甲醇介质中小麦秸秆催化转化制备乙酰丙酸甲酯Catalytic Conversion of Wheat Straw to Methyl Levulinate in Methanol
邓琳,常春,何玉远,白净,方书起
摘要(Abstract):
乙酰丙酸甲酯是一种用途广泛的新型生物质基化学品。以小麦秸秆为原料,研究了Al2(SO4)3·18H2O催化醇解小麦秸秆制备乙酰丙酸甲酯。首先考察了不同单因素对乙酰丙酸甲酯生成的影响,利用响应面实验优化了小麦秸秆转化生成乙酰丙酸甲酯的工艺条件,在反应温度为191℃,反应时间1.0 h,催化剂量1.15 mmol,秸秆质量1.01 g时,乙酰丙酸甲酯的平均产率达到53.4%(mol)。进一步利用X射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)和冷场发射扫描电镜(SEM)对催化剂进行表征。在此基础上,考察了催化剂的循环利用,结果表明Al2(SO4)3·18H2O易于回收,重复使用五次以上仍然具有良好的催化活性。该研究为小麦秸秆制备乙酰丙酸甲酯提供了一种绿色、有效的方法。
关键词(KeyWords): 小麦秸秆;生物质;醇解;乙酰丙酸甲酯;催化
基金项目(Foundation): 河南省自然科学基金(162300410247)
作者(Author): 邓琳,常春,何玉远,白净,方书起
参考文献(References):
- [1]Li H,Fang Z,Luo J,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.
- [2]LIU Qin(刘勤),WANG Shao-kang(王少康),HU Liang-long(胡良龙),et al.A case study on straw utilization patent(秸秆资源化利用专利活动实证研究)[J].Applied Chemical Industry(应用化工),2017,46(3):546-550.
- [3]Salapa I,Katsimpouras C,Topakas E,et al.Organosolv pretreatment of wheat straw for efficient ethanol production using various solvents[J].Biomass&Bioenergy,2017,100:10-16.
- [4]WANG Feng-qin(王风芹),XIE Yao-huan(谢媱嬛),SU Zeng-ping(苏增平),et al.Enzymatic composite detoxification improving effect ofbutanol fermentation from corn stover hydrolysate(酶法复合脱毒提高玉米秸秆水解液丁醇发酵效率)[J].Transactions of the Chinese Society of Agricultural Engineering(农业工程学报),2017,33(8):204-210.
- [5]ZHAO Na(赵娜),LI Bao-xia(李宝霞),HUA Mei-yu(华美玉).Effects of two metal salts on rice husk pyrolysis for bio-oil production(两种金属盐对稻壳热解生物油的影响)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2016,30(3):604-610.
- [6]CHANG Chun(常春),JIANG Xiao-xian(姜孝先),ZHANG Ting(张挺).A gas chromatography method for measurement of ethyl levulinate in biomass decomposition products(气相色谱法测定生物质醇解产物中的乙酰丙酸乙酯)[J].Journal of Zhengzhou University(Engineering Science)(郑州大学学报(工学版)),2013,34(2):1-3.
- [7]An R,Xu G,Chang C,et al.Efficient one-pot synthesis of n-butyl levulinate from carbohydrates catalyzed by Fe2(SO4)3[J].Journal of Energy Chemistry,2017,26(3):556-563.
- [8]PENG Lin-cai(彭林才),LIN Lu(林鹿),LI Hui(李辉).Conversion of biomass into levulinate esters as novel energy chemicals(生物质转化合成新能源化学品乙酰丙酸酯)[J].Progress in Chemistry(化学进展),2012,24(5):801-809.
- [9]Démolis A,Essayem N,Rataboul F.Synthesis and applications of alkyl levulinates[J].Acs Sustainable Chemistry&Engineering,2014,2(6):1338-1352.
- [10]Liu J,Yang B B,Wang X Q,et al.Glucose conversion to methyl levulinate catalyzed by metal ion-exchanged montmorillonites[J].Applied Clay Science,2017:118-124.
- [11]Zhou L,Zou H,Nan J,et al.Conversion of carbohydrate biomass to methyl levulinate with Al2(SO4)3,as a simple,cheap and efficient catalyst[J].Catalysis Communications,2014,50(18):13-16.
- [12]Ding D,Xi J,Wang J,et al.Production of methyl levulinate from cellulose:Selectivity and mechanism study[J].Green Chemistry,2015,17(7):4037-4044.
- [13]Feng J F,Jiang J C,Xu J M,et al.Preparation of methyl levulinate from fractionation of direct liquefied bamboo biomass[J].Applied Energy,2015,154:520-527.
- [14]Tominaga K I,Nemoto K,Kamimura Y,et al.A practical and efficient synthesis of methyl levulinate from cellulosic biomass catalyzed by an aluminum-based mixed acid catalyst system[J].RSC Advance,2016,6(69):65119-65124.
- [15]MAO Hua(茅花),HUANG He(黄和).Investigation on aluminum salfl3-dialkyl imidazolium salt catalyzed conversion of sucrose to methyl levulinate(离子液体-铝盐催化蔗糖制乙酰丙酸甲酯)[J].Chemical Industry And Engineering Progress(化工进展),2012,31(8):1816-1819.
- [16]CHANG Chun(常春),DENG Lin(邓琳),QI Xiao-ge(戚小各),et al.Progress of application of solid catalysts in levulinic acid and alkyl levulinates produced from biomass(固体催化剂在生物质转化乙酰丙酸和乙酰丙酸酯应用的研究进展)[J].Chemistry and Industry of Forest Products(林产化学与工业),2017,37(2):1-5.
- [17]CHANG Chun(常春),KONG Peng-fei(孔鹏飞),ZHAO Shi-qiang(赵世强).Study on production of ethyl levulinate from cellulose catalyzedby solid acid Al2(SO4)3·18H2O(Al2(SO4)3·18H2催化纤维素生成乙酰丙酸乙酯的实验研究)[J].Journal of Zhengzhou University(Engineering Science)郑州大学学报(工学版),2016,37(4):31-35.
- [18]Liu H M,Feng B,Sun R C.Acid-chlorite pretreatment and liquefaction of cornstalk in hot-compressed water for bio-oil production[J].Journal of Agricultural&Food Chemistry,2011,59(19):10524-31.
- [19]HE Xiao-liang(贺小亮),JIANG Jian-chun(蒋剑春),FENG Jun-feng(冯君锋),et al.Conversion of microcrystalline cellulose into methyl levulinate in mixed solvents(微晶纤维素复合溶剂醇解制备乙酰丙酸甲酯的研究)[J].Modern Chemical Industry(现代化工),2014,34(7):89-93.
- [20]Peng L,Tao R,Wu Y.Catalytic upgrading of biomass-derived furfuryl alcohol to butyl levulinate biofuel over common metal salts[J].Catalysts,2016,6(9):143-154.
- [21]YANG Hai-xia(杨海霞),SUN Qing(孙清),FU Yu-chuan(傅玉川),et al.Dehydration of methanol to dimethyl ether over A12(SO4)3/Si O2 catalysts(Al2(SO4)3·18H2O/Si O2催化甲醇脱水合成二甲醚)[J].Journal Of Molecular Catalysis(China)(分子催化),2009,23(2):139-144.
- [22]Shi W,Li J.A new deactivation mechanism of sulfate-promoted iron oxide[J].Catalysis Letters,2013,143(12):1285-1293.
- [23]Peng L,Lin L,Li H,et al.Acid-catalyzed direct synthesis of methyl levulinate from paper sludge in methanol medium[J].Bioresources,2013,4(8):5895-5907.
- [24]Peng L,Lin.L,Li H,et al.Conversion of carbohydrates biomass into levulinate esters using heterogeneous catalysts[J].Applied Energy,2011,12(88):4590-4596.