Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,...Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.展开更多
A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor phase ethylene feed stream, benzene and transalkylation feed stream. Especially the ...A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor phase ethylene feed stream, benzene and transalkylation feed stream. Especially the product stream containing ethylbenzene was used to heat the reactor vessel, which consisted of an alkylation section, an upper heat exchange section, and a bottom heat exchange section. In such a novel reactor, vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section. The process was demonstrated by the thermodynamic analysis and experimental results. In fact, during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction, the ethene conversion was above 95%, and the ethylbenzene selectivity was above 83% （only benzene feed） and even higher than 99% （benzene plus transalkylation feed）. At the same time, the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140-185℃ of temperature, 1.6-2.1 MPa of pressure, 3.0-5.5 of benzene/ethylene mole ratio, 4-6 v% of transalkylation feed/（benzene＋transalkylation feed）, 0.19-0.27 h^-1 of ethene space velocity, and 1000 g of 3998 catalyst loaded. Thus, compared with the conventional ethylbenzene synthesis route, the transalkylation reactor could be omitted in this novel industrial process.展开更多
Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the...Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the catalytic performance results, induction period and objective product were closely related to the reaction conditions. Lower space velocity led to longer induction period and higher propene yield. The optimal reaction temperature for propene production is around 150 ~C and it shifted to 100 ~C for ethene production. 1-Butene auto-metathesis predominated in the reaction network if the support with lower degree of sodium exchanged. And propene gradually became the dominant product upon increasing the support sodium exchange degree. 6Mo/H100Na0M-30A1 catalyst with a support of full sodium exchange degree exhibited the highest propene yield.展开更多
On basis of thermodynamic empirical equations, the thermodynamic parameters for the direct amination of isobutylene to tert‐butylamine, an atomically economic and green chemical reaction,were calculated. In particula...On basis of thermodynamic empirical equations, the thermodynamic parameters for the direct amination of isobutylene to tert‐butylamine, an atomically economic and green chemical reaction,were calculated. In particular, the equilibrium conversion of isobutylene under various reactionconditions close to those used in industry was calculated and discussed. Isobutylene amination is atemperature sensitive reaction due to its exothermic nature and isobutylene equilibrium conversiondecreases with temperature. However, kinetically, the amination reaction will be faster at ahigher temperature. Thus, there must be an optimum temperature for the reaction. A high pressureand n(NH3)/n(i‐C4H8) molar ratio promote the transformation of isobutylene to tert‐butylamine.Developing a highly efficient catalyst under mild reaction conditions is preferred for the aminationprocess. The reaction was investigated over a series of acidic zeolites. ZSM‐11 zeolite exhibited thebest performance with 14.2% isobutylene conversion (52.2% of the equilibrium conversion) and >99.0% tert‐butylamine selectivity. The effect of reaction conditions on the performance of the ZSM‐11 catalyst agreed with the thermodynamic results, which provides guidance for further catalyst development and reaction condition optimization.展开更多
The synthesis of ferrierite(FER)zeolite using piperidine as an organic structure‐directing agent was investigated.X‐ray diffraction,X‐ray fluorescence,N2‐adsorption,and scanning electron microscopy were used to ch...The synthesis of ferrierite(FER)zeolite using piperidine as an organic structure‐directing agent was investigated.X‐ray diffraction,X‐ray fluorescence,N2‐adsorption,and scanning electron microscopy were used to characterize the crystal phases,textural properties,and particle morphologies of the zeolite samples.The crystallization behavior of the FER zeolite was found to be directly related to crystallization temperature.At150?C,pure FER phase was observed throughout crystallization.At160–170?C,MWW phase appeared first and gradually transformed into FER phase over time,indicating that the FER phase was thermodynamically favored.In the piperidine‐Na2O‐H2O synthetic system,alkalinity proved to be the crucial factor determining the size and textural properties of FER zeolite.Furthermore,the obtained FER samples exhibited good catalytic performance in the skeletal isomerization of1‐butene.展开更多
The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out ov...The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out over zeolite catalysts possessing different topological structures, from one dimensional to three dimensional pore system, and from small 8-member ring pore（MRP） to medium 10 MRP and further to large 12 MRP zeolites, to disclose the relationship between the zeolite properties/topologies and their amination performance systematically under the mild reaction conditions. It was discovered that the pore structure and the acidities of zeolite catalysts played crucial roles in the isobutylene amination process, and suitable pore diameter（larger than 0.5 nm or with large side pockets/cups in the outside surface） and a certain number of mid-strong acid sites are indispensable to catalyze the amination reaction,while too strong acid strength was not conducive to the process of isobutylene amination. Among them,zeolites with topologies of BEA, MFI, MEL, MWW and EUO exhibited good amination performance, with which the isobutylene conversion was higher than 12.61%（>46.42% of the equilibrium conversion） under the studied mild reaction conditions. Due to the good amination performance and the large adjustable Si/Al;ratio range, ZSM-5 was selected to further study the effect of acidity on the amination performance systematically under the mild reaction conditions, and the activity-acidity relationship in the amination process was disclosed: the amination activity（isobutylene conversion） had a linear correlation with the amount of mid-strong B acidity under the studied conditions over ZSM-5 catalyst, which can provide guidance for further developing high-efficient amination catalyst under mild reaction conditions available for future industrial use.展开更多
The aromatization of light alkenes in liquefied petroleum gas (LPG) with and without dimethyl ether (DME) addition in the feed was investigated on a modified ZSM-5 catalyst.The results showed that under the given reac...The aromatization of light alkenes in liquefied petroleum gas (LPG) with and without dimethyl ether (DME) addition in the feed was investigated on a modified ZSM-5 catalyst.The results showed that under the given reaction conditions the selectivity of alkenes to high-octane gasoline blending components was markedly enhanced and the formation of propane and butanes was greatly suppressed with the addition of DME.It was also found that the distribution of C5+ components was changed a lot with DME addition into the LPG feed.The formation of branched hydrocarbons (mainly C6 C8 i-paraffin) and multi-methyl substituted aromatics,which are high octane number gasoline blending components,was promoted significantly,while the content of n-paraffins and olefins in C5+ components was decreased obviously,indicating that in addition to the oligomerization,cracking,hydrogen-transfer and dehydrogenation-cyclization of alkenes,the methylation of the formed aromatics and olefins intermediates also plays an important role in determining the product distribution due to the high reactivity of surface methoxy groups formed by DME.And this process,in combination with the syngas-to-methanol/DME technology,provides an alternative way to the production of high-octane gasoline from coal,natural gas or renewable raw materials.展开更多
The organic structure-directing agent(OSDA)-free synthesis of MCM-49 is strongly desired because OSDA makes synthesis cost expensive and environment unfriendly.In this work,an efficient,eco-friendly and simple route t...The organic structure-directing agent(OSDA)-free synthesis of MCM-49 is strongly desired because OSDA makes synthesis cost expensive and environment unfriendly.In this work,an efficient,eco-friendly and simple route to synthesize MCM-49 zeolite is developed,via seed-assistance,without deliberately adding OSDA,with ultraphonic aging treatment.For comparison,the effect of microwave aging,mechanical stirring aging and without any aging processes on the synthesis is investigated.Due to the acoustic cavitation,the ultraphonic aging treatment shows superiority over the others.Ultraphonic aging not only keeps the MCM-49 seed integrity but also promotes both the silica species and aluminum species to the solid phase,which is beneficial for the growth of MCM-49 and the suppression of MOR formation in the absence of OSDA.^(27)Al MAS NMR data show that the seed-assisted MCM-49 almost has no extra-framework aluminum,but dealumination will happen upon ammonium exchange.^(23)Na MAS NMR results demonstrate that the interaction between Na ions and framework of the seed-assisted MWW product is strengthened after calcination,which makes the exchange of Na species difficult.Alternatively,ammonium exchange upon the as-made sample is an effective method to remove Na species,which improves the micropore volume,external surface area,and acid amount of the seed-assisted MCM-49.展开更多
基金China Postdoctoral Science Foundation (2023M733451)Dalian Innovation Team in Key Areas(2020RT06)Engineering Research Center for Key Aromatic Compounds and LiaoNing Key Laboratory,Liaoning Provincial Natural Science Foundation (Doctoral Research Start-up Fund 2024-BSBA-37)。
文摘Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.
基金This work is supported by the National 973 Project of China (2009CB623501)
文摘A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor phase ethylene feed stream, benzene and transalkylation feed stream. Especially the product stream containing ethylbenzene was used to heat the reactor vessel, which consisted of an alkylation section, an upper heat exchange section, and a bottom heat exchange section. In such a novel reactor, vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section. The process was demonstrated by the thermodynamic analysis and experimental results. In fact, during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction, the ethene conversion was above 95%, and the ethylbenzene selectivity was above 83% （only benzene feed） and even higher than 99% （benzene plus transalkylation feed）. At the same time, the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140-185℃ of temperature, 1.6-2.1 MPa of pressure, 3.0-5.5 of benzene/ethylene mole ratio, 4-6 v% of transalkylation feed/（benzene＋transalkylation feed）, 0.19-0.27 h^-1 of ethene space velocity, and 1000 g of 3998 catalyst loaded. Thus, compared with the conventional ethylbenzene synthesis route, the transalkylation reactor could be omitted in this novel industrial process.
基金the National Natural Science Foundation of China(Grant No.20903088 and 21006104)
文摘Effects of space velocity, reaction temperature and support acidity on product distribution and induction period in 1-butene isomerization and metathesis over Mo/mordenite-alumina were investigated. As revealed by the catalytic performance results, induction period and objective product were closely related to the reaction conditions. Lower space velocity led to longer induction period and higher propene yield. The optimal reaction temperature for propene production is around 150 ~C and it shifted to 100 ~C for ethene production. 1-Butene auto-metathesis predominated in the reaction network if the support with lower degree of sodium exchanged. And propene gradually became the dominant product upon increasing the support sodium exchange degree. 6Mo/H100Na0M-30A1 catalyst with a support of full sodium exchange degree exhibited the highest propene yield.
基金supported by K. C. Wong Education FoundationYouth Innovation Promotion Association of CAS (20120155)Dalian Eminent Young Scientist Program (2015R009)~~
文摘On basis of thermodynamic empirical equations, the thermodynamic parameters for the direct amination of isobutylene to tert‐butylamine, an atomically economic and green chemical reaction,were calculated. In particular, the equilibrium conversion of isobutylene under various reactionconditions close to those used in industry was calculated and discussed. Isobutylene amination is atemperature sensitive reaction due to its exothermic nature and isobutylene equilibrium conversiondecreases with temperature. However, kinetically, the amination reaction will be faster at ahigher temperature. Thus, there must be an optimum temperature for the reaction. A high pressureand n(NH3)/n(i‐C4H8) molar ratio promote the transformation of isobutylene to tert‐butylamine.Developing a highly efficient catalyst under mild reaction conditions is preferred for the aminationprocess. The reaction was investigated over a series of acidic zeolites. ZSM‐11 zeolite exhibited thebest performance with 14.2% isobutylene conversion (52.2% of the equilibrium conversion) and >99.0% tert‐butylamine selectivity. The effect of reaction conditions on the performance of the ZSM‐11 catalyst agreed with the thermodynamic results, which provides guidance for further catalyst development and reaction condition optimization.
基金supported by the National Natural Science Foundation of China(21376235)Natural Science Foundation of Liaoning Province(201602740)~~
文摘The synthesis of ferrierite(FER)zeolite using piperidine as an organic structure‐directing agent was investigated.X‐ray diffraction,X‐ray fluorescence,N2‐adsorption,and scanning electron microscopy were used to characterize the crystal phases,textural properties,and particle morphologies of the zeolite samples.The crystallization behavior of the FER zeolite was found to be directly related to crystallization temperature.At150?C,pure FER phase was observed throughout crystallization.At160–170?C,MWW phase appeared first and gradually transformed into FER phase over time,indicating that the FER phase was thermodynamically favored.In the piperidine‐Na2O‐H2O synthetic system,alkalinity proved to be the crucial factor determining the size and textural properties of FER zeolite.Furthermore,the obtained FER samples exhibited good catalytic performance in the skeletal isomerization of1‐butene.
基金the financial support of K.C.Wong Education FoundationDalian Eminent Young Scientist Program(2015R009)
文摘The atomically economic and green chemical reaction of direct amination of isobutylene to tertbutylamine, particularly under the relative mild reaction conditions available for future industrial use,was carried out over zeolite catalysts possessing different topological structures, from one dimensional to three dimensional pore system, and from small 8-member ring pore（MRP） to medium 10 MRP and further to large 12 MRP zeolites, to disclose the relationship between the zeolite properties/topologies and their amination performance systematically under the mild reaction conditions. It was discovered that the pore structure and the acidities of zeolite catalysts played crucial roles in the isobutylene amination process, and suitable pore diameter（larger than 0.5 nm or with large side pockets/cups in the outside surface） and a certain number of mid-strong acid sites are indispensable to catalyze the amination reaction,while too strong acid strength was not conducive to the process of isobutylene amination. Among them,zeolites with topologies of BEA, MFI, MEL, MWW and EUO exhibited good amination performance, with which the isobutylene conversion was higher than 12.61%（>46.42% of the equilibrium conversion） under the studied mild reaction conditions. Due to the good amination performance and the large adjustable Si/Al;ratio range, ZSM-5 was selected to further study the effect of acidity on the amination performance systematically under the mild reaction conditions, and the activity-acidity relationship in the amination process was disclosed: the amination activity（isobutylene conversion） had a linear correlation with the amount of mid-strong B acidity under the studied conditions over ZSM-5 catalyst, which can provide guidance for further developing high-efficient amination catalyst under mild reaction conditions available for future industrial use.
基金supported by the "Action Plan of CAS to Support China’s New and Strategic Industries with Science and Technology(2012-2014)"the "Knowledge Innovation Program of the Chinese Academy of Sciences(S201041)""Youth Innovation Promotion Association CAS(2012-2015)"
文摘The aromatization of light alkenes in liquefied petroleum gas (LPG) with and without dimethyl ether (DME) addition in the feed was investigated on a modified ZSM-5 catalyst.The results showed that under the given reaction conditions the selectivity of alkenes to high-octane gasoline blending components was markedly enhanced and the formation of propane and butanes was greatly suppressed with the addition of DME.It was also found that the distribution of C5+ components was changed a lot with DME addition into the LPG feed.The formation of branched hydrocarbons (mainly C6 C8 i-paraffin) and multi-methyl substituted aromatics,which are high octane number gasoline blending components,was promoted significantly,while the content of n-paraffins and olefins in C5+ components was decreased obviously,indicating that in addition to the oligomerization,cracking,hydrogen-transfer and dehydrogenation-cyclization of alkenes,the methylation of the formed aromatics and olefins intermediates also plays an important role in determining the product distribution due to the high reactivity of surface methoxy groups formed by DME.And this process,in combination with the syngas-to-methanol/DME technology,provides an alternative way to the production of high-octane gasoline from coal,natural gas or renewable raw materials.
基金supported by the National Natural Science Foundation of China(U20A20120)Dalian Science and Technology Innovation Fund Project(2019J12GX027)+2 种基金LiaoNing Revitalization Talents Program(XLYC1901006 and XLYC1908010)Dalian Engineering Research Center for Key Aromatic CompoundsSTS Network Initiative of the CAS(KFJ-STS-QYZD-2021-17-001).
文摘The organic structure-directing agent(OSDA)-free synthesis of MCM-49 is strongly desired because OSDA makes synthesis cost expensive and environment unfriendly.In this work,an efficient,eco-friendly and simple route to synthesize MCM-49 zeolite is developed,via seed-assistance,without deliberately adding OSDA,with ultraphonic aging treatment.For comparison,the effect of microwave aging,mechanical stirring aging and without any aging processes on the synthesis is investigated.Due to the acoustic cavitation,the ultraphonic aging treatment shows superiority over the others.Ultraphonic aging not only keeps the MCM-49 seed integrity but also promotes both the silica species and aluminum species to the solid phase,which is beneficial for the growth of MCM-49 and the suppression of MOR formation in the absence of OSDA.^(27)Al MAS NMR data show that the seed-assisted MCM-49 almost has no extra-framework aluminum,but dealumination will happen upon ammonium exchange.^(23)Na MAS NMR results demonstrate that the interaction between Na ions and framework of the seed-assisted MWW product is strengthened after calcination,which makes the exchange of Na species difficult.Alternatively,ammonium exchange upon the as-made sample is an effective method to remove Na species,which improves the micropore volume,external surface area,and acid amount of the seed-assisted MCM-49.
