A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition(180 210 C)catalyzed by extremely low concentration sulfuric acid(0.01 mol/L)and the product isolation were dev...A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition(180 210 C)catalyzed by extremely low concentration sulfuric acid(0.01 mol/L)and the product isolation were developed in this study.Effects of different process variables towards the catalytic performance were performed as a function of reaction time.The results indicated that sulfuric acid concentration,temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate.An optimized yield of around 50%was achieved at 210 C for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L.The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n-dodecane was added to help distill the heavy fraction.The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate.The chemical composition and structural of lower heavy fraction were characterized by GC/MS,FTIR,1H-NMR and13C-NMR techniques.Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%.This pathway is efficient,environmentally benign and economical for the production of pure levulinate esters from cellulose.展开更多
Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesi...Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesis of n-butyl levulinate by esterification of levulinic acid with n-butanol using heteropolyacid （HPA） supported on acid-treated clay montmorillonite （K10）. 20% （w/w） dodecatungestophosphoric acid （DTPA） supported on K10 was found to be the most efficient catalyst with 97% levulinic acid conversion and 100% selectivity towards n-butyl levulinate. Effects of various process parameters were studied to examine the efficacy of 20% （w/w） DTPA/K10 for optimization of the activity.展开更多
Butyl levulinate（BL） is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the cat...Butyl levulinate（BL） is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the catalysis of metal sulfates was developed. The catalytic activity of a series of metal sulfates for the synthesis of BL from fructose was investigated. Among various metal sulfates, ferric sulfate Fe（SO）was found to be the most efficient catalyst, which gave a remarkably high BL yield of 62.8 mol% under the conditions of 463 K, 3 h, a catalyst dosage of 5.0 g/L, and fructose concentration of 25 g/L. Different carbohydrates including glucose, cellulose, inulin and sucrose were also used for one-pot synthesis of BL with the catalysis of Fe（SO）, showing the yields of 39.6, 30.5, 56.6 and 50.1 mol%, respectively. In addition,the recycling and reuse of Fe（SO）was studied by characterizing them using powder X-ray diffraction（XRD）, scanning electron microscope（SEM）, X-ray photoelectron spectroscopy（XPS）. A plausible reaction pathway for the one-pot synthesis of BL from fructose was proposed. This study provides a facile and feasible way for the synthesis of BL from biomass.展开更多
A series of metal salt-modified carbon catalysts had been prepared to study the selective transformation of various carbohydrates into ethyl levulinate in an ethanol medium. The specific textural and chemical characte...A series of metal salt-modified carbon catalysts had been prepared to study the selective transformation of various carbohydrates into ethyl levulinate in an ethanol medium. The specific textural and chemical characteristics of prepared carbon samples were identified by Raman, XRD, XPS, NH;-TPD, FT-IR and nitrogen physisorption. Various parameters such as ethanol/water volume ratio, Na Cl addition, reaction temperature, and catalyst dosage played a great role in ethyl levulinate production. A desirable ethyl levulinate yield of 58.0 mol% with a highest ROF（rate of ethyl levulinate formation per gram of catalyst per hour） value of 2148.3 μmol/(g;·h) was achieved at 468 K over FeCl;modified carbon catalyst with respect to fructose conversion. The recycling experiments revealed that the sulfonated carbon catalysts exhibited relatively satisfied activity and stability.展开更多
Furfural is directly converted to levulinate esters（isopropyl levulinate and furan-2-ylmethyl-levulinate） as potential biofuel feedstocks, through a combined catalytic strategy. Nb;O;-ZrO;mixed oxide microspheres ar...Furfural is directly converted to levulinate esters（isopropyl levulinate and furan-2-ylmethyl-levulinate） as potential biofuel feedstocks, through a combined catalytic strategy. Nb;O;-ZrO;mixed oxide microspheres are used as bifunctional catalysts for hydrogen-transfer hydrogenation and acid-catalyzed alcoholysis in isopropanol. Bifunctional catalysts improve sustainability of furfural conversion through process intensification. Hydrogen transfer hydrogenation from isopropanol avoids dangerous hydrogen gas, and abates process and environmental costs. Isopropyl levulinate and furan-2-ylmethyl-levulinate are the main products that can be applied as blending components in biodiesel or hydrocarbon fuels.展开更多
The production of?-valerolactone(GVL)from lignocellulosic biomass has become a focus of research owing to its potential applications in fuels and chemicals.In this study,(n)CuOx-CaCO3(where n is the molar ratio of Cu ...The production of?-valerolactone(GVL)from lignocellulosic biomass has become a focus of research owing to its potential applications in fuels and chemicals.In this study,(n)CuOx-CaCO3(where n is the molar ratio of Cu to Ca)compounds were prepared for the first time and shown to function as efficient bifunctional catalysts for the conversion of biomass-derived methyl levulinate(ML)into GVL,using methanol as the in-situ hydrogen source.Among the catalysts with varied Cu/Ca molar ratios,(3/2)CuOx-CaCO3 provided the highest GVL yield of 95.6% from ML.The incorporation of CaCO3 with CuO resulted in the formation of Cu+species in a CuOx-CaCO3 catalyst,which greatly facilitated the hydrogenation of ML.Notably,CuOx-CaCO3 also displayed excellent catalytic performance in the methanolysis products of cellulose,even in the presence of humins.Therefore,a facile two-step strategy for the production of GVL from cellulose could be developed over this robust and inexpensive catalyst,through the integration of cellulose methanolysis catalyzed by sulfuric acid,methanol reforming,and ML hydrogenation in methanol medium.展开更多
The present study highlighted the use of modified H-ZSM-5 （Meso-HZ-5） as heterogeneous catalyst for the synthesis of octyl levulinate biolubricant by catalytic esterification of biomass derived renewable levulinic a...The present study highlighted the use of modified H-ZSM-5 （Meso-HZ-5） as heterogeneous catalyst for the synthesis of octyl levulinate biolubricant by catalytic esterification of biomass derived renewable levulinic acid （LA） with n-octanol. The process variables such as catalyst loading （X1）, n-octanol to LA molar ratio （X2） and reaction temperature （X3） were optimized through response surface methodology （RSM）, using Box-Behnken model. Analysis of variance was performed to determine the adequacy and significance of the quadratic model. The yield of octyl levulinate was obtained to be 99% at optimum process parameters. The developed quadratic model was found to be adequate and statistically accurate with correlation value （R2） of 0.9971 to predict the yield of octyl levulinate biolubricant. The study was also extended on the validation of theoretical and experimental data, including catalyst reusability.展开更多
Methyl levulinate(ML)is a promising green candidate for bio-based diesel fuel and fuel additives.An efficient enzyme-catalyzed process to synthesize ML from levulinic acid(LA)in methanol was developed.The catalytic ac...Methyl levulinate(ML)is a promising green candidate for bio-based diesel fuel and fuel additives.An efficient enzyme-catalyzed process to synthesize ML from levulinic acid(LA)in methanol was developed.The catalytic activity of a series of lipases including Novozyme 435(N435),NRTL IM,and 40086 was screened,and the N435 was identified as the optimal biocatalyst for the process.The effects of lipase amount,methyl tert-butyl ether(MTBE)volume,methanol to LA molar ratio,reaction temperature,and magnetic stirrer speed on LA conversion and ML yield were investigated.The response surface methodology was adopted to optimize the enzymatic conversion process,and the model validation experiments showed that the predicted values corresponded well with the experimental values.A LA conversion of 90.1%and a ML yield of 89.8%were achieved under reaction conditions covering:a temperature of 45°C,a reaction time of 4.6 h,a N435 dosage of 26 mg,a methanol to LA molar ratio of 3.6:1,a MTBE volume of 3.85 mL,and a stirrer speed of 150 r/min.The N435 recycling experiment indicated that the lipase activity was quite high after 12 cycles.However,upon using crude LA prepared from carbohydrates as the reactant,the conversion of LA and the ML yield decreased due to impurities existing in the crude LA.展开更多
Levulinate esters are versatile chemicals that have been used in various fields. Herein, the production of ethyl levulinate（EL） from corn stover was investigated under microwave irradiation. Several reaction paramet...Levulinate esters are versatile chemicals that have been used in various fields. Herein, the production of ethyl levulinate（EL） from corn stover was investigated under microwave irradiation. Several reaction parameters, including acid concentration, reaction temperature, reaction time, and liquid-to-solid mass ratio, were investigated to evaluate the reaction conditions. Response surface methodology（RSM） was employed to optimize the reaction conditions for the production of EL. A quadratic polynomial model was fitted to the data with an R2 value of 0.93. The model validation results reflected a good fit between the experimental and predicted values. A high conversion yield（58.1 mol%） was obtained at the optimum conditions of 190℃, 30.4 min, 2.84 wt% acid, and 15 g/g liquid-to-solid mass ratio. Compared with conventional heating, microwave irradiation facilitated the conversion of corn stover to EL by dramatically shortening the reaction time from several hours to ～30 min. Thus, microwave-assisted conversion of corn stover to EL is an efficient way of utilizing a renewable biomass resource.展开更多
Ultrasound-assisted pretreatment under mild operating conditions has been investigated for intensification of delignification to facilitate the obtaining of ethyl levulinate from biomass. The effect of pH (2 - 12), te...Ultrasound-assisted pretreatment under mild operating conditions has been investigated for intensification of delignification to facilitate the obtaining of ethyl levulinate from biomass. The effect of pH (2 - 12), temperature (30°C - 70°C) and pretreatment time (0 - 120 minutes) has been studied for different biomass samples. The most favorable conditions were basic pH, temperature of 70°C and pretreatment time of 2 h, obtaining values of delignification near 80 percent. The ethyl levulinate is obtained in microwave directly via from samples before and after delignification and analyzed for GC-MS. The results evidenced better yields for the delignified samples.展开更多
In this study,sulfonic acid-functionalized lignin-montmorillonite complex(LMT-SO_(3)H)was pre-pared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid(LA)into n-butyl levulina...In this study,sulfonic acid-functionalized lignin-montmorillonite complex(LMT-SO_(3)H)was pre-pared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid(LA)into n-butyl levulinate(BL).An intermediate pseudo-butyl levulinate(p-BL)was determined by distilled water treatment and nuclear magnetic resonance(NMR)analysis,and a possible mech-anism for the esterification of LA is proposed.The effects of various process parameters were studied and the results showed that the LMT-SO_(3)H catalyst had the excellent catalytic perfor-mance for esterification of the LA.Under optimum reaction conditions,the yield of BL was 99.3%and the conversion of LA was 99.8%.The LMT-SO_(3)H catalyst exhibited strong acidic sites and high stability even after seven cycles of usage.Furthermore,esterification of the LA with various alcohols over the LMT-SO_(3)H was further investigated.展开更多
This work presents the formation of butyl levulinate,a potential fuel additive,and an excellent renewable chemical obtained by the butanolysis of furfuryl alcohol(FAL)over a solid acid catalyst.The butanolysis of furf...This work presents the formation of butyl levulinate,a potential fuel additive,and an excellent renewable chemical obtained by the butanolysis of furfuryl alcohol(FAL)over a solid acid catalyst.The butanolysis of furfuryl alcohol reaction is a strong function of acidity for which tungstated zirconia(WO_(3)-ZrO_(2)),a robust solid acid catalyst,and a sulfonated carbon catalyst were employed to produce high yields of butyl levulinate targeting a lower initial molar ratio of butanol to FAL.A maximum of 28 mol%yield of butyl levulinate was obtained with tungstated zirconia catalyst.Easily prepared sulfonated carbon catalyst at high reaction temperatures facilitated the complete conversion of reaction intermediate,2-butoxymethylfuran(2-BMF)through which butyl levulinate was formed,and as high as 80 mol%of butyl levulinate yield was produced at an initial mole ratio of 8.5:1 of butanol to FAL.The better results of sulfonated carbon catalyst could be attributed to the presence of-SO3H,carboxylic acid,and phenolic OH groups on the carbon surface.展开更多
The carbon reduction effect of bio-based levulinic acid chemicals is a matter of concern.This work reports the life cycle assessment of methyl levulinate based on local biomass refineries in China.The final LCA result...The carbon reduction effect of bio-based levulinic acid chemicals is a matter of concern.This work reports the life cycle assessment of methyl levulinate based on local biomass refineries in China.The final LCA results showed that the entire life cycle of methyl levulinate could reduce by approximately 24%of carbon emissions compared with fossil diesel of equal quality.To address the lack of effective uncertainty analysis in current LCA research on levulinic acid chemicals,this study conducted a comprehensive and detailed assessment of inventory data and utilized Taylor series expansion to obtain uncertainty of the LCA results.When connected to a localized background database,the LCA results showed high credibility.According to the sensitivity analysis and Aspen optimization results,further technical improvement schemes are proposed,including improving thermal efficiency,use of clean electricity,and use of clean methanol.Prospective analysis shows that combined implementation of the above strategies can further reduce the existing carbon emissions by more than half.展开更多
Ethyl levulinate(EL)is a key biomass-derived compounds due to its socio-economic benefits for the synthesis of commodity chemicals.Herein,we proposed an efficient one-step bamboo conversion to EL in ethanol,and a nove...Ethyl levulinate(EL)is a key biomass-derived compounds due to its socio-economic benefits for the synthesis of commodity chemicals.Herein,we proposed an efficient one-step bamboo conversion to EL in ethanol,and a novel stepwise fractionation to purify EL and lignocellulose degradation products.A proton acid,due to its high catalytic efficiency,yielded 26.65%EL in 120 min at 200℃.The productions of ethyl glucoside and 5-ethoxymethylfurfural were analyzed in terms of by-products formation.To the best of our knowledge,there is no single report on catalyst for one step synthesis of EL directly from bamboo,as well as a stepwise fractionation to purify EL.Due to similar physiochemical properties in each fraction,the platform molecules could broaden a new paradigm of bamboo biomass utilization for renewable energy and value-added biochemicals.In addition,glucose,ethyl glucoside,corn starch,and microcrystalline cellulose were also investigated as substrates,so that the reaction intermediates of this one-pot procedure were identified and a possible reaction mechanism was proposed.展开更多
The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previou...The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previous studies but always required complex synthetic method or harsh reaction conditions.In this work,biomass-derived chitosan was used to prepare nitrogen doped carbon.After the loading of Ru,the Ru/NC(NC:nitrogen-doped carbon)catalyst was employed in the solvent-free hydrogenation of levulinic acid under ambient hydrogen pressure at 50−80℃ to reach full conversion.The calcination temperature was optimized to get Ru/NC-800 catalyst with high intrinsic turnover frequency of 358 h^(−1).The apparent activation energy was studied by kinetic experiments.More significantly,the catalyst was small-scaled tested for 36 h in a fix-bed reactor with 620 g/day productivity of γ-valerolactone.The catalyst can be easily synthesized and have high activity and stability,underscoring the potential of future commercial production of γ-valerolactone from levulinic acid.展开更多
Valorization of renewable cellulose into initial platform chemicals(IPCs)generally suffers from low process efficiency owing to difficult depolymerization of recalcitrant cellulose and troublesome repolymerization of ...Valorization of renewable cellulose into initial platform chemicals(IPCs)generally suffers from low process efficiency owing to difficult depolymerization of recalcitrant cellulose and troublesome repolymerization of high-reactive intermediates to undesired humins.Herein,we report a double-protective strategy for cellulose depolymerization and orientated conversion to levulinic acid(LA),one of the important IPCs,by in-situ adding protective formaldehyde(HCHO).This approach initiates from the(hemi)acetalation of hydroxyl groups in cellulose with HCHO,causing controllable depolymerization to(hemi)acetalized glucose with increased rate kinetically and a new mechanism of its catalytic conversion to LA via(hemi)acetal-driven direct C1-C2 cleavage.As such,the cellulose-to-LA conversion is protectively proceeded with the repolymerization of reactive intermediates prevented remarkably,leading to an excellent LA yield of 87.3 mol% from high-loading microcrystalline cellulose(15.0 wt% in aqueous phase)in a biphasic solvent containing 2-methyltetrahydrofuran and water.The process efficiency,expressed as space-time yield,is improved by 3.6 fold when compared with a non-protective approach.This work highlights an advance in maximizing the utilization of biomass-derived carbons for high-efficiency production of important IPCs directly from cellulose for future biorefinery.展开更多
Effects of Zr/Ti molar ratio in SO42-/ZrO2-TiO2 solid acid catalyst calcined at different temperatures on its surface properties and catalytic activity were thoroughly investigated in this paper. The physicochemical c...Effects of Zr/Ti molar ratio in SO42-/ZrO2-TiO2 solid acid catalyst calcined at different temperatures on its surface properties and catalytic activity were thoroughly investigated in this paper. The physicochemical characteristics of prepared samples were determined by N2 adsorptiondesorption, XRD, NH3-TPD and XPS techniques, respectively. It was found that the crystallization temperature of the samples increased after the combination of ZrO2 and TiO2; and phase transformations from the anatase to the rutile of TiO2 species and the tetragonal to the monoclinic of ZrO2 species were effectively suppressed at higher temperature. The sample with a Zr/Ti molar ratio of 3/1 calcined at 450℃ showed the highest surface area and the most acid sites among all the tested samples. The acid site densities of samples were relatively closed to each other if they were calcined at the same temperature, however, decreased with the calcination temperature. The result indicates that the sulfur content in samples is a crucial factor to control the acid site density. Calcining the sample at 650℃ and higher temperatures resulted in a significant desorption of sulfate ion on the samples. The synthesized samples were evaluated as a potential catalyst for glucose conversion under the near-critical methanol conditions （200℃/4 MPa）. The results suggested that the relatively weaker acid sites of the catalyst were more favorable for the accumulation of methyl glucosides, while the moderate acid sites were responsible for the formation of methyl levulinate. The catalytic activity for methyl levulinate production almost increases linearly with the catalyst acid site density. The catalyst deactivation is due to the loss of sulfate ion and the two catalysts with Zr/Ti molar ratios of 3/1 and 1/3 could effectively alleviate the deactivation caused by sulfate solution in the reaction medium and can be reused after calcination with the reuse rate of over 90% in terms of the methyl levulinate selectivity.展开更多
The kinetics for production of ethyl levulinate from glucose in ethanol medium was investigated. The experiments were performed in various temperatures （433-473 K） and initial glucose concentrations （0.056-0.168 mo...The kinetics for production of ethyl levulinate from glucose in ethanol medium was investigated. The experiments were performed in various temperatures （433-473 K） and initial glucose concentrations （0.056-0.168 mol·L-1） with extremely low sulfuric acid as the catalyst. The results show that higher temperature can improve the conversion of glucose to ethyl levulinate, with higher yield of ethyl levulinate （44.79%, by mole） obtained at 473 K for 210 min. The kinetics follows a simplified first-order kinetic model. For the main and side reactions, the values of activation energy are 122.64 and 70.97 kJ·mo1-1, and the reaction orders are 0.985 and 0.998, respectively.展开更多
Conversion of biomass to chemicals or fuels under mild condition is still a challenge. As a platform molecule for chemicals and fuels, levulinic acid （LA） has been prepared by lique-faction of biomass at high pressu...Conversion of biomass to chemicals or fuels under mild condition is still a challenge. As a platform molecule for chemicals and fuels, levulinic acid （LA） has been prepared by lique-faction of biomass at high pressure. In order to carry out the conversion from wheat straw to LA at atmosphere pressure, continuous extraction of the reactive system by an organic solvent with a higher density than that of water was utilized for degradation of pretreated biomass. Yields of LA were measured by means of gas chromatography-mass spectrometry and nuclear magnetic resonance. The results revealed that a maximum yield of 30.66% of LA can be obtained from wheat straw. In addition, the effects of biomass pretreated conditions on the LA conversion have been studied. The study provides a new route to convert biomass to valuable chemicals at atmosphere pressure.展开更多
The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylf...The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylfurfural （5-HMF） and levulinic acid （LA）. The decomposition kinetics of 5-HMF and stability of LA in HTLW were further investigated. A kinetic model for glucose decomposition was proposed accordingly. In the model, a series of first-order reactions with the consideration of parallel by-reactions were used to illustrate the decomposition of glucose. The decomposition activation energies of glucose, 5-HMF, and LA were evaluated as 118.85, 95.40, and 31.29 kJ·mol^-1, respectively.展开更多
基金supported by the National Key Basic Research Program (2010CB732201) from the Ministry of Science and Technology of Chinathe State Key Laboratory Open Foundation of Pulp and Paper Engineering of China (201225)
文摘A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition(180 210 C)catalyzed by extremely low concentration sulfuric acid(0.01 mol/L)and the product isolation were developed in this study.Effects of different process variables towards the catalytic performance were performed as a function of reaction time.The results indicated that sulfuric acid concentration,temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate.An optimized yield of around 50%was achieved at 210 C for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L.The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n-dodecane was added to help distill the heavy fraction.The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate.The chemical composition and structural of lower heavy fraction were characterized by GC/MS,FTIR,1H-NMR and13C-NMR techniques.Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%.This pathway is efficient,environmentally benign and economical for the production of pure levulinate esters from cellulose.
基金S. Dharne thanks Director, NCL, Pune for permission to workas an M. E. (Chemical Engineering) project trainee
文摘Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesis of n-butyl levulinate by esterification of levulinic acid with n-butanol using heteropolyacid （HPA） supported on acid-treated clay montmorillonite （K10）. 20% （w/w） dodecatungestophosphoric acid （DTPA） supported on K10 was found to be the most efficient catalyst with 97% levulinic acid conversion and 100% selectivity towards n-butyl levulinate. Effects of various process parameters were studied to examine the efficacy of 20% （w/w） DTPA/K10 for optimization of the activity.
基金financially supported by the National Natural Science Foundation of China (nos.21176227 and U1404519)
文摘Butyl levulinate（BL） is a promising new candidate as diesel fuel and fuel additive. In this study, an efficient process for a one-pot synthesis of BL from biomass-derived carbohydrates in butanol medium with the catalysis of metal sulfates was developed. The catalytic activity of a series of metal sulfates for the synthesis of BL from fructose was investigated. Among various metal sulfates, ferric sulfate Fe（SO）was found to be the most efficient catalyst, which gave a remarkably high BL yield of 62.8 mol% under the conditions of 463 K, 3 h, a catalyst dosage of 5.0 g/L, and fructose concentration of 25 g/L. Different carbohydrates including glucose, cellulose, inulin and sucrose were also used for one-pot synthesis of BL with the catalysis of Fe（SO）, showing the yields of 39.6, 30.5, 56.6 and 50.1 mol%, respectively. In addition,the recycling and reuse of Fe（SO）was studied by characterizing them using powder X-ray diffraction（XRD）, scanning electron microscope（SEM）, X-ray photoelectron spectroscopy（XPS）. A plausible reaction pathway for the one-pot synthesis of BL from fructose was proposed. This study provides a facile and feasible way for the synthesis of BL from biomass.
基金supported by the Natural Science Foundation of Guangdong Province, China (2014A030310386, 2016A030313173, 2015A030312007)the National Natural Science Foundation of China (21472189)+2 种基金the National Basic Research Program of China (973 Program, 2012CB215304)Science and Technology Planning Project of Guangdong Province, China (2015A010106010)Open fund of Key Laboratory of Renewable Energy, Chinese Academy of Sciences (y507ja1001)
文摘A series of metal salt-modified carbon catalysts had been prepared to study the selective transformation of various carbohydrates into ethyl levulinate in an ethanol medium. The specific textural and chemical characteristics of prepared carbon samples were identified by Raman, XRD, XPS, NH;-TPD, FT-IR and nitrogen physisorption. Various parameters such as ethanol/water volume ratio, Na Cl addition, reaction temperature, and catalyst dosage played a great role in ethyl levulinate production. A desirable ethyl levulinate yield of 58.0 mol% with a highest ROF（rate of ethyl levulinate formation per gram of catalyst per hour） value of 2148.3 μmol/(g;·h) was achieved at 468 K over FeCl;modified carbon catalyst with respect to fructose conversion. The recycling experiments revealed that the sulfonated carbon catalysts exhibited relatively satisfied activity and stability.
基金supported by the National Natural Science Foundation of China (21403248, 21174148, 21101161, and 21304101)
文摘Furfural is directly converted to levulinate esters（isopropyl levulinate and furan-2-ylmethyl-levulinate） as potential biofuel feedstocks, through a combined catalytic strategy. Nb;O;-ZrO;mixed oxide microspheres are used as bifunctional catalysts for hydrogen-transfer hydrogenation and acid-catalyzed alcoholysis in isopropanol. Bifunctional catalysts improve sustainability of furfural conversion through process intensification. Hydrogen transfer hydrogenation from isopropanol avoids dangerous hydrogen gas, and abates process and environmental costs. Isopropyl levulinate and furan-2-ylmethyl-levulinate are the main products that can be applied as blending components in biodiesel or hydrocarbon fuels.
基金supported by the National Natural Science Foundation of China(21676223,21706223,21776234,21606188)the Fundamental Research Funds for the Central Universities(20720180084),the Energy development Foundation of Energy College,Xiamen University(2017NYFZ02)+1 种基金the Natural Science Foundation of Fujian Province of China(2018J01017)the Education Department of Fujian Province(JZ160398)~~
文摘The production of?-valerolactone(GVL)from lignocellulosic biomass has become a focus of research owing to its potential applications in fuels and chemicals.In this study,(n)CuOx-CaCO3(where n is the molar ratio of Cu to Ca)compounds were prepared for the first time and shown to function as efficient bifunctional catalysts for the conversion of biomass-derived methyl levulinate(ML)into GVL,using methanol as the in-situ hydrogen source.Among the catalysts with varied Cu/Ca molar ratios,(3/2)CuOx-CaCO3 provided the highest GVL yield of 95.6% from ML.The incorporation of CaCO3 with CuO resulted in the formation of Cu+species in a CuOx-CaCO3 catalyst,which greatly facilitated the hydrogenation of ML.Notably,CuOx-CaCO3 also displayed excellent catalytic performance in the methanolysis products of cellulose,even in the presence of humins.Therefore,a facile two-step strategy for the production of GVL from cellulose could be developed over this robust and inexpensive catalyst,through the integration of cellulose methanolysis catalyzed by sulfuric acid,methanol reforming,and ML hydrogenation in methanol medium.
基金supported by CSIR-XII FYP Networking Project BLB
文摘The present study highlighted the use of modified H-ZSM-5 （Meso-HZ-5） as heterogeneous catalyst for the synthesis of octyl levulinate biolubricant by catalytic esterification of biomass derived renewable levulinic acid （LA） with n-octanol. The process variables such as catalyst loading （X1）, n-octanol to LA molar ratio （X2） and reaction temperature （X3） were optimized through response surface methodology （RSM）, using Box-Behnken model. Analysis of variance was performed to determine the adequacy and significance of the quadratic model. The yield of octyl levulinate was obtained to be 99% at optimum process parameters. The developed quadratic model was found to be adequate and statistically accurate with correlation value （R2） of 0.9971 to predict the yield of octyl levulinate biolubricant. The study was also extended on the validation of theoretical and experimental data, including catalyst reusability.
基金This work was supported by the Natural Science Foundation of China(U1904122)the Program of Processing and Efficient Utilization of Biomass Resources of Henan Center for Outstanding Overseas Scientists(GZS2018004).
文摘Methyl levulinate(ML)is a promising green candidate for bio-based diesel fuel and fuel additives.An efficient enzyme-catalyzed process to synthesize ML from levulinic acid(LA)in methanol was developed.The catalytic activity of a series of lipases including Novozyme 435(N435),NRTL IM,and 40086 was screened,and the N435 was identified as the optimal biocatalyst for the process.The effects of lipase amount,methyl tert-butyl ether(MTBE)volume,methanol to LA molar ratio,reaction temperature,and magnetic stirrer speed on LA conversion and ML yield were investigated.The response surface methodology was adopted to optimize the enzymatic conversion process,and the model validation experiments showed that the predicted values corresponded well with the experimental values.A LA conversion of 90.1%and a ML yield of 89.8%were achieved under reaction conditions covering:a temperature of 45°C,a reaction time of 4.6 h,a N435 dosage of 26 mg,a methanol to LA molar ratio of 3.6:1,a MTBE volume of 3.85 mL,and a stirrer speed of 150 r/min.The N435 recycling experiment indicated that the lipase activity was quite high after 12 cycles.However,upon using crude LA prepared from carbohydrates as the reactant,the conversion of LA and the ML yield decreased due to impurities existing in the crude LA.
基金financially supported by the National Key R&D Program of China(no.2016YFE0112800)National Natural Science Foundation of China(no.31671572)
文摘Levulinate esters are versatile chemicals that have been used in various fields. Herein, the production of ethyl levulinate（EL） from corn stover was investigated under microwave irradiation. Several reaction parameters, including acid concentration, reaction temperature, reaction time, and liquid-to-solid mass ratio, were investigated to evaluate the reaction conditions. Response surface methodology（RSM） was employed to optimize the reaction conditions for the production of EL. A quadratic polynomial model was fitted to the data with an R2 value of 0.93. The model validation results reflected a good fit between the experimental and predicted values. A high conversion yield（58.1 mol%） was obtained at the optimum conditions of 190℃, 30.4 min, 2.84 wt% acid, and 15 g/g liquid-to-solid mass ratio. Compared with conventional heating, microwave irradiation facilitated the conversion of corn stover to EL by dramatically shortening the reaction time from several hours to ～30 min. Thus, microwave-assisted conversion of corn stover to EL is an efficient way of utilizing a renewable biomass resource.
文摘Ultrasound-assisted pretreatment under mild operating conditions has been investigated for intensification of delignification to facilitate the obtaining of ethyl levulinate from biomass. The effect of pH (2 - 12), temperature (30°C - 70°C) and pretreatment time (0 - 120 minutes) has been studied for different biomass samples. The most favorable conditions were basic pH, temperature of 70°C and pretreatment time of 2 h, obtaining values of delignification near 80 percent. The ethyl levulinate is obtained in microwave directly via from samples before and after delignification and analyzed for GC-MS. The results evidenced better yields for the delignified samples.
基金the financial support of the National Natural Science Foundation of China(Nos.21606082,21776068 and 21975070)Hunan Provincial Natural Science Foundation of China(No.2018JJ3334),and China Postdoctoral Science Foundation(No.2019M662787).
文摘In this study,sulfonic acid-functionalized lignin-montmorillonite complex(LMT-SO_(3)H)was pre-pared and employed as an efficient heterogeneous catalyst for the esterification of levulinic acid(LA)into n-butyl levulinate(BL).An intermediate pseudo-butyl levulinate(p-BL)was determined by distilled water treatment and nuclear magnetic resonance(NMR)analysis,and a possible mech-anism for the esterification of LA is proposed.The effects of various process parameters were studied and the results showed that the LMT-SO_(3)H catalyst had the excellent catalytic perfor-mance for esterification of the LA.Under optimum reaction conditions,the yield of BL was 99.3%and the conversion of LA was 99.8%.The LMT-SO_(3)H catalyst exhibited strong acidic sites and high stability even after seven cycles of usage.Furthermore,esterification of the LA with various alcohols over the LMT-SO_(3)H was further investigated.
基金supported in part by Japan Science and Technology Agency Strategic International Collaborative Research Program(JST SICORP)Grant Number JPMJSC18H1,Japan.U.Rthe financial support by JICA IITH-FRIENDSHIP(D1956755)scholarship for suppoeting this study。
文摘This work presents the formation of butyl levulinate,a potential fuel additive,and an excellent renewable chemical obtained by the butanolysis of furfuryl alcohol(FAL)over a solid acid catalyst.The butanolysis of furfuryl alcohol reaction is a strong function of acidity for which tungstated zirconia(WO_(3)-ZrO_(2)),a robust solid acid catalyst,and a sulfonated carbon catalyst were employed to produce high yields of butyl levulinate targeting a lower initial molar ratio of butanol to FAL.A maximum of 28 mol%yield of butyl levulinate was obtained with tungstated zirconia catalyst.Easily prepared sulfonated carbon catalyst at high reaction temperatures facilitated the complete conversion of reaction intermediate,2-butoxymethylfuran(2-BMF)through which butyl levulinate was formed,and as high as 80 mol%of butyl levulinate yield was produced at an initial mole ratio of 8.5:1 of butanol to FAL.The better results of sulfonated carbon catalyst could be attributed to the presence of-SO3H,carboxylic acid,and phenolic OH groups on the carbon surface.
基金supported by the National Key R&D Program of China(2018YFB1501600).
文摘The carbon reduction effect of bio-based levulinic acid chemicals is a matter of concern.This work reports the life cycle assessment of methyl levulinate based on local biomass refineries in China.The final LCA results showed that the entire life cycle of methyl levulinate could reduce by approximately 24%of carbon emissions compared with fossil diesel of equal quality.To address the lack of effective uncertainty analysis in current LCA research on levulinic acid chemicals,this study conducted a comprehensive and detailed assessment of inventory data and utilized Taylor series expansion to obtain uncertainty of the LCA results.When connected to a localized background database,the LCA results showed high credibility.According to the sensitivity analysis and Aspen optimization results,further technical improvement schemes are proposed,including improving thermal efficiency,use of clean electricity,and use of clean methanol.Prospective analysis shows that combined implementation of the above strategies can further reduce the existing carbon emissions by more than half.
基金supported by National Science Foundation of China(No.32001274).
文摘Ethyl levulinate(EL)is a key biomass-derived compounds due to its socio-economic benefits for the synthesis of commodity chemicals.Herein,we proposed an efficient one-step bamboo conversion to EL in ethanol,and a novel stepwise fractionation to purify EL and lignocellulose degradation products.A proton acid,due to its high catalytic efficiency,yielded 26.65%EL in 120 min at 200℃.The productions of ethyl glucoside and 5-ethoxymethylfurfural were analyzed in terms of by-products formation.To the best of our knowledge,there is no single report on catalyst for one step synthesis of EL directly from bamboo,as well as a stepwise fractionation to purify EL.Due to similar physiochemical properties in each fraction,the platform molecules could broaden a new paradigm of bamboo biomass utilization for renewable energy and value-added biochemicals.In addition,glucose,ethyl glucoside,corn starch,and microcrystalline cellulose were also investigated as substrates,so that the reaction intermediates of this one-pot procedure were identified and a possible reaction mechanism was proposed.
基金financially supported by the National Natural Science Foundation of China (No.21905266)the Fundamental Research Funds for the Central Universities (WK3530000013)。
文摘The conversion of levulinic acid to γ-valerolactone is one of the most important reactions from biomass platform molecule to value-added chemicals.Rubased catalysts have shown high activity and selectivity in previous studies but always required complex synthetic method or harsh reaction conditions.In this work,biomass-derived chitosan was used to prepare nitrogen doped carbon.After the loading of Ru,the Ru/NC(NC:nitrogen-doped carbon)catalyst was employed in the solvent-free hydrogenation of levulinic acid under ambient hydrogen pressure at 50−80℃ to reach full conversion.The calcination temperature was optimized to get Ru/NC-800 catalyst with high intrinsic turnover frequency of 358 h^(−1).The apparent activation energy was studied by kinetic experiments.More significantly,the catalyst was small-scaled tested for 36 h in a fix-bed reactor with 620 g/day productivity of γ-valerolactone.The catalyst can be easily synthesized and have high activity and stability,underscoring the potential of future commercial production of γ-valerolactone from levulinic acid.
基金financially supported by the National Natural Science Foundation of China(No.22378277)111 Center(B17030)+1 种基金the Basal Research Fund of the Central University(2016SCU04B06)the technical support from the Analysis and Test Center of Sichuan University。
文摘Valorization of renewable cellulose into initial platform chemicals(IPCs)generally suffers from low process efficiency owing to difficult depolymerization of recalcitrant cellulose and troublesome repolymerization of high-reactive intermediates to undesired humins.Herein,we report a double-protective strategy for cellulose depolymerization and orientated conversion to levulinic acid(LA),one of the important IPCs,by in-situ adding protective formaldehyde(HCHO).This approach initiates from the(hemi)acetalation of hydroxyl groups in cellulose with HCHO,causing controllable depolymerization to(hemi)acetalized glucose with increased rate kinetically and a new mechanism of its catalytic conversion to LA via(hemi)acetal-driven direct C1-C2 cleavage.As such,the cellulose-to-LA conversion is protectively proceeded with the repolymerization of reactive intermediates prevented remarkably,leading to an excellent LA yield of 87.3 mol% from high-loading microcrystalline cellulose(15.0 wt% in aqueous phase)in a biphasic solvent containing 2-methyltetrahydrofuran and water.The process efficiency,expressed as space-time yield,is improved by 3.6 fold when compared with a non-protective approach.This work highlights an advance in maximizing the utilization of biomass-derived carbons for high-efficiency production of important IPCs directly from cellulose for future biorefinery.
基金supported by the National Key Basic Research Program (2010CB732201) from the Ministry of Science and Technology of Chinathe Natural Science Foundation of China (U0733001, 50776035)the Basic Research Foundation from the Ministry of Education for Universities (2010121077)
文摘Effects of Zr/Ti molar ratio in SO42-/ZrO2-TiO2 solid acid catalyst calcined at different temperatures on its surface properties and catalytic activity were thoroughly investigated in this paper. The physicochemical characteristics of prepared samples were determined by N2 adsorptiondesorption, XRD, NH3-TPD and XPS techniques, respectively. It was found that the crystallization temperature of the samples increased after the combination of ZrO2 and TiO2; and phase transformations from the anatase to the rutile of TiO2 species and the tetragonal to the monoclinic of ZrO2 species were effectively suppressed at higher temperature. The sample with a Zr/Ti molar ratio of 3/1 calcined at 450℃ showed the highest surface area and the most acid sites among all the tested samples. The acid site densities of samples were relatively closed to each other if they were calcined at the same temperature, however, decreased with the calcination temperature. The result indicates that the sulfur content in samples is a crucial factor to control the acid site density. Calcining the sample at 650℃ and higher temperatures resulted in a significant desorption of sulfate ion on the samples. The synthesized samples were evaluated as a potential catalyst for glucose conversion under the near-critical methanol conditions （200℃/4 MPa）. The results suggested that the relatively weaker acid sites of the catalyst were more favorable for the accumulation of methyl glucosides, while the moderate acid sites were responsible for the formation of methyl levulinate. The catalytic activity for methyl levulinate production almost increases linearly with the catalyst acid site density. The catalyst deactivation is due to the loss of sulfate ion and the two catalysts with Zr/Ti molar ratios of 3/1 and 1/3 could effectively alleviate the deactivation caused by sulfate solution in the reaction medium and can be reused after calcination with the reuse rate of over 90% in terms of the methyl levulinate selectivity.
基金Supported by the National Natural Science Foundation of China(21176227)the State Key Laboratory of Motor Vehicle Biofuel Technology(2013011)
文摘The kinetics for production of ethyl levulinate from glucose in ethanol medium was investigated. The experiments were performed in various temperatures （433-473 K） and initial glucose concentrations （0.056-0.168 mol·L-1） with extremely low sulfuric acid as the catalyst. The results show that higher temperature can improve the conversion of glucose to ethyl levulinate, with higher yield of ethyl levulinate （44.79%, by mole） obtained at 473 K for 210 min. The kinetics follows a simplified first-order kinetic model. For the main and side reactions, the values of activation energy are 122.64 and 70.97 kJ·mo1-1, and the reaction orders are 0.985 and 0.998, respectively.
文摘Conversion of biomass to chemicals or fuels under mild condition is still a challenge. As a platform molecule for chemicals and fuels, levulinic acid （LA） has been prepared by lique-faction of biomass at high pressure. In order to carry out the conversion from wheat straw to LA at atmosphere pressure, continuous extraction of the reactive system by an organic solvent with a higher density than that of water was utilized for degradation of pretreated biomass. Yields of LA were measured by means of gas chromatography-mass spectrometry and nuclear magnetic resonance. The results revealed that a maximum yield of 30.66% of LA can be obtained from wheat straw. In addition, the effects of biomass pretreated conditions on the LA conversion have been studied. The study provides a new route to convert biomass to valuable chemicals at atmosphere pressure.
基金Supported by the National Natural Science Foundation of China （20674068） and the Natural Science Foundation of Zhejiang Province （Y405157）.
文摘The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylfurfural （5-HMF） and levulinic acid （LA）. The decomposition kinetics of 5-HMF and stability of LA in HTLW were further investigated. A kinetic model for glucose decomposition was proposed accordingly. In the model, a series of first-order reactions with the consideration of parallel by-reactions were used to illustrate the decomposition of glucose. The decomposition activation energies of glucose, 5-HMF, and LA were evaluated as 118.85, 95.40, and 31.29 kJ·mol^-1, respectively.
