NaCl辅助酸催化糠醛残渣合成乙酰丙酸

doi:10.3969/j.issn.0253-2417.2018.04.011

林产化学与工业 ›› 2018, Vol. 38 ›› Issue (4): 69-73.doi: 10.3969/j.issn.0253-2417.2018.04.011

NaCl辅助酸催化糠醛残渣合成乙酰丙酸

李淼, 刘秋梅, 蔡勤杰, 张素平

华东理工大学煤气化及能源化工教育部重点实验室, 生物质能研究中心, 上海 200237

收稿日期:2018-03-09 出版日期:2018-08-25 发布日期:2018-08-10
通讯作者: 张素平,教授,博士,研究方向为生物质能转化;E-mail:zsp@ecust.edu.cn。 E-mail:zsp@ecust.edu.cn
作者简介:李淼(1993-),女,黑龙江齐齐哈尔人,硕士生,主要从事生物质能源研究工作
基金资助:
国家高技术研究发展计划资助（2012AA101806）；国家自然科学基金资助项目（51176049）

Levulinic Acid Synthesis from Furfural Residue with Synergistic Effect of Catalyst and NaCl

LI Miao, LIU Qiumei, CAI Qinjie, ZHANG Suping

Laboratory of Coal Gasification and Energy and Chemical Engineering, Ministry of Education, East China University of Science and Technlolgy, Shanghai 200237, China

Received:2018-03-09 Online:2018-08-25 Published:2018-08-10

摘要/Abstract

摘要： 以玉米芯制糠醛的残渣为原料，在H₂SO₄（Brønsted酸）和Lewis酸一起作为催化剂，并加入NaCl为催化助剂的条件下，对比了4种Lewis酸（FeCl₃、LiCl、AlCl₃和ZnCl₂）的催化效果，同时探讨了助剂NaCl对制备乙酰丙酸的影响并优化工艺条件。研究结果表明：FeCl₃促进了糠醛渣中纤维素转化为乙酰丙酸，加入助剂NaCl，可促进纤维素的溶解，提高乙酰丙酸的产率及选择性。在温度200℃，H₂SO₄质量分数3%，含有催化剂的溶液与糠醛渣的液固比为6∶1（mL∶g），FeCl₃用量1.8%，NaCl用量7%时，乙酰丙酸产率69.18%，选择性89.46%，分别比不添加NaCl增加了15.3和21.9个百分点。

关键词: 糠醛残渣, FeCl₃, NaCl, 乙酰丙酸

Abstract: The effect of four kinds of metal chlorides (FeCl₃, LiCl, AlCl₃ and ZnCl₂) were compared for the preparation of levulinic acid(LA) with furfural residue as raw material using Brønsted acid combined with Lewis acid as catalyst, and NaCl as promoter. The process conditions for the preparation of levulinic acid were also optimized. Results showed that the conversion of furfural residue into levulinic acid was promoted by FeCl₃. The dissolution of cellulose was promoted and the yield and selectivity of levulinic acid were improved by adding NaCl. The reaction conditions for the preparation of levulinic acid were optimized as the follows:temperature of 200℃, H₂SO₄ mass fraction of 3%, ratio of solution containing catalyst and furfural residue 6:1 (mL:g), FeCl₃ addition amount of 1.8%, and NaCl addition amount of 7%. The levulinic acid yield of 69.18% and selectivity of 89.46% can be obtained at the optimum conditions, which were 15.3 and 21.9 percent point higher than that of without NaCl addition respectively.

Key words: furfural residue, FeCl₃, NaCl, levulinic acid

中图分类号:

TQ35

李淼, 刘秋梅, 蔡勤杰, 张素平. NaCl辅助酸催化糠醛残渣合成乙酰丙酸[J]. 林产化学与工业, 2018, 38(4): 69-73.

LI Miao, LIU Qiumei, CAI Qinjie, ZHANG Suping. Levulinic Acid Synthesis from Furfural Residue with Synergistic Effect of Catalyst and NaCl[J]. Chemistry and Industry of Forest Products, 2018, 38(4): 69-73.

参考文献

[1] DU X,LIU Y,WANG J,et al. Catalytic conversion of biomass-derived levulinic acid into γ-valerolactone using iridium nanoparticles supported on carbon nanotubes[J]. Chinese Journal of Catalysis,2013,34(5):993-1001.
[2] ZENG W,CHENG D G,ZHANG H,et al. Dehydration of glucose to levulinic acid over MFI-type zeolite in subcritical water at moderate conditions[J]. Reaction Kinetics,Mechanisms and Catalysis,2010,100(2):377-384.
[3] RUNGE T,ZHANG C. Two-stage acid-catalyzed conversion of carbohydrates into levulinic acid[J]. Industrial & Engineering Chemistry Research,2012,51(8):3265-3270.
[4] SONG C,LIU S,PENG X,et al. Catalytic conversion of carbohydrates to levulinate ester over heteropolyanion-based ionic liquids[J]. ChemSusChem,2016,9(23):3307-3316.
[5] PENG L,LIN L,ZHANG J,et al. Catalytic conversion of cellulose to levulinic acid by metal chlorides[J]. Molecules,2010,15(8):5258-5272.
[6] LI J,JIANG Z,HU L,et al. Selective conversion of cellulose in corncob residue to levulinic acid in an aluminum trichloride-sodium chloride system[J]. ChemSusChem,2014,7(9):2482-2488.
[7] VAN SOEST P J R J B,LEWIS B A. Methods for dietaryfiber,neutral detergent fiber,and nonstarchpolysaccharides in relation to animal nutrition[J]. Journal of Dairy Science,1991,74(10):3583-3597.
[8] CHANG C,CEN P,MA X. Levulinic acid production from wheat straw[J]. Bioresour Technol,2007,98(7):1448-1453.
[9] 王春英,王攀,漆新华,等. 三氯化铁催化蔗糖产乙酰丙酸的研究[J]. 化工时刊,2008,22(10):7-9. WANG C Y,WANGP,QI X H,et al. Study on catalytic effect of ferric chloride on production of acetylpropionic acid[J]. Chemical Industry Times,2008,22(10):7-9.
[10] GIRISUTA B,JANSSEN L P B M,HEERES H J. Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid[J]. Industrial & Engineering Chemistry Research,2007,46(6):1696-1708.
[11] HORVAT J,KLAIC' B,METELKO B,et al. Mechanism of levulinic acid formation[J]. Tetrahedron Letters,1985,26(17):2111-2114.
[12] REN H,ZHOU Y,LIU L. Selective conversion of cellulose to levulinic acid via microwave-assisted synthesis in ionic liquids[J]. Bioresource Technology,2013,129(2):616-619.
[13] CHOUDHARY V,MUSHRIF S H,HO C,et al. Insights into the interplay of lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media[J]. Journal of the American Chemical Society,2013,135(10):3997-4006.
[14] YAN L,GREENWOOD A A,HOSSAIN A,et al. A comprehensive mechanistic kinetic model for dilute acid hydrolysis of switchgrass cellulose to glucose,5-HMF and levulinic acid[J]. RSC Advances,2014,4(45):23492-23504.
[15] 李利军,李果,李伟,等. 三氯化铝催化赤砂糖制备乙酰丙酸的研究[J]. 化工时刊,2012,26(7):19-22. LI L J,LI G,LI W,et al. Study on preparation of levulinic acid from red sugar catalyzed by aluminum trichloride[J]. Chemical Industry Times,2012,26(7):19-22.
[16] PATIL S K R,HELTZEL J,LUND C R F. Comparison of structural features of humins formed catalytically from glucose,fructose,and 5-hydroxymethylfurfuraldehyde[J]. Energy & Fuels,2012,26(8):5281-5293.
[17] WANG H,GURAU G,PINGALI S V,et al. Physical insight into switchgrass dissolution in ionic liquid 1-ethyl-3-methylimidazolium acetate[J]. ACS Sustainable Chemistry & Engineering,2014,2(5):1264-1269.
[18] SHUAI L,PAN X. Hydrolysis of cellulose by cellulase-mimetic solid catalyst[J]. Energy & Environmental Science,2012,5(5):6889-6894.
[19] YANG Y,HU C W,ABU-OMAR M M. Conversion of carbohydrates and lignocellulosic biomass into 5-hydroxymethylfurfural using AlCl₃·6H₂O catalyst in a biphasic solvent system[J]. Green Chemistry,2012,14(2):509-513.

NaCl辅助酸催化糠醛残渣合成乙酰丙酸

Levulinic Acid Synthesis from Furfural Residue with Synergistic Effect of Catalyst and NaCl

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