ratio on the adsorption amount and adsorption isotherms of isobutene on NanZSM-5 were predicted. The results indicated that Si/Al ratio was important for the adsorption of isobutene and the adsorption amount was decreased as the Si/Al ratio was increased, which can be explained that the atomic charge of Na^＋ cation would influence greatly the π electrons of the isobutene double bond due to the Coulomb force. In addition, the adsorption sites of isobutene and interaction energy of isobutene with NanZSM-5 were also discussed.
文摘Dimerization of isobutene in liquid state to form high octane value gasoline components was investigated over a homemade novel ion exchange resin, SPPESK, which shows high activity and selectivity in isobutene dimerization under mild conditions.
基金supported by the National Natural Science Foundation of China (Nos.22038010,21878229,22108202,22008179,21978212,22078024)the Science and Technology Plans of Tianjin,China(Nos.19PTSYJC00020,20ZYJDJC00110,21ZYJDJC00040).
文摘Efficient separation of C4 olefins is of critical importance and a challenging task in petrochemical industry. Covalent organic frameworks(COFs) could be used as promising candidates for membrane-based isobutene/1,3-butadiene(i-C4H8/C4H6) separation. Owing to large amounts of COFs appearing, however, the rapid prediction of optimal COFs is imperative before experimental efforts. In this work, we combine molecular simulation and machine learning to study COF membranes for efficient isolation of i-C4H8 over C4H6. Using molecular simulation, four potential COF membranes, which possess both high membrane performance score (MPS) value and moderate membrane selectivity were screened out and the mechanism of membrane separation further revealed is an adsorption dominated process. Further, random forest(RF) model with high prediction accuracy(R2>0.84) was obtained and used for elucidating key factors in controlling the membrane selectivity and i-C4H8 permeability. Ultimately, the optimal COF features were obtained through structure-performance relationship study. Our results may trigger experimental efforts to accelerate the design of novel COFs with better i-C4H8/C4H6separation performance.
基金support of the National Natural Science Foundation of China(No.21802047)the Scientific Research Funds of Huaqiao University(No.600005-Z17Y0073),Xiamen,China.
文摘The spectral structures of acetamide-AlCl_(3)-based ionic liquid(IL)analogs were determined in detail through IR,NMR,and Raman spectroscopy.IR spectroscopy showed that 0.65AA-1.0AlCl_(3) was the coordination structure of Al and O atoms because of the resonance structure of acetamide.The mutual verification of the results of ^(27)Al NMR and ^(1)H NMR indicated that acetamide coexisted mainly in the form of cationic Al species and molecular Al species in xAA-1.0AlCl_(3),and AA/AlCl_(3) molar ratio affected the transformation of cationic Al species to molecular Al species.xAA-1.0AlCl_(3) was used as a green acidic catalyst for isobutene oligomerization,and the effects of AA/AlCl_(3) molar ratio,reaction temperature,reaction time,and volumetric ratio between IL analog and isobutene on product distribution were investigated.Optimal reaction conditions were AA/AlCl_(3) molar ratio of 0.75,reaction temperature of 60 C,reaction time of 30 min,and catalyst/i-C4¼volumetric ratio of 1.4 v/v.Under optimal conditions,isobutene conversion,(C8^(-)+C12^(-))selectivity,(C16^(-)+C20^(-))selectivity,and by-product selectivity were 85.26,80.20,6.80,and 13.00 wt%,respectively。
基金the State Key Fundamental Research Project(No.2006CB202504)the National Natural Science Foundation of China(No.20676140)Natural Science Foundation of Shanxi Province.
文摘The dehydrogenation of isobutane （IB） to produce isobutene coupled with reverse water gas shift in the presence of carbon dioxide was investigated over the catalyst Cr2O3 supported on active carbon （Cr2O3/AC）. The results illustrated that isobutane conversion and isobutene yield can be enhanced through the reaction coupling in the presence of carbon dioxide. Moreover, carbon dioxide can partially eliminate carbonaceous deposition on the catalyst and keep the active phase （Cr2O3）, which are then helpful to alleviate the catalyst deactivation.
基金supported by the National Natural Science Foundation of China (20806059)
文摘The effects of Bi on the catalytic performance of selective oxidation of isobutane to methacrolein over MoVO/AlPO4 catalyst were investigated by XRD, FT-Raman, XPS, UV-vis DRS techniques. The results show that the addition of Bi component into the MoVO/AlPO4 catalyst obviously improves the catalytic performance, and the selectivity to methacrolein can increase from 14.2% to 45.1% with the increase of Bi/V molar ratio from 0 to 1. Combining the characterization results with the reaction evaluation, it is concluded that the catalytic activities of the MoV0.3Bix/AlPO4 catalysts are related to the crystalline phase composition and the dispersion of molybdenum and vanadium oxides species in general, and also to the V5＋/V4＋ molar ratio on the surface in particular.
基金supported by the Natural Science Foundation of Tianjin, China (no. 15JCYBJC20900)
文摘This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–gel method. The effects of calcinating temperature and the addition of CaCO_3 as a pore-enlarging agent on texture structure and catalytic performance in isobutane dehydrogenation to isobutene were investigated. Characterization of N_2 sorption,mechanical strength tests,and optical photographs confirmed that the obtained carbon materials had high mechanical strength,a good degree of sphericity,and a large surface area. Introducing CaCO_3 as a pore-enlarging agent during the preparation process promoted the formation of a mesoporous structure of carbon spheres and evidently increased the surface area and oxygen content,which can improve isobutane conversion and isobutene selectivity of these carbon spheres. The conversion of isobutane reached up to 28% for this spherical activated carbon,and the selectivity of isobutene reached up to 96%. Isobutane conversion increased with an increase in calcination temperature due to an increase in the oxygen content,whereas the selectivity of isobutene decreased due to the slight decrease in the specific surface area.
基金the Deanship of Scientific Research at King Saud University for funding the work through the research group project No RGP-VPP-025
文摘Molybdenum based oxide catalysts Mo-H,Mo-Fe,Mo-Ce,and Mo-Sn were prepared by calcining H3PMo12O40,Fe1.5 PMo 12O40,Ce1.5PMo12O40,and Sn1.5 PMo12O40 heteropolyanion precursors at700℃,respectively.The prepared oxides have been characterized and tested for the dehydrogenation of isobutane(IB)to isobutene in the presence of CO2.The effects of temperature,time on stream,and CO2 /IB ratio were investigated.It was found that α-and-MoO3 phases were present in all catalysts.Catalytic tests showed that increasing the reaction temperature increased both the conversion and isobutene selectivity,whereas increasing the CO2 /IB molar ratio increased the conversion but decreased the selectivity for isobutene.Iron was found to be an effective additive element for the enhancement of catalytic activity compared with Ce and Sn.
基金supported by National Natural Science Foundation of China (No. 21776214)State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, China
文摘In this study, a series of novel Pt-Ni bimetallic catalysts supported on LaFeO_3/SiO_2 with different amounts of Ni were prepared by the lattice atomic-confined reduction of LaFe_(1-x)(Ni, Pt)_xO_3/SiO_2 perovskite precursors and applied in isobutane dehydrogenation to isobutene reaction. The catalysts were characterized by X-ray diffraction, H_2-temperature-programmed reduction, Brunauer-Emmett-Teller analysis, transmission electron microscopy, energy dispersive X-ray, CO chemisorption, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The as-synthesized Pt-Ni bimetallic catalysts possessed smaller most probable particle size with tunable Pt-Ni interaction, depending on the Ni content. The catalyst with Ni content of 3.0 wt% showed excellent activity and stability(the isobutane conversion and isobutene selectivity remained at about 38% and 92%, respectively, after 310 min) for the isobutane dehydrogenation reaction. It also provided approximately six times turnover frequency of the catalyst without Ni. The excellent activity and stability of the 3.0 wt% Ni-containing catalyst can be attributed to its small metal nanoparticles with high dispersion and suitable Pt-Ni interaction. Moreover, the Pt(Ni)-LaFeO_3/SiO_2 catalyst with Ni content of 3.0 wt% had been run for more than 35 h without obvious loss of activity,indicating its long-term stability, and the decrease in the Pt-Ni interaction that accompanied the formation of the FeNi alloy phase was thought to be responsible for the slight decrease in activity.
