文献类型：期刊文献

中文题名：固体磷酸铁催化纤维素液化制备乙酰丙酸及乙酰丙酸甲酯

英文题名：Preparation of Levulinic Acid and Methyl Levulinate from Cellulose Catalyzed by Solid Iron Phosphate

作者：魏琳珊[1,2,3] 赵佳平[2] 叶俊[1,2] 王奎[1,2] 蒋剑春[1,2,3]

第一作者：魏琳珊

机构：[1]中国林业科学研究院林业新技术研究所,北京100091;[2]中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点实验室,江苏省生物质能源与材料重点实验室,江苏南京210042;[3]南京林业大学江苏省林业资源高效加工利用协同创新中心,江苏南京210037

年份：2020

卷号：40

期号：5

起止页码：69-74

中文期刊名：林产化学与工业

外文期刊名：Chemistry and Industry of Forest Products

收录：CSTPCD;;Scopus;北大核心:【北大核心2017】；CSCD:【CSCD2019_2020】；

基金：中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2016SY028)。

语种：中文

中文关键词：纤维素;乙酰丙酸/酯;催化;固体磷酸铁

外文关键词：cellulose;levulinic acid/levulinates;catalyze;solid iron phosphate

分类号：TQ35

摘要：以纤维素为原料、固体FePO 4为催化剂,在水/甲醇溶液中制备乙酰丙酸及乙酰丙酸甲酯。通过比较液体酸、金属氯盐、金属硫酸盐以及磷酸铁的催化作用发现,FePO 4催化作用下纤维素的转化效率、乙酰丙酸及乙酰丙酸甲酯的总产率均与H 2SO 4、Al 2(SO 4)3催化作用结果相当。其催化作用主要归结为固体FePO 4通过水解形成Br nsted酸及Lewis酸酸性位点,为纤维素水解、葡萄糖异构化及脱水形成乙酰丙酸/酯提供催化活性,实现纤维素定向液化选择性制备乙酰丙酸及乙酰丙酸甲酯。在反应温度220℃、反应时间2 h、微晶纤维素2 g、水/甲醇体积比1∶19(溶剂总体积40 mL)、催化剂用量1.5 g的最佳反应条件下,乙酰丙酸及乙酰丙酸甲酯总收率为62.2%。FT-IR、XRD及TG/DTG对纤维素、固体残渣和FePO 4催化剂表征结果表明:反应后纤维素得到了有效地液化,催化剂则通过重结晶形式从溶剂体系中分离。考虑到FePO 4良好的催化活性和循环利用特性,该工艺的工业化还需要进一步的系统研究。
Levulinic acid and methyl levulinate were synthesized from cellulose with using solid FePO 4 as catalyst in water/methanol medium.By comparing the catalytic results of liquid acid,metal chloride,metal sulfate and FePO 4,the results showed that FePO 4 displayed a nearly result in both conversion efficiency of cellulose and yields of levulinic acid and methyl levulinate as comparable to the catalytic effects of H 2SO 4 and Al 2(SO 4)3.The catalytic effect of solid FePO 4 was mainly attributed to form Br nsted and Lewis acidic sites,which provide catalytic activity for cellulose hydrolysis,glucose isomerization and dehydration to form levulinic acid/ester.The total yield of levulinic acid and methyl levulinatewas 62.2%under optimal the best technological conditions of reaction temperature at 220℃,reaction time for 2 h,2 g of microcrystalline cellulose,water/methanol volume ratio of 1∶19(total solvent volume 40 mL)and 1.5 g of catalyst dosage.The characterization of cellulose,solid residue and FePO 4 catalyst were conducted by FT-IR,XRD and TG/DTG techniques,and the results indicated that the cellulose was efficiently liquefied and then the catalyst was recycled by recrystallization.The formation of levulinates was conducted by the methanolysis and hydrolysis of cellulose,while methyl glucoside(MLG)was an important intermediate and its conversion was affected by the reaction time and the catalyst dosage.Further systematical research of this new technique is further required before the process could be industrialized considering the excellent catalytic activity and recycling characteristic of FePO 4.