The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (I...The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.展开更多
A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation proc...A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.展开更多
Preparation of biodiesel from waste oils containing 72% of free fatty acids catalyzed by a novel Br?nsted acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate([BHSO_3MIM][HSO_4]) was systematically invest...Preparation of biodiesel from waste oils containing 72% of free fatty acids catalyzed by a novel Br?nsted acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate([BHSO_3MIM][HSO_4]) was systematically investigated.The optimum molar ratio of methanol to waste oils,catalyst amount,reaction temperature and reaction time were 8/1,10%(based on the mass of waste oils),140°C and 6 h,respectively,under which the obtained yield of biodiesel reached 94.9%.Also,[BHSO_3MIM][HSO_4] as a catalyst still retained around 97% of its original catalytic activity after successive re-use of 5 batches(6 h per batch),showing the excellent operational stability.Moreover,the acidic IL [BHSO_3MIM][HSO_4] was able to ef ficiently catalyze conversions of waste oils with different amounts of FFAs(free fatty acids) into biodiesel,and showed tremendous application potential.Therefore,an ef ficient and environmentally friendly catalyst is provided for the synthesis of biodiesel from waste oils with high acid value.展开更多
The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C_4 alkylation process. Due to their unique properties, ionic liquids(ILs) are thought ...The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C_4 alkylation process. Due to their unique properties, ionic liquids(ILs) are thought to be new potential acid catalysts for C_4 alkylation. An analysis of the regular and modified chloroaluminate ILs, novel Br?nsted ILs and composite ILs used in isobutane/butene alkylation shows that the use of either ILs or ILs coupled with mineral acid as homogeneous catalysts can help to greatly adjust the acid strength. By modifying the structural parameters of the cations and anions of the ILs, the solubility of the reactants could also be adjusted, which in turn displays a positive effect on improving the activity of ILs. Immobilization of ILs is an effective way to modulate the surface adsorption/desorption properties and acid strength distribution of the solid acid catalysts. Such a process has a tremendous potential to reduce the deactivation of catalyst and enhance the activity of the solid acid catalyst. The development of novel acid catalysts for C_4 alkylation is a comprehensive consideration of acid strength and its distribution, interfacial properties and transport characteristics.展开更多
The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designe...The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designed and synthesized via the free radical copolymerization of ionic liquid monomers,sodium p-styrenesulfonate,and crosslinkers,followed by acidification.The 31P nuclear magnetic resonance chemical shifts of adsorbed trimethylphosphine oxide indicated that the synthesized SAPILs presented moderate and single acid strength.The thermogravimetric analysis results in the temperature range of 300–345°C revealed that the synthesized SAPILs were more stable than the commercial resin Amberlite IR-120(H)(245°C).Cryogenic scanning electron microscopy testing demonstrated that SAPILs presented unique three-dimensional(3D)honeycomb structure in water,which was ascribed to the swelling-induced self-assembly of the molecules.Moreover,we used SAPILs with micron-sized honeycomb structure in water as catalysts for the hydrolysis of cyclohexyl acetate to cyclohexanol,and determined that their catalytic activity was much higher than that of homogeneous acid catalysts.The equilibrium concentrations of all reaction components inside and outside the synthesized SAPILs were quantitatively analyzed using a series of simulated reaction mixtures.Depending on the reaction mixture,the concentration of cyclohexyl acetate inside SAPIL-1 was 7.5–23.3 times higher than that outside of it,which suggested the high enrichment ability of SAPILs for cyclohexyl acetate.The excellent catalytic performance of SAPILs was attributed to their 3D honeycomb structure in water and high enrichment ability for cyclohexyl acetate,which opened up new avenues for designing highly efficient heterogeneous acid catalysts that could eventually replace conventional homogeneous acid catalysts.展开更多
1-Butyl-3-methylimidazolium bromochloroaluminate ([bmim]Br-AlCl3) ionic liquid was used as an acid catalyst for removal of trace olefins from the aromatic hydrocarbons. The influence of various reaction parameters s...1-Butyl-3-methylimidazolium bromochloroaluminate ([bmim]Br-AlCl3) ionic liquid was used as an acid catalyst for removal of trace olefins from the aromatic hydrocarbons. The influence of various reaction parameters such as reaction time, temperature, dosage and acid strength of catalyst was investigated. The experimental results demonstrated that the ionic liquid exhibited excellent activity under mild reaction conditions, with the conversion of olefins reaching 98.84% and the bromine index of the aromatics varying from 1129 to 13. On the basis of the results obtained, thereof, a possible reaction mechanism was proposed.展开更多
We experimentally studied the catalytic performances of a series of Brrnsted-Lewis acidic N-methyl-2-pyrrolidonium metal chlorides ([Hnmp]Cl/MClx, where M=Fe, Zn, A1, or Cu) for the hydrolysis of microcrystalline ce...We experimentally studied the catalytic performances of a series of Brrnsted-Lewis acidic N-methyl-2-pyrrolidonium metal chlorides ([Hnmp]Cl/MClx, where M=Fe, Zn, A1, or Cu) for the hydrolysis of microcrystalline cellulose (MCC) and cotton to produce reducing sugar. A variety of factors, such as temperature, time, ionic liquid (IL) species, IL dosage, and the concentra- tion of the metal chloride were investigated. [Hnmp]Cl/FeCl3 presented the best hydrolysis performance, affording a 98.8% yield of total reducing sugar from MCC (1 h, 100 ℃, 0.1 g MCC, 0.2 g acidic IL, 2.0 g [Bmim]Cl as solvent), which is better than or comparable to results previously obtained with other -SO3H functionalized acidic ILs. The hydrolysis performances of [Hnmp]Cl/MClx were rationalized using density functional theory calculations, which indicated that interactions between the metal chlorides and the cellulose, including charge-transfer interactions are important in the hydrolysis of cellulose and degra- dation of glucose. This work shows that Bronsted-Lewis acidic ILs are potential catalysts for the hydrolysis of cellulose to produce sugar.展开更多
A series of ammonium-bifunctionalized ionic liquid extractants (ammonium-Bif-ILEs) combined with a number of anions, in- cluding carboxylic acids and 1,3-diketonates, have been prepared and studied in this report. T...A series of ammonium-bifunctionalized ionic liquid extractants (ammonium-Bif-ILEs) combined with a number of anions, in- cluding carboxylic acids and 1,3-diketonates, have been prepared and studied in this report. Their extraction behavior and properties toward rare earth ions (REs(III)) are systematically investigated in chloride media as a function of important param- eters such as aqueous phase pH, salting-out agent concentrations, and extraction temperature. The separation performance of ammonium-Bif-ILEs toward REs(III) are systematically discussed. The results demonstrate that ammonium-Bif-ILEs have a synergistic effect between the cation and anions in separation of REs(III). The influences of different anions on separation fac- tor (β) values are further studied. By comparison, ammonium-Bif-ILEs containing 1,3-diketonates have more potential appli- cations in La(III)/RE(III) separation than those containing carboxylic acids.展开更多
文摘The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.
基金supported by the National Key Projects for Fundamental Research and Development of China(2016YFB0600903)the National Natural Science Foundation of China(91434107,21506226,21476245)the Key Research Program of Frontier Sciences of Chinese Academy of Sciences(QYZDY-SSW-JSC011)~~
文摘A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.
基金Supported by the National Natural Science Foundation of China(21676104,21336002,21376096)the Open Funding Project of the State Key Laboratory of Bioreactor Engineeringthe Program of State Key Laboratory of Pulp and Paper Engineering(2017ZD05)
文摘Preparation of biodiesel from waste oils containing 72% of free fatty acids catalyzed by a novel Br?nsted acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate([BHSO_3MIM][HSO_4]) was systematically investigated.The optimum molar ratio of methanol to waste oils,catalyst amount,reaction temperature and reaction time were 8/1,10%(based on the mass of waste oils),140°C and 6 h,respectively,under which the obtained yield of biodiesel reached 94.9%.Also,[BHSO_3MIM][HSO_4] as a catalyst still retained around 97% of its original catalytic activity after successive re-use of 5 batches(6 h per batch),showing the excellent operational stability.Moreover,the acidic IL [BHSO_3MIM][HSO_4] was able to ef ficiently catalyze conversions of waste oils with different amounts of FFAs(free fatty acids) into biodiesel,and showed tremendous application potential.Therefore,an ef ficient and environmentally friendly catalyst is provided for the synthesis of biodiesel from waste oils with high acid value.
基金Supported by the National Natural Science Foundation of China(21276163,21576168)
文摘The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C_4 alkylation process. Due to their unique properties, ionic liquids(ILs) are thought to be new potential acid catalysts for C_4 alkylation. An analysis of the regular and modified chloroaluminate ILs, novel Br?nsted ILs and composite ILs used in isobutane/butene alkylation shows that the use of either ILs or ILs coupled with mineral acid as homogeneous catalysts can help to greatly adjust the acid strength. By modifying the structural parameters of the cations and anions of the ILs, the solubility of the reactants could also be adjusted, which in turn displays a positive effect on improving the activity of ILs. Immobilization of ILs is an effective way to modulate the surface adsorption/desorption properties and acid strength distribution of the solid acid catalysts. Such a process has a tremendous potential to reduce the deactivation of catalyst and enhance the activity of the solid acid catalyst. The development of novel acid catalysts for C_4 alkylation is a comprehensive consideration of acid strength and its distribution, interfacial properties and transport characteristics.
文摘The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designed and synthesized via the free radical copolymerization of ionic liquid monomers,sodium p-styrenesulfonate,and crosslinkers,followed by acidification.The 31P nuclear magnetic resonance chemical shifts of adsorbed trimethylphosphine oxide indicated that the synthesized SAPILs presented moderate and single acid strength.The thermogravimetric analysis results in the temperature range of 300–345°C revealed that the synthesized SAPILs were more stable than the commercial resin Amberlite IR-120(H)(245°C).Cryogenic scanning electron microscopy testing demonstrated that SAPILs presented unique three-dimensional(3D)honeycomb structure in water,which was ascribed to the swelling-induced self-assembly of the molecules.Moreover,we used SAPILs with micron-sized honeycomb structure in water as catalysts for the hydrolysis of cyclohexyl acetate to cyclohexanol,and determined that their catalytic activity was much higher than that of homogeneous acid catalysts.The equilibrium concentrations of all reaction components inside and outside the synthesized SAPILs were quantitatively analyzed using a series of simulated reaction mixtures.Depending on the reaction mixture,the concentration of cyclohexyl acetate inside SAPIL-1 was 7.5–23.3 times higher than that outside of it,which suggested the high enrichment ability of SAPILs for cyclohexyl acetate.The excellent catalytic performance of SAPILs was attributed to their 3D honeycomb structure in water and high enrichment ability for cyclohexyl acetate,which opened up new avenues for designing highly efficient heterogeneous acid catalysts that could eventually replace conventional homogeneous acid catalysts.
基金the Sinopec Zhenhai Refining & Chemical Company for financial support
文摘1-Butyl-3-methylimidazolium bromochloroaluminate ([bmim]Br-AlCl3) ionic liquid was used as an acid catalyst for removal of trace olefins from the aromatic hydrocarbons. The influence of various reaction parameters such as reaction time, temperature, dosage and acid strength of catalyst was investigated. The experimental results demonstrated that the ionic liquid exhibited excellent activity under mild reaction conditions, with the conversion of olefins reaching 98.84% and the bromine index of the aromatics varying from 1129 to 13. On the basis of the results obtained, thereof, a possible reaction mechanism was proposed.
基金supported by the National Natural Science Foundation of China (21176021, 21276020)Fundamental Research Funds for the Central Universities (YS1401)+1 种基金the National High Technology Research and Development Program of China (2012AA- 101803)the Deanship of Scientific Research at King Saud University for funding the work through the research group project (RG-1436-026)
文摘We experimentally studied the catalytic performances of a series of Brrnsted-Lewis acidic N-methyl-2-pyrrolidonium metal chlorides ([Hnmp]Cl/MClx, where M=Fe, Zn, A1, or Cu) for the hydrolysis of microcrystalline cellulose (MCC) and cotton to produce reducing sugar. A variety of factors, such as temperature, time, ionic liquid (IL) species, IL dosage, and the concentra- tion of the metal chloride were investigated. [Hnmp]Cl/FeCl3 presented the best hydrolysis performance, affording a 98.8% yield of total reducing sugar from MCC (1 h, 100 ℃, 0.1 g MCC, 0.2 g acidic IL, 2.0 g [Bmim]Cl as solvent), which is better than or comparable to results previously obtained with other -SO3H functionalized acidic ILs. The hydrolysis performances of [Hnmp]Cl/MClx were rationalized using density functional theory calculations, which indicated that interactions between the metal chlorides and the cellulose, including charge-transfer interactions are important in the hydrolysis of cellulose and degra- dation of glucose. This work shows that Bronsted-Lewis acidic ILs are potential catalysts for the hydrolysis of cellulose to produce sugar.
基金supported by the National Basic Research Program of China (2012CBA01202)the National Natural Science Foundation of China (51174184, 21401110)+1 种基金the Key Research Program of the Chinese Academy of Sciences (KGZD-EW-201-1)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (14KJB150019)
文摘A series of ammonium-bifunctionalized ionic liquid extractants (ammonium-Bif-ILEs) combined with a number of anions, in- cluding carboxylic acids and 1,3-diketonates, have been prepared and studied in this report. Their extraction behavior and properties toward rare earth ions (REs(III)) are systematically investigated in chloride media as a function of important param- eters such as aqueous phase pH, salting-out agent concentrations, and extraction temperature. The separation performance of ammonium-Bif-ILEs toward REs(III) are systematically discussed. The results demonstrate that ammonium-Bif-ILEs have a synergistic effect between the cation and anions in separation of REs(III). The influences of different anions on separation fac- tor (β) values are further studied. By comparison, ammonium-Bif-ILEs containing 1,3-diketonates have more potential appli- cations in La(III)/RE(III) separation than those containing carboxylic acids.