Atropisomeric phosphines are crucial for asymmetric catalysis but remain synthetically challenging.Herein,an N-heterocyclic carbene(NHC)catalyzed esterification reaction of dialdehydes with arylboronic acids was devel...Atropisomeric phosphines are crucial for asymmetric catalysis but remain synthetically challenging.Herein,an N-heterocyclic carbene(NHC)catalyzed esterification reaction of dialdehydes with arylboronic acids was developed,successfully constructing the framework of axially chiral phosphorus compounds.Mechanistic studies have revealed that the reaction initially undergoes a desymmetrization process,followed by a kinetic resolution pathway,affording a series of axially chiral phosphorus compounds with high enantioselectivity(up to 92%ee).展开更多
A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spe...A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and elemental analysis, which showed that it was an amorphous carbon material composed of aromatic carbon sheets in random orientations. Sulfonic acid groups were present on the surface at a density of 0.81 mmol/g. The carbon solid acid catalyst showed better performance than HZSM‐5 for the esterification of cyclohexene with formic acid. At a3：1 molar ratio of formic acid to cyclohexene, catalyst loading of 0.07 g/mL of cyclohexene, and reaction time of 1 h at 413 K, the cyclohexene conversion was 88.4% with 97.3% selectivity to cyclohexyl formate. The carbon solid acid catalyst showed better reusability than HZSM‐5 because its large pores were minimally affected by the accumulation of oligomerized cyclohexene, which deactivated HZSM‐5. The activity of the carbon solid acid catalyst decreased somewhat in the first two recycles due to the leaching of polycyclic aromatic hydrocarbon containing –SO3H groups and then it remained constant in the following reuse.展开更多
Fhnctionalized ionic liquid samples （bmim-PW12） were synthesized by 1-butyl-3-methyl- imidazolium bromide （bmimBr） and 12-phosphotungstic heteropolyacid （PW12）. The samples were annealed at 100-450 ℃ and were c...Fhnctionalized ionic liquid samples （bmim-PW12） were synthesized by 1-butyl-3-methyl- imidazolium bromide （bmimBr） and 12-phosphotungstic heteropolyacid （PW12）. The samples were annealed at 100-450 ℃ and were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, thermal gravity-DTG, brunauer emmett teller, and NHa-temperature programmed desorption. The results showed that the bmim-PW12 samples were crystal and maintained intact Keggin structure. The organic parts of those samples were partly decomposed at a temperature more than 350 ℃. The sample annealed at 400 ℃ exhibited nano-porous structure, strong acidity, and excellent catalytic activity on the esterification of n-butanol with acetic acid. The higher ester yield was obtained when the mass ratio of catalyst over the reactants amount was 5% for bmim-PW12 catalyst annealed at 400 ℃.展开更多
Esterification of carboxylic acid with equimolar amounts alcohol can be efficiently catalyzed by biphasic 4-(benzylamino)formoyldiphenylammonium triflate (BDPAT, 3) in good yield. The catalyst can be easily recovered...Esterification of carboxylic acid with equimolar amounts alcohol can be efficiently catalyzed by biphasic 4-(benzylamino)formoyldiphenylammonium triflate (BDPAT, 3) in good yield. The catalyst can be easily recovered without loss of activity.展开更多
Sludge palm oil （SPO） is an attractive feedstock and a significant raw material for biodiesel production. The use of SPO can lower the cost ofbiodiesel production significantly. In this study biodiesel fuel was prod...Sludge palm oil （SPO） is an attractive feedstock and a significant raw material for biodiesel production. The use of SPO can lower the cost ofbiodiesel production significantly. In this study biodiesel fuel was produced from SPO by esterification process using P-toluenesulfonic acid （PTSA） as acid catalyst in different dosages in presence of methanol to convert free fatty acid （FFA） to fatty acid methyl ester （FAME）. Batch esterification process of SPO was carried out to study the influence of PTSA dosage （0.25-10% wt/wt）, molar ratio of methanol to SPO （6：1-20：1）, temperature （40-80 ℃）, reaction time （30-120 min）. The effects of those parameters on the yield of crude biodiesel and conversion of FFA to FAME were monitored. The optimum condition for batch esterification process was 0.75% wt/wt, 10：1 molar ratio, 60 ℃ temperature and 60 minutes reaction time.展开更多
From both fundamental and practical perspectives, the production of chemicals from biomass re-sources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoic...From both fundamental and practical perspectives, the production of chemicals from biomass re-sources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoichiometric or excess quantities of base, which leads to high energy consump-tion, leaching problems, and side reactions. In this study, we investigated the high-efficiency oxida-tive esterification of furfural to methylfuroate by molecular oxygen with a Co-N-C/MgO catalyst. The catalyst was prepared by direct pyrolysis of a cobalt（Ⅱ） phenanthroline complex on MgO at 800℃ under N2 atmosphere. From furfural, 93.0% conversion and 98.5% selectivity toward methylfuroate were achieved under 0.5 MPa O2 with reaction at 100 ℃ for 12 h without a basic additive. The con-version and selectivity were much higher than those obtained with cobalt catalysts produced by pyrolysis of a cobalt（Ⅱ） phenanthroline complex on activated carbon or typical basic supports, in-cluding NaX, NaY, and CaO. X-ray photoelectron spectroscopy, X-ray diffraction, transmission elec-tron microscopy, and experimental results revealed that the high efficiency of Co-N-C/MgO for pro-duction of methylfuroate was closely related to the cobalt-nitrogen-doped carbon species and its catalytic ability in hydrogen abstraction. In contrast, Co-N-C（HCl） that synthesized by removing MgO with HCl from Co-N-C/MgO, as the catalyst produced mainly an acetal as a condensation prod-uct, and chloride ions had a negative effect on the oxidative esterification. Although the catalytic performance of the cobalt-nitrogen-doped carbon species was greatly affected by HCl treatment, it could be recovered to a great extent by addition of MgO. Moreover, changes in the oxygen pressure hardly affected the oxidative esterification of furfural with Co-N-C/MgO. This study not only pro-vides an effective approach to prepare methylfuroate, but also for designing high-performance non-precious metal catalysts for the oxidative esterification of biomass-derived compounds.展开更多
随着人工智能(AI)技术的迅猛发展,AI for Science(AI4S)正逐渐成为科学研究的新范式,尤其在化学领域的实验方法上引发了一场革命。本研究创新性地引入了自驱动实验室(SDL)的概念,旨在解决未来化学研究中的挑战,并探索其在基础化学实验中...随着人工智能(AI)技术的迅猛发展,AI for Science(AI4S)正逐渐成为科学研究的新范式,尤其在化学领域的实验方法上引发了一场革命。本研究创新性地引入了自驱动实验室(SDL)的概念,旨在解决未来化学研究中的挑战,并探索其在基础化学实验中的AI数字化升级应用。研究团队采用了可循环利用的固体酸作为催化剂,以乙酸和苄醇的酯化反应为研究对象,开发了一种相对低成本、适用于教学的反应条件优化闭环系统。该系统由基于芯曙光自动合成仪的自动化反应器、自主设计的液相自动进样监控系统,以及基于Python的决策优化算法所组成。本研究展示了在现有条件下如何克服硬件兼容性和算法优化的挑战,为化学实验的未来创新发展奠定了坚实的基础。展开更多
La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorptio...La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorption, FTIR spectroscopic analysis, thermogravimetric analysis, and the total amount of acidity of catalyst was estimated by TPD of NH3. The results indicate that lanthanum has been incorporated into SBA-15 molecular sieve. The prepared materials（La-SO42-/SBA-15） keep the highly ordered mesoporous two-dimensional hexagonal structure and do not change the mesoporous channel structure of the support SBA-15. The catalyst showed best catalytic activity in the synthesis of n-butyl acetate. The optimum conditions of the esterification by orthogonal experiments were studied： the molar ratio of n-butanol to acetic acid 1：1.2, the amount of catalyst 7.5%, reaction time 80 min. The yield of n-butyl acetate could reach 93.2% under the optimum conditions. The catalyst was recyclable, cost effective and environmental friendly.展开更多
A self-made lipase preparation from Candida sp. 99-125 was used for the production of biodiesel through enzymatic esterification of fatty acids. The crude lipase powder and fermentation broth were immobilized on a che...A self-made lipase preparation from Candida sp. 99-125 was used for the production of biodiesel through enzymatic esterification of fatty acids. The crude lipase powder and fermentation broth were immobilized on a cheap fiber cloth carrier. The conditions of lipase-catalyzed esterification between long-chain fatty acids and methanol in a solvent system were investigated in detail, including the temperature, pH value, substrate concentration, solvent, absorbent agent, enzyme dosage and purity, immobilization method, the mode of addition of substrate. The results show that reaction temperature, pH of lipase micro-environment, substrate concentration, enzyme dosage and purity affect the esterification strongly. Several new methods and enzymatic procedures for improving the enzymatic reaction involving the process cost are also discussed, such as fossil diesel fuel as reaction solvent, immobilization method, multi-step gradient addition of methanol. The esterification degree of 92.8% was obtained with oleic acid and methanol under the optimal reaction condition after 12.5 h reaction time. The half-life of the immobilized lipase preparation from crude free lipase powder for esterification was 15 days.展开更多
The esterification of free fatty acids(FFA) in waste cooking oil with methanol in the presence of Fe2(SO4)3/C(ferric sulfate/active carbon) catalyst was studied.The effects of different temperature,methanol/FFA mole r...The esterification of free fatty acids(FFA) in waste cooking oil with methanol in the presence of Fe2(SO4)3/C(ferric sulfate/active carbon) catalyst was studied.The effects of different temperature,methanol/FFA mole ratio and amount of catalyst on the conversion of FFA were investigated.The results demonstrated that under optimal esterification conditions the final acid value of the resultant system can be reduced to ～1(mg KOH)·g-1,which met fully the requirements in post-treatment for efficient separation of glycerin and biodiesel.The kinetics of the esterification were also investigated under different temperatures.The results indicated that the rate-control step could be attributed to the surface reaction and the esterification processes can be well-depicted by the as-calculated kinetic formula in the range of the experimental conditions.展开更多
An efficient esterification of ferrocenecarboxylic acid with substituted phenols has been achieved using DCC / DMAP protocol in ionic liquids. The corresponding esters are produced in high yields.
Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia load...Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia loadings from different magnesium precursors and hydrochloric acid molar concentrations. The Mg O–SBA-15 supports and Pd–Pb/Mg O–SBA-15 catalysts were characterized by several analysis methods. The results revealed that the addition of Mg O improved the ordered structure of SBA-15 supports and provided surface alkalinity of SBA-15 supports. The average size of the Pd3 Pb particles on magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts was smaller than that on the pure silica-based Pd–Pb/SBA-15 catalysts. The experiments on catalyst performance showed that the magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts had higher activity than pure silica-based Pd–Pb/SBA-15 catalysts, showing the strong dependence of catalytic activity on the average size of active particles. The difference of activity between Pd–Pb/SBA-15 catalysts and Pd–Pb/Mg O–SBA-15 catalysts was due to the discrepant structural properties and surface alkalinity provided by Mg O, which led to the different Pd3 Pb particle sizes and then resulted in the different number of active sites. Besides magnesia loadings, other factors, such as hydrochloric acid molar concentration and magnesium precursors, had considerable influences on the catalytic activity.展开更多
Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sul...Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sulfuric acid.The swelling ability of acidic PILs was greatly affected by cross-linker content and chain length of 3-alkyl-substituents on imidazolium.Cross-linked network structures could be observed from the cryogenic scanning electron microscopy(cryo-SEM)images of the swollen acidic PILs in formic acid.Acidic PILs with network structures in swollen state exhibited excellent activities in the esterification of cyclohexene and formic acid,and the catalytic activities were in positive correlation with their swelling abilities.Acidic PIL with 3-octyl-substituent and 2.5 mol%DVB(PIL-C8-2.5DVB-HSO4)had the highest swelling ability in formic acid and exhibited comparable catalytic activities with homogeneous catalysts such as sulfuric acid and p-toluenesulfonic acid.展开更多
Esterification of methyl alcohol with acetic acid catalysed by Amberlyst-15 (cation-exchange resin) was carried out in a batch reactor in the temperature ranging between 318-338 K, at atmospheric pressure. The reactio...Esterification of methyl alcohol with acetic acid catalysed by Amberlyst-15 (cation-exchange resin) was carried out in a batch reactor in the temperature ranging between 318-338 K, at atmospheric pressure. The reaction rate increased with increase in catalyst concentration and reaction temperature, but decreased with an increase in water concentration. Stirrer speed had virtually no effect on the rate under the experimental conditions. The rate data were correlated with a second-order kinetic model based on homogeneous reaction. The apparent activation energy was found to be 22.9kJ mol-1 for the formation of methyl acetate. The methyl acetate production was carried out as batch and continuous in a packed bed reactive distillation column with high purity methyl acetate produced.展开更多
基金Project supported by the Natural Science Foundation of Henan Province(Nos.232300421234,252300421726)the Leading Talents in Scientific and Technological Innovation in Shangqiu(No.SQRC202212004)the Program of Ecological Environmental Protection in the Area of Old Course of Yellow River of Shangqiu Normal University。
文摘Atropisomeric phosphines are crucial for asymmetric catalysis but remain synthetically challenging.Herein,an N-heterocyclic carbene(NHC)catalyzed esterification reaction of dialdehydes with arylboronic acids was developed,successfully constructing the framework of axially chiral phosphorus compounds.Mechanistic studies have revealed that the reaction initially undergoes a desymmetrization process,followed by a kinetic resolution pathway,affording a series of axially chiral phosphorus compounds with high enantioselectivity(up to 92%ee).
基金supported by the National Natural Science Foundation of China(2123600121176056)+1 种基金the Programme for 100 Excellent Talents in Universities of Hebei Province(II)(BR2-208)the Natural Science Foundation of Hebei Province(B2015202228)~~
文摘A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and elemental analysis, which showed that it was an amorphous carbon material composed of aromatic carbon sheets in random orientations. Sulfonic acid groups were present on the surface at a density of 0.81 mmol/g. The carbon solid acid catalyst showed better performance than HZSM‐5 for the esterification of cyclohexene with formic acid. At a3：1 molar ratio of formic acid to cyclohexene, catalyst loading of 0.07 g/mL of cyclohexene, and reaction time of 1 h at 413 K, the cyclohexene conversion was 88.4% with 97.3% selectivity to cyclohexyl formate. The carbon solid acid catalyst showed better reusability than HZSM‐5 because its large pores were minimally affected by the accumulation of oligomerized cyclohexene, which deactivated HZSM‐5. The activity of the carbon solid acid catalyst decreased somewhat in the first two recycles due to the leaching of polycyclic aromatic hydrocarbon containing –SO3H groups and then it remained constant in the following reuse.
文摘Fhnctionalized ionic liquid samples （bmim-PW12） were synthesized by 1-butyl-3-methyl- imidazolium bromide （bmimBr） and 12-phosphotungstic heteropolyacid （PW12）. The samples were annealed at 100-450 ℃ and were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, thermal gravity-DTG, brunauer emmett teller, and NHa-temperature programmed desorption. The results showed that the bmim-PW12 samples were crystal and maintained intact Keggin structure. The organic parts of those samples were partly decomposed at a temperature more than 350 ℃. The sample annealed at 400 ℃ exhibited nano-porous structure, strong acidity, and excellent catalytic activity on the esterification of n-butanol with acetic acid. The higher ester yield was obtained when the mass ratio of catalyst over the reactants amount was 5% for bmim-PW12 catalyst annealed at 400 ℃.
文摘Esterification of carboxylic acid with equimolar amounts alcohol can be efficiently catalyzed by biphasic 4-(benzylamino)formoyldiphenylammonium triflate (BDPAT, 3) in good yield. The catalyst can be easily recovered without loss of activity.
文摘Sludge palm oil （SPO） is an attractive feedstock and a significant raw material for biodiesel production. The use of SPO can lower the cost ofbiodiesel production significantly. In this study biodiesel fuel was produced from SPO by esterification process using P-toluenesulfonic acid （PTSA） as acid catalyst in different dosages in presence of methanol to convert free fatty acid （FFA） to fatty acid methyl ester （FAME）. Batch esterification process of SPO was carried out to study the influence of PTSA dosage （0.25-10% wt/wt）, molar ratio of methanol to SPO （6：1-20：1）, temperature （40-80 ℃）, reaction time （30-120 min）. The effects of those parameters on the yield of crude biodiesel and conversion of FFA to FAME were monitored. The optimum condition for batch esterification process was 0.75% wt/wt, 10：1 molar ratio, 60 ℃ temperature and 60 minutes reaction time.
基金supported by the National Natural Science Foundation of China(21233008,21643013,21690084)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020300)the Youth Innovation Promotion Association CAS(2013121)~~
文摘From both fundamental and practical perspectives, the production of chemicals from biomass re-sources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoichiometric or excess quantities of base, which leads to high energy consump-tion, leaching problems, and side reactions. In this study, we investigated the high-efficiency oxida-tive esterification of furfural to methylfuroate by molecular oxygen with a Co-N-C/MgO catalyst. The catalyst was prepared by direct pyrolysis of a cobalt（Ⅱ） phenanthroline complex on MgO at 800℃ under N2 atmosphere. From furfural, 93.0% conversion and 98.5% selectivity toward methylfuroate were achieved under 0.5 MPa O2 with reaction at 100 ℃ for 12 h without a basic additive. The con-version and selectivity were much higher than those obtained with cobalt catalysts produced by pyrolysis of a cobalt（Ⅱ） phenanthroline complex on activated carbon or typical basic supports, in-cluding NaX, NaY, and CaO. X-ray photoelectron spectroscopy, X-ray diffraction, transmission elec-tron microscopy, and experimental results revealed that the high efficiency of Co-N-C/MgO for pro-duction of methylfuroate was closely related to the cobalt-nitrogen-doped carbon species and its catalytic ability in hydrogen abstraction. In contrast, Co-N-C（HCl） that synthesized by removing MgO with HCl from Co-N-C/MgO, as the catalyst produced mainly an acetal as a condensation prod-uct, and chloride ions had a negative effect on the oxidative esterification. Although the catalytic performance of the cobalt-nitrogen-doped carbon species was greatly affected by HCl treatment, it could be recovered to a great extent by addition of MgO. Moreover, changes in the oxygen pressure hardly affected the oxidative esterification of furfural with Co-N-C/MgO. This study not only pro-vides an effective approach to prepare methylfuroate, but also for designing high-performance non-precious metal catalysts for the oxidative esterification of biomass-derived compounds.
文摘随着人工智能(AI)技术的迅猛发展,AI for Science(AI4S)正逐渐成为科学研究的新范式,尤其在化学领域的实验方法上引发了一场革命。本研究创新性地引入了自驱动实验室(SDL)的概念,旨在解决未来化学研究中的挑战,并探索其在基础化学实验中的AI数字化升级应用。研究团队采用了可循环利用的固体酸作为催化剂,以乙酸和苄醇的酯化反应为研究对象,开发了一种相对低成本、适用于教学的反应条件优化闭环系统。该系统由基于芯曙光自动合成仪的自动化反应器、自主设计的液相自动进样监控系统,以及基于Python的决策优化算法所组成。本研究展示了在现有条件下如何克服硬件兼容性和算法优化的挑战,为化学实验的未来创新发展奠定了坚实的基础。
基金the Graduate Student Innovation Scientific Research Projects of Heilongjiang Province, China (No.YJSCX2007-0282-HLJ)
文摘La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorption, FTIR spectroscopic analysis, thermogravimetric analysis, and the total amount of acidity of catalyst was estimated by TPD of NH3. The results indicate that lanthanum has been incorporated into SBA-15 molecular sieve. The prepared materials（La-SO42-/SBA-15） keep the highly ordered mesoporous two-dimensional hexagonal structure and do not change the mesoporous channel structure of the support SBA-15. The catalyst showed best catalytic activity in the synthesis of n-butyl acetate. The optimum conditions of the esterification by orthogonal experiments were studied： the molar ratio of n-butanol to acetic acid 1：1.2, the amount of catalyst 7.5%, reaction time 80 min. The yield of n-butyl acetate could reach 93.2% under the optimum conditions. The catalyst was recyclable, cost effective and environmental friendly.
基金Supported by the National Natural Science Foundation of China (No. 20176020) and 863 Hi-Technology Research and Deve-lopment Program of China (No. 2002AA514030)
文摘A self-made lipase preparation from Candida sp. 99-125 was used for the production of biodiesel through enzymatic esterification of fatty acids. The crude lipase powder and fermentation broth were immobilized on a cheap fiber cloth carrier. The conditions of lipase-catalyzed esterification between long-chain fatty acids and methanol in a solvent system were investigated in detail, including the temperature, pH value, substrate concentration, solvent, absorbent agent, enzyme dosage and purity, immobilization method, the mode of addition of substrate. The results show that reaction temperature, pH of lipase micro-environment, substrate concentration, enzyme dosage and purity affect the esterification strongly. Several new methods and enzymatic procedures for improving the enzymatic reaction involving the process cost are also discussed, such as fossil diesel fuel as reaction solvent, immobilization method, multi-step gradient addition of methanol. The esterification degree of 92.8% was obtained with oleic acid and methanol under the optimal reaction condition after 12.5 h reaction time. The half-life of the immobilized lipase preparation from crude free lipase powder for esterification was 15 days.
文摘The esterification of free fatty acids(FFA) in waste cooking oil with methanol in the presence of Fe2(SO4)3/C(ferric sulfate/active carbon) catalyst was studied.The effects of different temperature,methanol/FFA mole ratio and amount of catalyst on the conversion of FFA were investigated.The results demonstrated that under optimal esterification conditions the final acid value of the resultant system can be reduced to ～1(mg KOH)·g-1,which met fully the requirements in post-treatment for efficient separation of glycerin and biodiesel.The kinetics of the esterification were also investigated under different temperatures.The results indicated that the rate-control step could be attributed to the surface reaction and the esterification processes can be well-depicted by the as-calculated kinetic formula in the range of the experimental conditions.
文摘An efficient esterification of ferrocenecarboxylic acid with substituted phenols has been achieved using DCC / DMAP protocol in ionic liquids. The corresponding esters are produced in high yields.
基金Supported by the Key Program of the National Natural Science Foundation of China(21036007)the National High-Tech Project of China(2012AA062903)
文摘Novel Mg O–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein(MAL) with methanol to methyl methacrylate(MMA). The Mg O–SBA-15 supports were synthesized with different magnesia loadings from different magnesium precursors and hydrochloric acid molar concentrations. The Mg O–SBA-15 supports and Pd–Pb/Mg O–SBA-15 catalysts were characterized by several analysis methods. The results revealed that the addition of Mg O improved the ordered structure of SBA-15 supports and provided surface alkalinity of SBA-15 supports. The average size of the Pd3 Pb particles on magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts was smaller than that on the pure silica-based Pd–Pb/SBA-15 catalysts. The experiments on catalyst performance showed that the magnesia-modified Pd–Pb/Mg O–SBA-15 catalysts had higher activity than pure silica-based Pd–Pb/SBA-15 catalysts, showing the strong dependence of catalytic activity on the average size of active particles. The difference of activity between Pd–Pb/SBA-15 catalysts and Pd–Pb/Mg O–SBA-15 catalysts was due to the discrepant structural properties and surface alkalinity provided by Mg O, which led to the different Pd3 Pb particle sizes and then resulted in the different number of active sites. Besides magnesia loadings, other factors, such as hydrochloric acid molar concentration and magnesium precursors, had considerable influences on the catalytic activity.
基金This work was supported by the National Natural Science Foundation of China(21773068,21811530273,21573072)the National Key Research and Development Program of China(2017YFA0403102)Shanghai Leading Academic Discipline Project(B409).
文摘Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sulfuric acid.The swelling ability of acidic PILs was greatly affected by cross-linker content and chain length of 3-alkyl-substituents on imidazolium.Cross-linked network structures could be observed from the cryogenic scanning electron microscopy(cryo-SEM)images of the swollen acidic PILs in formic acid.Acidic PILs with network structures in swollen state exhibited excellent activities in the esterification of cyclohexene and formic acid,and the catalytic activities were in positive correlation with their swelling abilities.Acidic PIL with 3-octyl-substituent and 2.5 mol%DVB(PIL-C8-2.5DVB-HSO4)had the highest swelling ability in formic acid and exhibited comparable catalytic activities with homogeneous catalysts such as sulfuric acid and p-toluenesulfonic acid.
基金the Research Fund of Istanbul University. Project number: 944/090597.
文摘Esterification of methyl alcohol with acetic acid catalysed by Amberlyst-15 (cation-exchange resin) was carried out in a batch reactor in the temperature ranging between 318-338 K, at atmospheric pressure. The reaction rate increased with increase in catalyst concentration and reaction temperature, but decreased with an increase in water concentration. Stirrer speed had virtually no effect on the rate under the experimental conditions. The rate data were correlated with a second-order kinetic model based on homogeneous reaction. The apparent activation energy was found to be 22.9kJ mol-1 for the formation of methyl acetate. The methyl acetate production was carried out as batch and continuous in a packed bed reactive distillation column with high purity methyl acetate produced.
