Esterification is an important process in the food industry and can be carried out via homogeneous or heterogeneous catalysis.The homogeneous catalyst,despite providing high conversion,can cause corrosion in reactors,...Esterification is an important process in the food industry and can be carried out via homogeneous or heterogeneous catalysis.The homogeneous catalyst,despite providing high conversion,can cause corrosion in reactors,which is not observed with the use of heterogeneous catalysts.However,some of these catalysts require a high process temperature and may lose their catalytic activity with reuse.Thus,catalytic membranes have been proposed as a promising alternative.The combination of catalysis and separation in a single module provides greater conversion,reduction of excess reagents,compact industrial plant,making the process more efficient.Within this context,this work aims to present a literature review on the catalytic membrane for the synthesis of esters,improving the understanding of the production and development.This review examines the materials,catalysts used,and synthetic pathways.A comparison between the methods,as well as limitations and gaps in the literature,are highlighted.展开更多
The fermentation for succinic acid production outperforms other methods by low energy consumption and environmental benignity,with the resulting products mainly as disodium succinate(DSA).By directly esterifying DSA u...The fermentation for succinic acid production outperforms other methods by low energy consumption and environmental benignity,with the resulting products mainly as disodium succinate(DSA).By directly esterifying DSA using CO_(2) and CH3OH,it is expected to avoid the use of inorganic acids.By high-resolution mass spectrometry analysis and theoretical calculation,this study establishes that the reaction consists of three steps,i.e.,first forming 3-carboxypropanoate,then monomethyl succinate(MMS),and finally dimethyl succinate(DMS).A detailed kinetic analysis is further performed,the results demonstrate that the transformation of DSA to MMS is regarded to be a second-order reaction for reactant DSA,while the transformation of MMS to DMS is a first-order reaction for reactant MMS.The activation energy for the generation of MMS from DSA is 37.15 kJ·mol^(-1),and that for the generation of DMS from MMS is 85.80 kJ·mol^(-1),indicating the latter one is the rate-determining step.展开更多
We described a novel polymer-lipase conjugate for high-efficient esterification of vitamin E using vitamin E and succinic anhydride as the substrates in nonaqueous media.In this work,the monomer,N-isopropylacrylamide(...We described a novel polymer-lipase conjugate for high-efficient esterification of vitamin E using vitamin E and succinic anhydride as the substrates in nonaqueous media.In this work,the monomer,N-isopropylacrylamide(NIPAM),was grafted onto Candida rugosa lipase(CRL)to synthesize poly(NIPAM)(pNIPAM)-CRL conjugate by atom transfer radical polymerization via the initiator coupled on the surface of CRL.The result showed that the catalytic efficiencies of pNIPAM-CRL conjugates(19.5-30.3 L·s^(-1)·mmol^(-1))were at least 7 times higher than that of free CRL(2.36 L·s^(-1)·mmol^(-1))in DMSO.It was attributed to a significant increase in Kcat of the conjugates in nonaqueous media.The synthesis catalyzed by pNIPAM-CRL co njugates was influenced by the length and density of the grafted polymer,water content,solvent polarity and molar ratio of the substrates.In the optimal synthesis,the reaction time was shortened at least 7 times,and yields of vitamin E succinate by pNIPAM-g-CRL and free CRL were obtained to be 75.4%and 6.6%at 55℃after the reaction for 1.5 h.The result argued that conjugation with pNIPAM induced conformational change of the lid on CRL based on hydrophobic interaction,thus providing a higher possibility of catalysis-favorable conformation on CRL in nonaqueous media.Moreover,pNIPAM conjugation improved the thermal stability of CRL greatly,and the stability improved further with an increase of chain length of pNIPAM.At the optimal reaction conditions(55℃and 1.5 h),pNIPAM-g-CRL also exhibited good reusability in the enzymatic synthesis of vitamin E succinate and kept~70%of its catalytic activity after ten consecutive cycles.The research demonstrated that pNIPAM-g-CRL was a more competitive biocatalyst in the enzymatic synthesis of vitamin E succinate and exhibited good application potential under harsh industrial conditions.展开更多
Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold lo...Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.展开更多
The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor.The reaction was conducted in the temperature range of 323.15 to 368.15 K with t...The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor.The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure.The measurement data were regression with the pseudo-homogeneous(P-H),Eley-Rideal(E-R),and Langmuir-Hinshelwood(L-H)heterogeneous kinetic models.Independent adsorption experiments were implemented to gain the adsorption equilibrium constants of four components.Among the above three models,the L-H model exhibited the best fitting results.The stability of NKC-9 was evaluated by long-term running with the yield of methyl methacrylate no decrease during 3000 h operation.The structure and physicochemical properties of the new and used catalyst were performed by several characterizations including thermogravimetric analysis(TG),scanning electron microscope(SEM),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FT-IR)and so on.展开更多
As an important organic,isobutyl acetate(IbAc)has been widely used in industries because of its good biodegradability,low surface tension,and other properties.The industrial production of IbAc is usually catalyzed by ...As an important organic,isobutyl acetate(IbAc)has been widely used in industries because of its good biodegradability,low surface tension,and other properties.The industrial production of IbAc is usually catalyzed by sulfuric acid.However,the use of sulfuric acid has the drawbacks of causing considerable corrosion to equipment and being difficult to be separated.In this work,n-sulfopropyl-3-methylpyridinium trifluoromethanesulfonate([HSO_(3)-PMPY][CF_(3)SO_(3)])Bronsted acidic ionic liquid(BAIL)was used as the catalyst and the catalytic activity,solubility,and corrosiveness were evaluated for the esterification of acetic acid with isobutanol.The reaction kinetics and chemical equilibrium were systemically studied.Compared to conventional acid catalysts,[HSO_(3)-PMPY][CF_(3)SO_(3)]showed higher catalytic activity,more excellent reusability,more favorable phase separation,and non-corrosiveness.Three kinetic equations based on ideal homogeneous(IH),non-ideal homogeneous(NIH),and modified nonideal homogeneous(NIH-M)models were established and correlated with the experimental data to determine the parameters and errors.The NIH-M model exhibited the best agreement with the experimental data,owing to its prediction considering the non-ideality and the self-catalysis effect of acetic acid in this system.Besides,the error of NIH-M model fitting was mainly caused by the difference in solubility between[HSO_(3)-PMPY][CF_(3)SO_(3)]with reactants and products in the reaction system.Furthermore,the applicability of the NIH-M model was investigated by simulating the esterification of acetic acid with three short-chain alcohols(ethanol,n-butanol,and isobutanol)catalyzed by BAILs.The NIH-M model displayed an acceptable simulation for this type of acetic acid esterification reaction catalyzed by BAILs at different ranges of the BAILs concentration and temperature.This study confirmed the industrial prospects of[HSO_(3)-PMPY][CF_(3)SO_(3)]in isobutyl acetate production and the applicability of the NIH-M kinetic model in the esterification of acetic acid.展开更多
In this study,lipases of CALB(Candida antarctica lipase B),TLL(Thermomyces lanuginosa lipase),RML(Rhizomucor miehei lipase),CALA(Candida antarctica lipase A)and LU(Lecitase?Ultra)were encapsulated into the nucleotideh...In this study,lipases of CALB(Candida antarctica lipase B),TLL(Thermomyces lanuginosa lipase),RML(Rhizomucor miehei lipase),CALA(Candida antarctica lipase A)and LU(Lecitase?Ultra)were encapsulated into the nucleotidehybrid metal coordination polymers(CPs)for diacylglyerols(DAG)preparation.Guanosine 5'-monophosphate(GMP)and adenosine 5'-monophosphate(AMP)were used as coordinating molecules,and metal ions of Fe^(3+),Ba^(2+),Mn^(2+),Ni^(2+)and Cr^(3+)were applied to prepare matrix.Results indicated that,besides Ba^(2+)with AMP,all other metal ions can coordinate with AMP and GMP to generate CPs.In addition,the AMP/Ni was amorphous when standing temperature was 4℃,while it was crystalline when standing temperature was from 30 to 180℃.DAG content from 47.55%to 64.99%was obtained from glycerolysis by CALB@GMP/Ba,RML@GMP/Ba,TLL@GMP/Ba,RML@GMP/Mn and TLL@GMP/Mn.Additionally,CALB@GMP/Fe showed selectivity towards DAG formation in the esterification and DAG content up to 61.88%was obtained.展开更多
In polyester fiber industrial processes,the prediction of key performance indicators is vital for product quality.The esterification process is an indispensable step in the polyester polymerization process.It has the ...In polyester fiber industrial processes,the prediction of key performance indicators is vital for product quality.The esterification process is an indispensable step in the polyester polymerization process.It has the characteristics of strong coupling,nonlinearity and complex mechanism.To solve these problems,we put forward a multi-output Gaussian process regression(MGPR)model based on the combined kernel function for the polyester esterification process.Since the seasonal and trend decomposition using loess(STL)can extract the periodic and trend characteristics of time series,a combined kernel function based on the STL and the kernel function analysis is constructed for the MGPR.The effectiveness of the proposed model is verified by the actual polyester esterification process data collected from fiber production.展开更多
In the course of organic synthesis, particularly for multi-step synthesis or natural product total synthesis, the selection of appropriate protective groups for the intended functionality is crucial in order to achiev...In the course of organic synthesis, particularly for multi-step synthesis or natural product total synthesis, the selection of appropriate protective groups for the intended functionality is crucial in order to achieve chemoselective synthetic goals. The development of many useful protective groups has been reported based on the functionality of the anilino group. Herein, we discuss our study of various protective groups and the processes we used to establish compatibility with anilino functionality via the implementation of Oxone-mediated oxidative esterification in methanol. The results and the details of our experiments are reported herein.展开更多
In this work, a series of SO4^2-/TiO2/γ-Al2O3 solid acid catalysts were synthesized by impregnation method, in which nano-TiO2 was prepared by sol–gel method, and then the nano-TiO2 sol was loaded on porous γ-Al2O3...In this work, a series of SO4^2-/TiO2/γ-Al2O3 solid acid catalysts were synthesized by impregnation method, in which nano-TiO2 was prepared by sol–gel method, and then the nano-TiO2 sol was loaded on porous γ-Al2O3 supporter through impregnation. The structure and property of catalyst were characterized by XRD, N2-BET,SEM, TEM, XPS, NH3-TPD, Pyridine-IR and FT-IR. In addition, the catalyst of chelate bidentate coordination acid center model was established. The catalytic performance test was carried out in the esterification of n-butyl alcohol with lauric acid and the catalyst showed excellent activity. The experimental results showed that the medium strength acid sites were more dominant active sites than the strong and weak acid sites for the rapid esterification reaction. Its kinetic behaviors and activation energy were studied for the esterification under the catalytic reaction condition.展开更多
The esterification of lauric acid with methanol could be efficiently catalyzed by ZrOCl2·8H2O, and this reaction was studied to develop a green method for biodiesel production. The influencing factors, such as am...The esterification of lauric acid with methanol could be efficiently catalyzed by ZrOCl2·8H2O, and this reaction was studied to develop a green method for biodiesel production. The influencing factors, such as amount of catalyst, reaction time and molar ratio of acid to methanol, were investigated. The results indicated that the ZrOCl2·8H2O catalyst showed high catalytic activity, and gave a 97.0% methyl laurate conversion rate under the following optimized conditions, viz.: a lauric acid/methanol molar ratio of 1:10, a catalyst dosage of 4%, and a reaction duration of 2 h at methanol refluxing temperature. The catalyst could be easily recovered while its activity could be well retained after three cycles. The ZrOCl2·8H2O catalyst also exhibited excellent catalytic activity for the esterification of different free long-chain fatty acids(including nonedible oils with high acid value) with different short carbon chain alcohols. Therefore, the ZrOCl2·8H2O catalyst has good potential for the synthesis of biodiesel from low-cost feedstocks such as waste vegetable oils and non-edible oils.展开更多
A series of supported intermetallic Pb-Pb catalysts were prepared with the impregnation method by changing the support(silica,molecular sieve or γ-alumina)and the pore size.The chemical states of the two metals were ...A series of supported intermetallic Pb-Pb catalysts were prepared with the impregnation method by changing the support(silica,molecular sieve or γ-alumina)and the pore size.The chemical states of the two metals were characterized by XPS analysis,the process for producing methyl methacrylate based on the direct oxidative esterification of methacrolein with methanol in the presence of oxygen was performed in a slurry reactor with the above-mentioned catalysts.The influence of the calcination temperature and the kinds of support as well as the pore size on catalytic activity had been extensively investigated.Under the conditions of temperature at 80℃,catalyst 3.8%(ω)and the reaction time 2 h,the conversion rate of methacrolein reached 85%,the selectivity and the yield of methyl methacrylate were 90% and 76.5%,respectively.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
In this work,a series of novel proton-gradient-transfer acid complexes(PGTACs)were developed.Their physicochemical properties,including thermal stability,melting point,and Hammett acidity,were measured.The effects of ...In this work,a series of novel proton-gradient-transfer acid complexes(PGTACs)were developed.Their physicochemical properties,including thermal stability,melting point,and Hammett acidity,were measured.The effects of catalyst loading,reaction temperature,and substrate expansion on the catalytic performance were systematically studied.It is found that the combination of bidentate N-heterocycle and H;SO;(1:2 M ratio)could form simultaneously N–H covalent bond and N…H hydrogen bond,which makes the PGTACs excellent catalysts integrate the advantages of strong acids(high catalytic activity)and ionic liquids(phase separation)in the esterification reaction.Moreover,these PGTACs can be reused by convenient phase separation without obvious diminution of catalytic activity.It is concluded that these PGTACs are potential alternative candidates for esterification reaction in the process of industrial catalysis.展开更多
Introduction Although the application of microwave technique has been reported as a new type of energy source chemically, it is only in recent years that this technique has been used as the energy source for organic s...Introduction Although the application of microwave technique has been reported as a new type of energy source chemically, it is only in recent years that this technique has been used as the energy source for organic synthesis. In 1986, R. Gedye, et al., published the report of the benzoate synthesis from the respective reactions between benzene carboxylic acid and methanol, propanol or butanol under microwave heating and the catalysis of H<sub>2</sub>SO<sub>4</sub>.展开更多
The dynamic analysis and optimal design of reactive extraction are challenging due to high nonlinearity of model equations and tough decision of judging criteria. In this work, a dynamic rate-based method is developed...The dynamic analysis and optimal design of reactive extraction are challenging due to high nonlinearity of model equations and tough decision of judging criteria. In this work, a dynamic rate-based method is developed on g PROMS platform to get easy access to the solutions of reactive extraction with phase splitting. Based on rigorous criteria, dynamic analysis from initial state to final equilibrium(e.g., evolution of phase composition, mass transfer rate and reaction rate) and optimal design of operating conditions(e.g., extractant dosage and feed molar ratio) are achieved. To illustrate the method, the esterification of n-hexyl acetate is taken as an example. The approach proves to be reliable in the analysis and optimization of the exemplified system, which provides instructive reference for further process design and simulation of reactive extraction.展开更多
To prepare polymer supported ionic liquids(PSILs)as effective catalysts for esterification,the free radical suspension copolymerization of vinylbenzyl chloride(VBC,monomer),styrene(St,monomer)and divinylbenzene(DVB,cr...To prepare polymer supported ionic liquids(PSILs)as effective catalysts for esterification,the free radical suspension copolymerization of vinylbenzyl chloride(VBC,monomer),styrene(St,monomer)and divinylbenzene(DVB,crosslinker)with the addition of n-heptane(porogen)was carried out for the fabrication of the porous polymer(PVD)microsphere as support,followed by the immobilization of sulfonic acid-functionalized ionic liquids by the successive treatment of benzimidazole(BIm),1,3-propane sultone and sulfuric acid(H2SO4)or trifluoromethanesulfonic acid(CF3SO3H).The effects of the compositions of DVB and n-heptane on the internal structure of the polymer supports were investigated,and it was found that the support with 40 wt%DVB and 60 wt%n-heptane(with relative to the monomer)could endow the final PSILs with the relatively optimal catalytic performance.The preliminary experiment in the batch reactor indicated that PSILs herein exhibited higher catalytic activities than commercial Amberlyst 46 resin for the esterification of propanoic acid(PROAc)with n-propanol(PROOH).Consequently,the optimal PSILs catalyst,PVD-[Bim-SO3H]HSO4,was selected for further study in the batch reactive distillation column because of low cost and its ease of preparation.The yield of propyl ropionate(PROPRO)could reach up to 97.78%at the optimized conditions of PROOH/PROAc molar ratio(2:1)and catalyst dosage(2.0 wt%).The investigation of the reaction kinetic manifested that the calculated results of second order pseudo-homogeneous kinetic model were in good agreement with experimental values.The pre-exponential factor and activation energy were 4.12×107 L·mol-1·min-1 and 60.57 k J·mol-1,respectively.It is worth noting that the PSILs catalyst could be simply recovered and reused with relatively satisfactory decrease in the catalytic activity,which made it an environmental friendly and promising catalyst in the industrial application.展开更多
Utilization of biomass-derived materials or chemicals plays a significant role in reducing the dependence of unsustainable resources of petroleum and coal. A series of sulfonated glucose-derived solid acids(SGSAs) wer...Utilization of biomass-derived materials or chemicals plays a significant role in reducing the dependence of unsustainable resources of petroleum and coal. A series of sulfonated glucose-derived solid acids(SGSAs) were developed in this study through a one-step method. These catalysts were characterized by XRD, FT-IR, SEM,and BET to determine their physiochemical properties, and their acid content was measured by acid–base titration. The catalytic performances of SGSA catalysts were evaluated in two esterification reactions: propionic acid or oleic acid with methanol(a typical reaction to upgrade biodiesel). Conversion of oleic acid and selectivity of methyl oleate can reach as high as 93.3% and 94.7% respectively over SGSA-6, which has the highest -SO3 H density. Moreover, regeneration of spent catalysts by sulfuric acid solution can significantly enhance their stability and reusability.展开更多
Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indiu...Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indium reagent, in many cases. Based on this method of methyl esterification of benzaldehyde derivatives, we further explored an application to heterocyclic aldehydes. The reactions were examined using methanol as well as other alcohols in order to establish a suitable range.展开更多
Producing 2-ethyl-1-hexyl thioglycolate(ETE)via esterification reaction with thioglycolic acid(TGA)aqueous solution as raw material by reactive-separation coupling technology is a promising process intensification met...Producing 2-ethyl-1-hexyl thioglycolate(ETE)via esterification reaction with thioglycolic acid(TGA)aqueous solution as raw material by reactive-separation coupling technology is a promising process intensification method.To choose suitable reactive-separation coupling strategy,the kinetic studies of the esterification of TGA with 2-ethyl-1-hexanol(EHL)were carried out in a batch system.The commercial ion exchange resin was employed as an eco-friendly catalyst.The effects of temperature,catalyst concentration and molar ratio were determined.It was interesting to observe that the equilibrium conversion of TGA increased with the increase of catalyst mass fraction due to the adsorption of product water onto resin surface.The activity-based pseudo-homogeneous(PH),Eley-Rideal(ER)and Langmuir-Hinshelwood-Ho ugen-Watson(LHHW)models were used to fit the kinetics data of the resin-catalyzed reaction.The models of ER and LHHW performed better than the PH model.The kinetics of the TGA-self-catalyzed reaction was also determined.An activity-based homogeneous kinetics model could well describe this self-catalyzed reaction.These results would be meaningful to the selection and design of an appropriate reactionseparation strategy for the production of ETE,to realize the process intensification.展开更多
基金support from CAPES-Coorde nação de Aperfeiçoamento de Pessoal de Nível Superior(PROEX and PrInt Programs)CNPq-Conselho Nacional de Desenvolvimento Científico e Tecnológico(307576/2018-3 and 420275/2018-5)and FAPESC-Fundação de AmparoàPesquisa do Estado de Santa Catarina.
文摘Esterification is an important process in the food industry and can be carried out via homogeneous or heterogeneous catalysis.The homogeneous catalyst,despite providing high conversion,can cause corrosion in reactors,which is not observed with the use of heterogeneous catalysts.However,some of these catalysts require a high process temperature and may lose their catalytic activity with reuse.Thus,catalytic membranes have been proposed as a promising alternative.The combination of catalysis and separation in a single module provides greater conversion,reduction of excess reagents,compact industrial plant,making the process more efficient.Within this context,this work aims to present a literature review on the catalytic membrane for the synthesis of esters,improving the understanding of the production and development.This review examines the materials,catalysts used,and synthetic pathways.A comparison between the methods,as well as limitations and gaps in the literature,are highlighted.
基金Natural Science Foundation of Shanxi Province(202203021221069 and 202103021223063)National Natural Science Foundation of China(21706172).
文摘The fermentation for succinic acid production outperforms other methods by low energy consumption and environmental benignity,with the resulting products mainly as disodium succinate(DSA).By directly esterifying DSA using CO_(2) and CH3OH,it is expected to avoid the use of inorganic acids.By high-resolution mass spectrometry analysis and theoretical calculation,this study establishes that the reaction consists of three steps,i.e.,first forming 3-carboxypropanoate,then monomethyl succinate(MMS),and finally dimethyl succinate(DMS).A detailed kinetic analysis is further performed,the results demonstrate that the transformation of DSA to MMS is regarded to be a second-order reaction for reactant DSA,while the transformation of MMS to DMS is a first-order reaction for reactant MMS.The activation energy for the generation of MMS from DSA is 37.15 kJ·mol^(-1),and that for the generation of DMS from MMS is 85.80 kJ·mol^(-1),indicating the latter one is the rate-determining step.
基金financially supported by the National Key Research and Development Program of China (2021YFC2102801)National Natural Science Foundation of China (21878221)+1 种基金the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (21621004)the Haihe Laboratory of Sustainable Chemical Transformations for financial support.
文摘We described a novel polymer-lipase conjugate for high-efficient esterification of vitamin E using vitamin E and succinic anhydride as the substrates in nonaqueous media.In this work,the monomer,N-isopropylacrylamide(NIPAM),was grafted onto Candida rugosa lipase(CRL)to synthesize poly(NIPAM)(pNIPAM)-CRL conjugate by atom transfer radical polymerization via the initiator coupled on the surface of CRL.The result showed that the catalytic efficiencies of pNIPAM-CRL conjugates(19.5-30.3 L·s^(-1)·mmol^(-1))were at least 7 times higher than that of free CRL(2.36 L·s^(-1)·mmol^(-1))in DMSO.It was attributed to a significant increase in Kcat of the conjugates in nonaqueous media.The synthesis catalyzed by pNIPAM-CRL co njugates was influenced by the length and density of the grafted polymer,water content,solvent polarity and molar ratio of the substrates.In the optimal synthesis,the reaction time was shortened at least 7 times,and yields of vitamin E succinate by pNIPAM-g-CRL and free CRL were obtained to be 75.4%and 6.6%at 55℃after the reaction for 1.5 h.The result argued that conjugation with pNIPAM induced conformational change of the lid on CRL based on hydrophobic interaction,thus providing a higher possibility of catalysis-favorable conformation on CRL in nonaqueous media.Moreover,pNIPAM conjugation improved the thermal stability of CRL greatly,and the stability improved further with an increase of chain length of pNIPAM.At the optimal reaction conditions(55℃and 1.5 h),pNIPAM-g-CRL also exhibited good reusability in the enzymatic synthesis of vitamin E succinate and kept~70%of its catalytic activity after ten consecutive cycles.The research demonstrated that pNIPAM-g-CRL was a more competitive biocatalyst in the enzymatic synthesis of vitamin E succinate and exhibited good application potential under harsh industrial conditions.
基金Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(YPML-2023050269)the Fundamental Research Funds for the Central Universities(226-2023-00085,226-2023-00057).
文摘Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.
基金the National Natural Science Fund for Distinguished Young Scholars(22025803)supported by the National Natural Science Foundation of China(22178338)+1 种基金the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(YLU-DNL Fund 2021018)the financial support of project“Research and development and industrial application of new catalytic materials for green synthesis of MMA to replace highly toxic HCN”(Hebei,20374002D)。
文摘The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor.The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure.The measurement data were regression with the pseudo-homogeneous(P-H),Eley-Rideal(E-R),and Langmuir-Hinshelwood(L-H)heterogeneous kinetic models.Independent adsorption experiments were implemented to gain the adsorption equilibrium constants of four components.Among the above three models,the L-H model exhibited the best fitting results.The stability of NKC-9 was evaluated by long-term running with the yield of methyl methacrylate no decrease during 3000 h operation.The structure and physicochemical properties of the new and used catalyst were performed by several characterizations including thermogravimetric analysis(TG),scanning electron microscope(SEM),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FT-IR)and so on.
基金supported by the National Natural Science Foundation of China(22168004)the Natural Science Foundation of Guangxi Province(2017GXNSFDA198047)the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2019Z010,2021Z013)。
文摘As an important organic,isobutyl acetate(IbAc)has been widely used in industries because of its good biodegradability,low surface tension,and other properties.The industrial production of IbAc is usually catalyzed by sulfuric acid.However,the use of sulfuric acid has the drawbacks of causing considerable corrosion to equipment and being difficult to be separated.In this work,n-sulfopropyl-3-methylpyridinium trifluoromethanesulfonate([HSO_(3)-PMPY][CF_(3)SO_(3)])Bronsted acidic ionic liquid(BAIL)was used as the catalyst and the catalytic activity,solubility,and corrosiveness were evaluated for the esterification of acetic acid with isobutanol.The reaction kinetics and chemical equilibrium were systemically studied.Compared to conventional acid catalysts,[HSO_(3)-PMPY][CF_(3)SO_(3)]showed higher catalytic activity,more excellent reusability,more favorable phase separation,and non-corrosiveness.Three kinetic equations based on ideal homogeneous(IH),non-ideal homogeneous(NIH),and modified nonideal homogeneous(NIH-M)models were established and correlated with the experimental data to determine the parameters and errors.The NIH-M model exhibited the best agreement with the experimental data,owing to its prediction considering the non-ideality and the self-catalysis effect of acetic acid in this system.Besides,the error of NIH-M model fitting was mainly caused by the difference in solubility between[HSO_(3)-PMPY][CF_(3)SO_(3)]with reactants and products in the reaction system.Furthermore,the applicability of the NIH-M model was investigated by simulating the esterification of acetic acid with three short-chain alcohols(ethanol,n-butanol,and isobutanol)catalyzed by BAILs.The NIH-M model displayed an acceptable simulation for this type of acetic acid esterification reaction catalyzed by BAILs at different ranges of the BAILs concentration and temperature.This study confirmed the industrial prospects of[HSO_(3)-PMPY][CF_(3)SO_(3)]in isobutyl acetate production and the applicability of the NIH-M kinetic model in the esterification of acetic acid.
基金the National Natural Science Foundation of China(31772000)。
文摘In this study,lipases of CALB(Candida antarctica lipase B),TLL(Thermomyces lanuginosa lipase),RML(Rhizomucor miehei lipase),CALA(Candida antarctica lipase A)and LU(Lecitase?Ultra)were encapsulated into the nucleotidehybrid metal coordination polymers(CPs)for diacylglyerols(DAG)preparation.Guanosine 5'-monophosphate(GMP)and adenosine 5'-monophosphate(AMP)were used as coordinating molecules,and metal ions of Fe^(3+),Ba^(2+),Mn^(2+),Ni^(2+)and Cr^(3+)were applied to prepare matrix.Results indicated that,besides Ba^(2+)with AMP,all other metal ions can coordinate with AMP and GMP to generate CPs.In addition,the AMP/Ni was amorphous when standing temperature was 4℃,while it was crystalline when standing temperature was from 30 to 180℃.DAG content from 47.55%to 64.99%was obtained from glycerolysis by CALB@GMP/Ba,RML@GMP/Ba,TLL@GMP/Ba,RML@GMP/Mn and TLL@GMP/Mn.Additionally,CALB@GMP/Fe showed selectivity towards DAG formation in the esterification and DAG content up to 61.88%was obtained.
基金Natural Science Foundation of Shanghai,China(No.19ZR1402300)。
文摘In polyester fiber industrial processes,the prediction of key performance indicators is vital for product quality.The esterification process is an indispensable step in the polyester polymerization process.It has the characteristics of strong coupling,nonlinearity and complex mechanism.To solve these problems,we put forward a multi-output Gaussian process regression(MGPR)model based on the combined kernel function for the polyester esterification process.Since the seasonal and trend decomposition using loess(STL)can extract the periodic and trend characteristics of time series,a combined kernel function based on the STL and the kernel function analysis is constructed for the MGPR.The effectiveness of the proposed model is verified by the actual polyester esterification process data collected from fiber production.
文摘In the course of organic synthesis, particularly for multi-step synthesis or natural product total synthesis, the selection of appropriate protective groups for the intended functionality is crucial in order to achieve chemoselective synthetic goals. The development of many useful protective groups has been reported based on the functionality of the anilino group. Herein, we discuss our study of various protective groups and the processes we used to establish compatibility with anilino functionality via the implementation of Oxone-mediated oxidative esterification in methanol. The results and the details of our experiments are reported herein.
基金Sichuan University and laboratory for their support.
文摘In this work, a series of SO4^2-/TiO2/γ-Al2O3 solid acid catalysts were synthesized by impregnation method, in which nano-TiO2 was prepared by sol–gel method, and then the nano-TiO2 sol was loaded on porous γ-Al2O3 supporter through impregnation. The structure and property of catalyst were characterized by XRD, N2-BET,SEM, TEM, XPS, NH3-TPD, Pyridine-IR and FT-IR. In addition, the catalyst of chelate bidentate coordination acid center model was established. The catalytic performance test was carried out in the esterification of n-butyl alcohol with lauric acid and the catalyst showed excellent activity. The experimental results showed that the medium strength acid sites were more dominant active sites than the strong and weak acid sites for the rapid esterification reaction. Its kinetic behaviors and activation energy were studied for the esterification under the catalytic reaction condition.
基金financially supported by the Chunhui Project of the Ministry of Education of China (Z122007)
文摘The esterification of lauric acid with methanol could be efficiently catalyzed by ZrOCl2·8H2O, and this reaction was studied to develop a green method for biodiesel production. The influencing factors, such as amount of catalyst, reaction time and molar ratio of acid to methanol, were investigated. The results indicated that the ZrOCl2·8H2O catalyst showed high catalytic activity, and gave a 97.0% methyl laurate conversion rate under the following optimized conditions, viz.: a lauric acid/methanol molar ratio of 1:10, a catalyst dosage of 4%, and a reaction duration of 2 h at methanol refluxing temperature. The catalyst could be easily recovered while its activity could be well retained after three cycles. The ZrOCl2·8H2O catalyst also exhibited excellent catalytic activity for the esterification of different free long-chain fatty acids(including nonedible oils with high acid value) with different short carbon chain alcohols. Therefore, the ZrOCl2·8H2O catalyst has good potential for the synthesis of biodiesel from low-cost feedstocks such as waste vegetable oils and non-edible oils.
基金Supported by the National Natural Science Foundation of China(No.20436050)and the National High Technology Development Program of China(No.2004AA649240).
文摘A series of supported intermetallic Pb-Pb catalysts were prepared with the impregnation method by changing the support(silica,molecular sieve or γ-alumina)and the pore size.The chemical states of the two metals were characterized by XPS analysis,the process for producing methyl methacrylate based on the direct oxidative esterification of methacrolein with methanol in the presence of oxygen was performed in a slurry reactor with the above-mentioned catalysts.The influence of the calcination temperature and the kinds of support as well as the pore size on catalytic activity had been extensively investigated.Under the conditions of temperature at 80℃,catalyst 3.8%(ω)and the reaction time 2 h,the conversion rate of methacrolein reached 85%,the selectivity and the yield of methyl methacrylate were 90% and 76.5%,respectively.
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sponsored by the National Natural Science Foundation of China(Nos.21576129 and 21878141)the Natural Science Foundation of Jiangsu Province(BK20190310)for financial supports
文摘In this work,a series of novel proton-gradient-transfer acid complexes(PGTACs)were developed.Their physicochemical properties,including thermal stability,melting point,and Hammett acidity,were measured.The effects of catalyst loading,reaction temperature,and substrate expansion on the catalytic performance were systematically studied.It is found that the combination of bidentate N-heterocycle and H;SO;(1:2 M ratio)could form simultaneously N–H covalent bond and N…H hydrogen bond,which makes the PGTACs excellent catalysts integrate the advantages of strong acids(high catalytic activity)and ionic liquids(phase separation)in the esterification reaction.Moreover,these PGTACs can be reused by convenient phase separation without obvious diminution of catalytic activity.It is concluded that these PGTACs are potential alternative candidates for esterification reaction in the process of industrial catalysis.
文摘Introduction Although the application of microwave technique has been reported as a new type of energy source chemically, it is only in recent years that this technique has been used as the energy source for organic synthesis. In 1986, R. Gedye, et al., published the report of the benzoate synthesis from the respective reactions between benzene carboxylic acid and methanol, propanol or butanol under microwave heating and the catalysis of H<sub>2</sub>SO<sub>4</sub>.
基金Supported by the National Natural Science Foundation of China(21776074,21576081,2181101120).
文摘The dynamic analysis and optimal design of reactive extraction are challenging due to high nonlinearity of model equations and tough decision of judging criteria. In this work, a dynamic rate-based method is developed on g PROMS platform to get easy access to the solutions of reactive extraction with phase splitting. Based on rigorous criteria, dynamic analysis from initial state to final equilibrium(e.g., evolution of phase composition, mass transfer rate and reaction rate) and optimal design of operating conditions(e.g., extractant dosage and feed molar ratio) are achieved. To illustrate the method, the esterification of n-hexyl acetate is taken as an example. The approach proves to be reliable in the analysis and optimization of the exemplified system, which provides instructive reference for further process design and simulation of reactive extraction.
基金The National Natural Science Foundation of China(21576053,91534106)the Natural Science Foundation of Fujian Province(2016J01689).
文摘To prepare polymer supported ionic liquids(PSILs)as effective catalysts for esterification,the free radical suspension copolymerization of vinylbenzyl chloride(VBC,monomer),styrene(St,monomer)and divinylbenzene(DVB,crosslinker)with the addition of n-heptane(porogen)was carried out for the fabrication of the porous polymer(PVD)microsphere as support,followed by the immobilization of sulfonic acid-functionalized ionic liquids by the successive treatment of benzimidazole(BIm),1,3-propane sultone and sulfuric acid(H2SO4)or trifluoromethanesulfonic acid(CF3SO3H).The effects of the compositions of DVB and n-heptane on the internal structure of the polymer supports were investigated,and it was found that the support with 40 wt%DVB and 60 wt%n-heptane(with relative to the monomer)could endow the final PSILs with the relatively optimal catalytic performance.The preliminary experiment in the batch reactor indicated that PSILs herein exhibited higher catalytic activities than commercial Amberlyst 46 resin for the esterification of propanoic acid(PROAc)with n-propanol(PROOH).Consequently,the optimal PSILs catalyst,PVD-[Bim-SO3H]HSO4,was selected for further study in the batch reactive distillation column because of low cost and its ease of preparation.The yield of propyl ropionate(PROPRO)could reach up to 97.78%at the optimized conditions of PROOH/PROAc molar ratio(2:1)and catalyst dosage(2.0 wt%).The investigation of the reaction kinetic manifested that the calculated results of second order pseudo-homogeneous kinetic model were in good agreement with experimental values.The pre-exponential factor and activation energy were 4.12×107 L·mol-1·min-1 and 60.57 k J·mol-1,respectively.It is worth noting that the PSILs catalyst could be simply recovered and reused with relatively satisfactory decrease in the catalytic activity,which made it an environmental friendly and promising catalyst in the industrial application.
基金Supported by the Natural Science Key Project of the Jiangsu Higher Education Institutions(15KJA220001)Jiangsu Province Six Talent Peaks Project(2016-XCL-043)+1 种基金the Young Natural Science Foundation of Jiangsu Province(BK20170918)the National Natural Science Foundation of China(NNSFC 21706134)
文摘Utilization of biomass-derived materials or chemicals plays a significant role in reducing the dependence of unsustainable resources of petroleum and coal. A series of sulfonated glucose-derived solid acids(SGSAs) were developed in this study through a one-step method. These catalysts were characterized by XRD, FT-IR, SEM,and BET to determine their physiochemical properties, and their acid content was measured by acid–base titration. The catalytic performances of SGSA catalysts were evaluated in two esterification reactions: propionic acid or oleic acid with methanol(a typical reaction to upgrade biodiesel). Conversion of oleic acid and selectivity of methyl oleate can reach as high as 93.3% and 94.7% respectively over SGSA-6, which has the highest -SO3 H density. Moreover, regeneration of spent catalysts by sulfuric acid solution can significantly enhance their stability and reusability.
文摘Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indium reagent, in many cases. Based on this method of methyl esterification of benzaldehyde derivatives, we further explored an application to heterocyclic aldehydes. The reactions were examined using methanol as well as other alcohols in order to establish a suitable range.
基金the financial support for this work from the National Natural Science Foundation of China(No.21706034)the Guiding Project of Fujian Province(No.2018H0016)+1 种基金the Open Foundation of State Key Laboratory of Chemical Engineering(No.SKL-ChE-18B02)the Integration of Industry,Education and Research of Fujian Province(No.2018Y4008).
文摘Producing 2-ethyl-1-hexyl thioglycolate(ETE)via esterification reaction with thioglycolic acid(TGA)aqueous solution as raw material by reactive-separation coupling technology is a promising process intensification method.To choose suitable reactive-separation coupling strategy,the kinetic studies of the esterification of TGA with 2-ethyl-1-hexanol(EHL)were carried out in a batch system.The commercial ion exchange resin was employed as an eco-friendly catalyst.The effects of temperature,catalyst concentration and molar ratio were determined.It was interesting to observe that the equilibrium conversion of TGA increased with the increase of catalyst mass fraction due to the adsorption of product water onto resin surface.The activity-based pseudo-homogeneous(PH),Eley-Rideal(ER)and Langmuir-Hinshelwood-Ho ugen-Watson(LHHW)models were used to fit the kinetics data of the resin-catalyzed reaction.The models of ER and LHHW performed better than the PH model.The kinetics of the TGA-self-catalyzed reaction was also determined.An activity-based homogeneous kinetics model could well describe this self-catalyzed reaction.These results would be meaningful to the selection and design of an appropriate reactionseparation strategy for the production of ETE,to realize the process intensification.
