超低酸催化纤维素一锅法制取糠醛工艺优化
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摘要
5-乙氧基甲基糠醛(5-ethoxymethylfurfural,EMF)是一种新型液体生物燃料,具有较高的能量密度和优良的燃烧性能,被视为未来潜在的燃料替代物。该文利用酸质量为乙醇质量0.1%的硫酸催化纤维素与乙醇在高压反应釜中一锅法制取EMF。首先进行单因素试验,然后利用响应面Box-Behnken模型研究不同影响因素对超低酸催化纤维素制取EMF收率的影响,对EMF制取工艺条件进行优化。结果表明:在反应时间、反应温度和底物浓度3个影响因素中,反应时间对超低酸催化纤维素一锅法制取EMF收率影响最大。根据Box-Behnken模型获得最佳反应条件:反应温度200℃、反应时间75 min、底物浓度30 g/L进行试验验证,EMF实际平均收率为14.93%,与理论预测值相对误差为2.03%,说明该模型具有较好的预测性。该研究首次提出以超低酸催化纤维素直接制取EMF,并优化了超低酸催化纤维素制取EMF的工艺条件,可为成本低廉、产量丰富的纤维素生物质制取EMF提供借鉴和参考。
With the inevitable depletion of non-renewable petroleum resources and the rising environmental concerns, renewable biomass has been regarded as a potential resource for sustainable supply of biofuels. The development of simple, cheap and sustainable catalytic process for the production of biofuels has become a major target. Among the promising biofuels, EMF(5-ethoxymethylfurfural) has been considered as a new generation of biofuel or fuel additive due to its unique properties, such as its liquid characteristics under room temperature, non-toxicity, high lubricity, stable flashpoint and excellent flow properties under cold conditions. Recently, an increasing number of reports have been focused on the direct conversion of carbohydrates and platform chemicals such as 5-hydroxymethylfurfural(HMF), fructose, sucrose, or inulin into EMF catalyzed by different catalysts. However, from a point of view that raw materials are cheap and rich, it is more valuable to use cellulose or cellulosic biomass instead of model compounds, such as HMF and fructose, for the production of EMF. In the existing researches, cellulose was usually used as raw material to be converted into intermediate product HMF, 5-chloromethylfurfural(CMF) or 5-bromomethylfurfural(BMF), and so on, and then the target product EMF was obtained through the intermediate product. Using cheap and renewable cellulose as the raw material, and ethanol as the solvent, and combining the dehydration of cellulose to HMF, followed by the etherification of HMF to EMF in one-pot, is a more attractive reaction pathway. This one-pot reaction avoids the isolation and purification of HMF, which saves time, energy and solvent. The side reaction of process using extremely low sulfuric acid is slight, in which standard grade stainless steel facility can be used instead of high nickel alloy, which has a significant cost advantage in the equipment. In this paper, sulfuric acid with ultra low mass concentration(0.1% of the mass of ethanol) was used as catalyst to catalyze cellulose and ethanol to produce EMF in one-pot reaction. The effects of temperature, reaction time and substrate concentration on EMF yield were firstly studied and then the response surface methodology was used to design experiments to optimize the reaction conditions. The interactions of factors and the optimum reaction conditions were obtained. The results showed that the reaction temperature was the factor that mostly impacted the one-pot EMF production from cellulose and ethanol catalyzed by sulfuric acid with ultra low mass concentration. The maximum mean EMF yield of 14.93% was obtained under the optimum reaction conditions: reaction temperature of 200 ℃, reaction time of 75 min and substrate concentration of 30 g/L, with the prediction error of 2.03%, which showed that the model had a good fitting property. Compared to other studies, the study showed that EMF can be obtained directly from cellulose catalyzed by extremely low acid in one-pot reaction for the first time. The process conditions for producing EMF from cellulose catalyzed by extremely low acid in one-pot reaction had been optimized. This study can provide reference for the EMF one-pot production from much cheaper and abundant cellulosic biomass such as agricultural wastes catalyzed by sulfuric acid with extremely low concentration.
With the inevitable depletion of non-renewable petroleum resources and the rising environmental concerns, renewable biomass has been regarded as a potential resource for sustainable supply of biofuels. The development of simple, cheap and sustainable catalytic process for the production of biofuels has become a major target. Among the promising biofuels, EMF(5-ethoxymethylfurfural) has been considered as a new generation of biofuel or fuel additive due to its unique properties, such as its liquid characteristics under room temperature, non-toxicity, high lubricity, stable flashpoint and excellent flow properties under cold conditions. Recently, an increasing number of reports have been focused on the direct conversion of carbohydrates and platform chemicals such as 5-hydroxymethylfurfural(HMF), fructose, sucrose, or inulin into EMF catalyzed by different catalysts. However, from a point of view that raw materials are cheap and rich, it is more valuable to use cellulose or cellulosic biomass instead of model compounds, such as HMF and fructose, for the production of EMF. In the existing researches, cellulose was usually used as raw material to be converted into intermediate product HMF, 5-chloromethylfurfural(CMF) or 5-bromomethylfurfural(BMF), and so on, and then the target product EMF was obtained through the intermediate product. Using cheap and renewable cellulose as the raw material, and ethanol as the solvent, and combining the dehydration of cellulose to HMF, followed by the etherification of HMF to EMF in one-pot, is a more attractive reaction pathway. This one-pot reaction avoids the isolation and purification of HMF, which saves time, energy and solvent. The side reaction of process using extremely low sulfuric acid is slight, in which standard grade stainless steel facility can be used instead of high nickel alloy, which has a significant cost advantage in the equipment. In this paper, sulfuric acid with ultra low mass concentration(0.1% of the mass of ethanol) was used as catalyst to catalyze cellulose and ethanol to produce EMF in one-pot reaction. The effects of temperature, reaction time and substrate concentration on EMF yield were firstly studied and then the response surface methodology was used to design experiments to optimize the reaction conditions. The interactions of factors and the optimum reaction conditions were obtained. The results showed that the reaction temperature was the factor that mostly impacted the one-pot EMF production from cellulose and ethanol catalyzed by sulfuric acid with ultra low mass concentration. The maximum mean EMF yield of 14.93% was obtained under the optimum reaction conditions: reaction temperature of 200 ℃, reaction time of 75 min and substrate concentration of 30 g/L, with the prediction error of 2.03%, which showed that the model had a good fitting property. Compared to other studies, the study showed that EMF can be obtained directly from cellulose catalyzed by extremely low acid in one-pot reaction for the first time. The process conditions for producing EMF from cellulose catalyzed by extremely low acid in one-pot reaction had been optimized. This study can provide reference for the EMF one-pot production from much cheaper and abundant cellulosic biomass such as agricultural wastes catalyzed by sulfuric acid with extremely low concentration.
引文
[1]Zhang Zehui,Huber G W.Catalytic oxidation of carbohydrates into organic acids and furan chemicals[J].Chemical Society Reviews,2018,47(4):1351-1390.
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[3]Huang Yaobing,Yang Tao,Lin Yuting,et al.Facile and high-yield synthesis of methyl levulinate from cellulose[J].Green Chemistry,2018,20(6):1323-1334.
[4]Hu Lei,Lin Lu,Wu Zhen,et al.Recent advances in catalytic transformation of biomass-derived 5-hydroxymethylfurfural into the innovative fuels and chemicals[J].Renewable&Sustainable Energy Reviews,2017,74:230-257.
[5]Liu Anqiu,Liu Bing,Wang Yimei,et al.Efficient one-pot synthesis of 5-ethoxymethylfurfural from fructose catalyzed by heteropolyacid supported on K-10 clay[J].Fuel,2014,117:68-73.
[6]Liu Bing,Zhang Zehui,Huang Kecheng.Cellulose sulfuric acid as a bio-supported and recyclable solid acid catalyst for the synthesis of 5-hydroxymethylfurfural and 5-ethoxymethylfurfural from fructose[J].Cellulose.2013,20(4):2081-2089.
[7]Liu Anqiu,Zhang Zehui,Fang Zhongfeng,et al.Synthesis of5-ethoxymethylfurfural from 5-hydroxymethylfurfural and fructose in ethanol catalyzed by MCM-41 supported phosphotungstic acid[J].Journal of Industrial and Engineering Chemistry,2014,20:1977-1984.
[8]Xu Guizhuan,Chen Binglin,Zheng Zhangbin,et al.One-pot ethanolysis of carbohydrates to promising biofuels:5-ethoxymethylfurfural and ethyl levulinate:One-pot ethanolysis of carbohydrates to biofuels[J].Asia-Pacific Journal of Chemical Engineering,2017,12(4):527-535.
[9]Yuan Ziliang,Zhang Zehui,Zheng Judun,et al.Efficient synthesis of promising liquid fuels 5-ethoxymethylfurfural from carbohydrates[J].Fuel,2015,150:236-242.
[10]Chen Tao,Peng Lincai,Yu Xin,et al.Magnetically recyclable cellulose-derived carbonaceous solid acid catalyzed the biofuel5-ethoxymethylfurfural synthesis from renewable carbohydrates[J].Fuel,2018,219:344-352.
[11]Guo Haixin,Duereh A,Hiraga Y,et al.Perfect recycle and mechanistic role of hydrogen sulfate ionic liquids as additive in ethanol for efficient conversion of carbohydrates into5-ethoxymethylfurfural[J].Chemical Engineering Journal,2017,323:287-294.
[12]Kumari P K,Rao B S,Padmakar D,et al.Lewis acidity induced heteropoly tungustate catalysts for the synthesis of5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural[J].Molecular Catalysis,2018,448:108-115.
[13]Lew C M,Rajabbeigi N,Tsapatisis M.One-pot synthesis of5-(ethoxymethylfurfural)from glucose using Sn-BEA and amberlyst catalysts[J].Industrial&Engineering Chemistry Research,2012,51(14):5364-5366.
[14]Deng Lin,Chang Chun,An Ran,et al.Metal sulfatescatalyzed butanolysis of cellulose:Butyl levulinate production and optimization[J].Cellulose,2017,24(12):1-13.
[15]Bredihhin A,Maeorg U,Vares L.Evaluation of carbohydrates and lignocellulosic biomass from different wood species as raw material for the synthesis of 5-bromomethyfurfural[J].Carbohydrate Research,2013,375:63-67.
[16]Mascal M,Nikitin E B.Direct,high-yield conversion of cellulose into biofuel[J].Angewandte Chemie International Edition,2008,47(41):7924-7926.
[17]Mascal M,Nikitin E B.High-yield conversion of plant biomass into the key value-added feedstocks 5-(hydroxymethyl)furfural,levulinic acid,and levulinic esters via 5-(chloromethyl)furfural[J].Green Chemistry,2010,12(3):370-373.
[18]Xiao Shaohua,Liu Bing,Wang Yimei,et al.Efficient conversion of cellulose into biofuel precursor 5-hydroxymethylfurfural in dimethyl sulfoxide–ionic liquid mixtures[J].Bioresource Technology,2014,151:361-366.
[19]Xu Guizhuan,Chang Chun,Zhu Weina,et al.A comparative study on direct production of ethyl levulinate from glucose in ethanol media catalysed by different acid catalysts[J].Chemical Papers,2013,67(11):1355-1363.
[20]Yang Yu,Hu Changwei,Abu-Omar M M.Conversion of glucose into furans in the presence of Al Cl3 in an ethanolwater solvent system[J].Bioresource Technology,2012,116:190-194.
[21]Yin Shanshan,Sun Jie,Liu Bing,et al.Magnetic material grafted cross-linked imidazolium based polyionic liquids:an efficient acid catalyst for the synthesis of promising liquid fuel 5-ethoxymethylfurfural from carbohydrates[J].Journal of Materials Chemistry A,2015,3(9):4992-4999.
[22]Zhao Shiqiang,Xu Guizhuan,Chang Junli,et al.Direct production of ethyl levulinate from carbohydrates catalyzed by H-ZSM-5 supported phosphotungstic acid.[J].Bioresources,2015,10(2):2223-2234.
[23]Peng Lincai,Lin Lu,Li Hui.Extremely low sulfuric acid catalyst system for synthesis of methyl levulinate from glucose[J].Industrial Crops&Products,2012,40:136-144.
[24]Xu Guizhuan,Chang Chun,Fang Shuqi,et al.Cellulose reactivity in ethanol at elevate temperature and the kinetics of one-pot preparation of ethyl levulinate from cellulose[J].Renewable Energy,2015,78:583-589.
[25]Chang Chun,Xu Guizhuan,Zhu Weina,et al.One-pot production of a liquid biofuel candidate—Ethyl levulinate from glucose and furfural residues using a combination of extremely low sulfuric acid and zeolite USY[J].Fuel,2015,140:365-370.
[26]Peng Lincai,Lin Lu,Li Hui,et al.Acid-catalyzed direct synthesis of methyl levulinate from paper sludge in methanol medium[J].Bioresources,2013,8(4):5895-5907.
[27]Zuo Miao,Le Kai,Feng Yunchao,et al.An effective pathway for converting carbohydrates to biofuel 5-ethoxymethylfurfural via 5-hydroxymethylfurfural with deep eutectic solvents(DESs)[J].Industrial Crops&Products,2018,112:18-23.
[28]Sun Yingnan,Zhang Qingqing,Zhang Panpan,et al.Nitrogen-doped carbon-based acidic ionic liquid hollow nanospheres for efficient and selective conversion of fructose to 5-ethoxymethylfurfural and ethyl levulinate[J].ACS Sustainable Chemistry&Engineering,2018,6(5):6771-6782.
[29]Thombal R S,Jadhav V H.Application of glucose derived magnetic solid acid for etherification of 5-HMF to 5-EMF,dehydration of sorbitol to isosorbide,and esterification of fatty acids[J].Tetrahedron Letters,2016,57(39):4398-4400.
[30]Zhao Shiqiang,Xu Guizhuan,Chang Chun,et al.Direct conversion of carbohydrates into ethyl levulinate with potassium phosphotungstate as an efficient catalyst[J].Catalysts,2015,5(4):1897-1910.
[31]Wu Xiaoyu,Fu Jie,Lu Xiuyang.One-pot preparation of methyl levulinate from catalytic alcoholysis of cellulose in near-critical methanol[J].Carbohydrate Research,2012,358:37-39.
[32]Li Hu,Fang Zhen,Luo Jia,et al.Direct conversion of biomass components to the biofuel methyl levulinate catalyzed by acid-base bifunctional zirconia-zeolites[J].Applied Catalysis B Environmental,2017,200:182-191.
[33]Saravanamurugan S,Riisager A.Zeolite catalyzed transformation of carbohydrates to alkyl levulinates[J].Chemcatchem,2013,5(7):1754-1757.
[34]Rataboul F,Essayem N.Cellulose reactivity in supercritical methanol in the presence of solid acid catalysts:Direct synthesis of methyl-levulinate[J].Industrial&Engineering Chemistry Research,2011,50(2):699-704.
[35]Amarasekara A S,Wiredu B.Acidic ionic liquid catalyzed one-pot conversion of cellulose to ethyl levulinate and levulinic acid in ethanol-water solvent system[J].Bioenergy Research,2014,7(4):1237-1243.
[2]Bai Yuanyuan,Wei Lu,Yang Mengfei,et al.Three-step cascade over one single catalyst:Synthesis of 5-(ethoxymethyl)furfural from glucose over hierarchical lamellar multi-functional zeolite catalyst[J].Journal of Materials Chemistry A,2018,6(17):7693-7705.
[3]Huang Yaobing,Yang Tao,Lin Yuting,et al.Facile and high-yield synthesis of methyl levulinate from cellulose[J].Green Chemistry,2018,20(6):1323-1334.
[4]Hu Lei,Lin Lu,Wu Zhen,et al.Recent advances in catalytic transformation of biomass-derived 5-hydroxymethylfurfural into the innovative fuels and chemicals[J].Renewable&Sustainable Energy Reviews,2017,74:230-257.
[5]Liu Anqiu,Liu Bing,Wang Yimei,et al.Efficient one-pot synthesis of 5-ethoxymethylfurfural from fructose catalyzed by heteropolyacid supported on K-10 clay[J].Fuel,2014,117:68-73.
[6]Liu Bing,Zhang Zehui,Huang Kecheng.Cellulose sulfuric acid as a bio-supported and recyclable solid acid catalyst for the synthesis of 5-hydroxymethylfurfural and 5-ethoxymethylfurfural from fructose[J].Cellulose.2013,20(4):2081-2089.
[7]Liu Anqiu,Zhang Zehui,Fang Zhongfeng,et al.Synthesis of5-ethoxymethylfurfural from 5-hydroxymethylfurfural and fructose in ethanol catalyzed by MCM-41 supported phosphotungstic acid[J].Journal of Industrial and Engineering Chemistry,2014,20:1977-1984.
[8]Xu Guizhuan,Chen Binglin,Zheng Zhangbin,et al.One-pot ethanolysis of carbohydrates to promising biofuels:5-ethoxymethylfurfural and ethyl levulinate:One-pot ethanolysis of carbohydrates to biofuels[J].Asia-Pacific Journal of Chemical Engineering,2017,12(4):527-535.
[9]Yuan Ziliang,Zhang Zehui,Zheng Judun,et al.Efficient synthesis of promising liquid fuels 5-ethoxymethylfurfural from carbohydrates[J].Fuel,2015,150:236-242.
[10]Chen Tao,Peng Lincai,Yu Xin,et al.Magnetically recyclable cellulose-derived carbonaceous solid acid catalyzed the biofuel5-ethoxymethylfurfural synthesis from renewable carbohydrates[J].Fuel,2018,219:344-352.
[11]Guo Haixin,Duereh A,Hiraga Y,et al.Perfect recycle and mechanistic role of hydrogen sulfate ionic liquids as additive in ethanol for efficient conversion of carbohydrates into5-ethoxymethylfurfural[J].Chemical Engineering Journal,2017,323:287-294.
[12]Kumari P K,Rao B S,Padmakar D,et al.Lewis acidity induced heteropoly tungustate catalysts for the synthesis of5-ethoxymethyl furfural from fructose and 5-hydroxymethylfurfural[J].Molecular Catalysis,2018,448:108-115.
[13]Lew C M,Rajabbeigi N,Tsapatisis M.One-pot synthesis of5-(ethoxymethylfurfural)from glucose using Sn-BEA and amberlyst catalysts[J].Industrial&Engineering Chemistry Research,2012,51(14):5364-5366.
[14]Deng Lin,Chang Chun,An Ran,et al.Metal sulfatescatalyzed butanolysis of cellulose:Butyl levulinate production and optimization[J].Cellulose,2017,24(12):1-13.
[15]Bredihhin A,Maeorg U,Vares L.Evaluation of carbohydrates and lignocellulosic biomass from different wood species as raw material for the synthesis of 5-bromomethyfurfural[J].Carbohydrate Research,2013,375:63-67.
[16]Mascal M,Nikitin E B.Direct,high-yield conversion of cellulose into biofuel[J].Angewandte Chemie International Edition,2008,47(41):7924-7926.
[17]Mascal M,Nikitin E B.High-yield conversion of plant biomass into the key value-added feedstocks 5-(hydroxymethyl)furfural,levulinic acid,and levulinic esters via 5-(chloromethyl)furfural[J].Green Chemistry,2010,12(3):370-373.
[18]Xiao Shaohua,Liu Bing,Wang Yimei,et al.Efficient conversion of cellulose into biofuel precursor 5-hydroxymethylfurfural in dimethyl sulfoxide–ionic liquid mixtures[J].Bioresource Technology,2014,151:361-366.
[19]Xu Guizhuan,Chang Chun,Zhu Weina,et al.A comparative study on direct production of ethyl levulinate from glucose in ethanol media catalysed by different acid catalysts[J].Chemical Papers,2013,67(11):1355-1363.
[20]Yang Yu,Hu Changwei,Abu-Omar M M.Conversion of glucose into furans in the presence of Al Cl3 in an ethanolwater solvent system[J].Bioresource Technology,2012,116:190-194.
[21]Yin Shanshan,Sun Jie,Liu Bing,et al.Magnetic material grafted cross-linked imidazolium based polyionic liquids:an efficient acid catalyst for the synthesis of promising liquid fuel 5-ethoxymethylfurfural from carbohydrates[J].Journal of Materials Chemistry A,2015,3(9):4992-4999.
[22]Zhao Shiqiang,Xu Guizhuan,Chang Junli,et al.Direct production of ethyl levulinate from carbohydrates catalyzed by H-ZSM-5 supported phosphotungstic acid.[J].Bioresources,2015,10(2):2223-2234.
[23]Peng Lincai,Lin Lu,Li Hui.Extremely low sulfuric acid catalyst system for synthesis of methyl levulinate from glucose[J].Industrial Crops&Products,2012,40:136-144.
[24]Xu Guizhuan,Chang Chun,Fang Shuqi,et al.Cellulose reactivity in ethanol at elevate temperature and the kinetics of one-pot preparation of ethyl levulinate from cellulose[J].Renewable Energy,2015,78:583-589.
[25]Chang Chun,Xu Guizhuan,Zhu Weina,et al.One-pot production of a liquid biofuel candidate—Ethyl levulinate from glucose and furfural residues using a combination of extremely low sulfuric acid and zeolite USY[J].Fuel,2015,140:365-370.
[26]Peng Lincai,Lin Lu,Li Hui,et al.Acid-catalyzed direct synthesis of methyl levulinate from paper sludge in methanol medium[J].Bioresources,2013,8(4):5895-5907.
[27]Zuo Miao,Le Kai,Feng Yunchao,et al.An effective pathway for converting carbohydrates to biofuel 5-ethoxymethylfurfural via 5-hydroxymethylfurfural with deep eutectic solvents(DESs)[J].Industrial Crops&Products,2018,112:18-23.
[28]Sun Yingnan,Zhang Qingqing,Zhang Panpan,et al.Nitrogen-doped carbon-based acidic ionic liquid hollow nanospheres for efficient and selective conversion of fructose to 5-ethoxymethylfurfural and ethyl levulinate[J].ACS Sustainable Chemistry&Engineering,2018,6(5):6771-6782.
[29]Thombal R S,Jadhav V H.Application of glucose derived magnetic solid acid for etherification of 5-HMF to 5-EMF,dehydration of sorbitol to isosorbide,and esterification of fatty acids[J].Tetrahedron Letters,2016,57(39):4398-4400.
[30]Zhao Shiqiang,Xu Guizhuan,Chang Chun,et al.Direct conversion of carbohydrates into ethyl levulinate with potassium phosphotungstate as an efficient catalyst[J].Catalysts,2015,5(4):1897-1910.
[31]Wu Xiaoyu,Fu Jie,Lu Xiuyang.One-pot preparation of methyl levulinate from catalytic alcoholysis of cellulose in near-critical methanol[J].Carbohydrate Research,2012,358:37-39.
[32]Li Hu,Fang Zhen,Luo Jia,et al.Direct conversion of biomass components to the biofuel methyl levulinate catalyzed by acid-base bifunctional zirconia-zeolites[J].Applied Catalysis B Environmental,2017,200:182-191.
[33]Saravanamurugan S,Riisager A.Zeolite catalyzed transformation of carbohydrates to alkyl levulinates[J].Chemcatchem,2013,5(7):1754-1757.
[34]Rataboul F,Essayem N.Cellulose reactivity in supercritical methanol in the presence of solid acid catalysts:Direct synthesis of methyl-levulinate[J].Industrial&Engineering Chemistry Research,2011,50(2):699-704.
[35]Amarasekara A S,Wiredu B.Acidic ionic liquid catalyzed one-pot conversion of cellulose to ethyl levulinate and levulinic acid in ethanol-water solvent system[J].Bioenergy Research,2014,7(4):1237-1243.