硫酸盐催化转化木质纤维制备乙酰丙酸和乙酰丙酸酯的研究进展

doi:10.3969/j.issn.1673-5854.2022.04.007

生物质化学工程 ›› 2022, Vol. 56 ›› Issue (4): 49-57.doi: 10.3969/j.issn.1673-5854.2022.04.007

硫酸盐催化转化木质纤维制备乙酰丙酸和乙酰丙酸酯的研究进展

魏琳珊¹^,²(), 叶俊¹^,², 王奎¹^,², 蒋剑春¹^,²^,*()

1. 中国林业科学研究院林产化学工业研究所; 江苏省生物质能源与材料重点实验室; 国家林业和草原局林产化学工程重点实验室; 林木生物质低碳高效利用国家工程研究中心; 江苏南京 210042
2. 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

收稿日期:2021-03-22 出版日期:2022-07-30 发布日期:2022-07-23
通讯作者: 蒋剑春 E-mail:1076321913@qq.com;jiangic@icifp.cn
作者简介:蒋剑春, 院士, 博士生导师, 研究领域: 生物质能源与材料; E-mail: jiangic@icifp.cn
魏琳珊(1995-), 女, 辽宁铁岭人, 硕士生, 研究方向为生物质能源; E-mail: 1076321913@qq.com
基金资助:
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助资金(CAFYBB2018 GD002-04)

Research Progress on Preparation of Levulinic Acid and Esters from Lignocellulose by Sulfate Catalyst

Linshan WEI¹^,²(), Jun YE¹^,², Kui WANG¹^,², Jianchun JIANG¹^,²^,*()

1. Institute of Chemical Industry of Forest Products, CAF; Key Lab. of Biomass Energy and Material, Jiangsu Province; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2021-03-22 Online:2022-07-30 Published:2022-07-23
Contact: Jianchun JIANG E-mail:1076321913@qq.com;jiangic@icifp.cn

摘要/Abstract

摘要：

以木质纤维原料非均相催化转化制备高附加值平台化合物乙酰丙酸和乙酰丙酸酯为研究对象, 对以硫酸盐为催化体系的木质纤维定向转化生成乙酰丙酸和乙酰丙酸酯的国内外的研究进展和趋势进行了综述。文章概述了乙酰丙酸及乙酰丙酸酯在工业产业中的应用情况; 重点比较了不同硫酸盐催化木质纤维制备乙酰丙酸及乙酰丙酸酯的过程, 并对不同溶剂体系协同作用下的木质纤维转化为乙酰丙酸和乙酰丙酸酯过程的影响规律进行了深入分析, 总结了硫酸盐类催化剂催化木质纤维定向转化的过程机理。同时针对现有工艺存在的问题进行了分析, 展望了该研究领域的发展方向。

关键词: 木质纤维, 乙酰丙酸, 乙酰丙酸酯, 催化, 硫酸盐

Abstract:

In this paper, the heterogeneous catalytic conversions of lignocellulose to high value-added platform compounds of levulinic acid and esters were studied. The research progress and trend of the direct conversion of lignocellulose to levulinic acid and esters using sulfate as catalytic system at home and abroad were reviewed. Firstly, the basic information of levulinic acid/esters and their application in industrial production were summarized. The preparation process of levulinic acid/esters using different sulfate catalysts was compared, and the law of the conversion of lignocellulose to levulinic acid/esters under the synergy effects of different solvent systems was deeply analyzed. And, the mechanism of direct conversion of lignocellulose catalyzed by sulfate catalysts was also summarized. Finally, the problems of existing process were discussed, and the development direction of this research field was prospected.

Key words: lignocellulose, levulinic acid, levulinic esters, catalytic, sulfate

中图分类号:

TQ35

魏琳珊, 叶俊, 王奎, 蒋剑春. 硫酸盐催化转化木质纤维制备乙酰丙酸和乙酰丙酸酯的研究进展[J]. 生物质化学工程, 2022, 56(4): 49-57.

Linshan WEI, Jun YE, Kui WANG, Jianchun JIANG. Research Progress on Preparation of Levulinic Acid and Esters from Lignocellulose by Sulfate Catalyst[J]. Biomass Chemical Engineering, 2022, 56(4): 49-57.

图/表 9

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参考文献 49

1	LEUNG D Y C , WU R , LEUNG R K H . A review on biodiesel production using catalyzed transesterification[J]. Applied Energy, 2010, 87 (4): 1083- 1095. doi: 10.1016/j.apenergy.2009.10.006
2	SAIKAT D , SUDIPTA D , BASUDEB S , et al. Advances in conversion of hemicellulosic biomass to furfural and upgrading to biofuels[J]. Catalysis Science & Technology, 2012, 2, 2025- 2036.
3	CHANG C , CEN P L , MA X J . Levulinic acid production from wheat straw[J]. Bioresource Technology, 2007, 98 (7): 1448- 1453. doi: 10.1016/j.biortech.2006.03.031
4	DAIANE B B , MAGALE K D R , TIELE M R , et al. Cleaner production: Levulinic acid from rice husks[J]. Journal of Cleaner Production, 2013, 47, 96- 101. doi: 10.1016/j.jclepro.2013.01.035
5	CHEN H Z , YU B , JIN S Y . Production of levulinic acid from steam exploded rice straw via solid superacid, S₂O₈^2-/ZrO₂"-" SiO₂ "-" Sm₂O₃[J]. Bioresource Technology, 2011, 102 (3): 3568- 3570. doi: 10.1016/j.biortech.2010.10.018
6	FANG Q , HANNA M A . Experimental studies for levulinic acid production from whole kernel grain sorghum[J]. Bioresource Technology, 2002, 81 (3): 187- 192. doi: 10.1016/S0960-8524(01)00144-4
7	KANG M , SEUNG W K , KIM J , et al. Optimization of levulinic acid production from Gelidium amansii[J]. Renewable Energy, 2013, 54, 173- 179. doi: 10.1016/j.renene.2012.08.028
8	ANNA M R G , CLAUDIA A , ERIKA R , et al. From giant reed to levulinic acid and gamma-valerolactone: A high yield catalytic route to valeric biofuels[J]. Applied Energy, 2013, 102, 157- 162. doi: 10.1016/j.apenergy.2012.05.061
9	HUBER G W , IBORRA S , CORMA A . Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering[J]. Chemical Reviews, 2006, 106 (9): 4044- 4098. doi: 10.1021/cr068360d
10	JEAN-PAUL L , RICHARD P , PAUL M , et al. Valeric biofuels: A platform of cellulosic transportation fuels[J]. Angewandte Chemie, 2010, 122 (26): 4479- 4483.
11	SHEN J , WYMAN C E . Hydrochloric acid-catalyzed levulinic acid formation from cellulose: Data and kinetic model to maximize yields[J]. AIChE Journal, 2012, 58 (1): 236- 246. doi: 10.1002/aic.12556
12	彭红, 刘玉环, 张锦胜, 等. 生物质生产乙酰丙酸研究进展[J]. 化工进展, 2009, 28 (12): 2237- 2241. doi: 10.3321/j.issn:1000-6613.2009.12.030
13	HEM J , BRYUAN R M , JOE T , et al. Ethyl levulinate: A potential bio-based diluent for biodiesel which improves cold flow properties[J]. Biomass Bioenergy, 2011, 35, 3262- 3266. doi: 10.1016/j.biombioe.2011.04.020
14	CHRISTENSEN E , WILLIAMS A , PAUL S , et al. Properties and performance of levulinate esters as diesel blend components[J]. Energy Fuels, 2011, 25 (11): 5422- 5428. doi: 10.1021/ef201229j
15	薛宝祺, 王树起. 果糖酸钙的制备方法及应用CN1304923[P]. 2001-07-25.
16	THOMASJ S , ADRIAAN R P H , WHEELER M C . Energy densification of levulinic acid by thermal deoxygenation[J]. Green Chemistry, 2010, 12, 1353- 1356. doi: 10.1039/c005067a
17	JOSEPH J B , MOENS L , ELLIOTT D C , et al. Production of levulinic acid and use as a platform chemical for derived products[J]. Resources, Conservation & Recycling, 2000, 28 (3): 227- 239.
18	SEEHRA J S , JORDAN P M . 5-Aminolevulinic acid dehydratase: Alkylation of an essential thiol in the bovine-liver enzyme by active-site-directed reagents[J]. European Journal of Biochemistry, 1981, 113 (3): 435- 446. doi: 10.1111/j.1432-1033.1981.tb05083.x
19	ALEXANDER G Z , NATALYA E K , NIKOLAY V I , et al. Variation in the regioselectivity of levulinic acid bromination in ionic liquids[J]. Tetrahedron Letters, 2009, 51 (3): 545- 547.
20	MASCAL M , DUTTA S . Synthesis of the natural herbicide δ-aminolevulinic acid from cellulose-derived 5-(chloromethyl) furfural[J]. Green Chemistry, 2011, 13, 40- 41. doi: 10.1039/C0GC00548G
21	GUO Y , LI K , YU X , et al. Mesoporous H₃PW₁₂O₄₀-silica composite: Efficient and reusable solid acid catalyst for the synthesis of diphenolic acid from levulinic acid[J]. Applied Catalysis B, Environmental, 2007, 81 (3): 182- 191.
22	LI K , HU J , LI W , et al. Design of mesostructured H₃PW₁₂O₄₀-silica materials with controllable ordered and disordered pore geometries and their application for the synthesis of diphenolic acid[J]. Journal of Materials Chemistry, 2009, 19, 8628- 8638. doi: 10.1039/b910416j
23	VAN DE VYVER S , GEBOERS J , HELSEN S , et al. Thiol-promoted catalytic synthesis of diphenolic acid with sulfonated hyperbranched poly(arylene oxindole)s[J]. Chemical Communications, 2012, 48, 3497- 3499. doi: 10.1039/c2cc30239j
24	何柱生, 赵立芳. 分子筛负载TiO₂/SO₄^2-催化合成乙酰丙酸乙酯的研究[J]. 化学研究与应用, 2001, (5): 537- 539. doi: 10.3969/j.issn.1004-1656.2001.05.018
25	刘道君, 刘莹. γ-戊内酯合成新工艺的研究[J]. 香料香精化妆品, 1999, (4): 1- 4.
26	常春, 马晓建, 岑沛霖. 新型绿色平台化合物乙酰丙酸的生产及应用研究进展[J]. 化工进展, 2005, (4): 350- 356. doi: 10.3321/j.issn:1000-6613.2005.04.003
27	张一宾, 周燚. 5-氨基乙酰丙酸的植物生理活性[J]. 世界农药, 2000, (3): 8- 14.
28	杨永祥, 王耀. 富万钾有机钾肥对促进作物生长及提高作物产量和品质的效果[J]. 陕西农业科学, 1997, 2, 47- 48.
29	BOZELL J J . Chemicals and Materials from Renewable Resources[M]. Washington, DC: American Chemical Society, 2001: 51- 63.
30	ALEXANDRE D , NADINE E , FRANCK R . Synthesis and applications of alkyl levulinates[J]. ACS Sustainable Chemistry Engineering, 2014, 2, 1338- 1352. doi: 10.1021/sc500082n
31	DANIEL J H . An examination of biorefining processes, catalysts and challenges[J]. Catalysis Today, 2008, 145 (1): 138- 151.
32	常春, 岑沛霖, 马晓建. 利用乙酰丙酸合成双酚酸的工艺研究[J]. 高校化学工程学报, 2007, (1): 106- 110.
33	HUANG Y B , YANG T , LIN Y T , et al. Facile and high-yield synthesis of methyl levulinate from cellulose[J]. Green Chemistry, 2018, 20, 1323- 1334. doi: 10.1039/C7GC02883K
34	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.
35	PENG L C , LI H , LIN L , et al. Effect of metal salts existence during the acid-catalyzed conversion of glucose in methanol medium[J]. Catalysis Communications, 2015, 59 (59): 10- 13.
36	HUANG Y B , YANG T , ZHOU M C , et al. Microwave-assisted alcoholysis of furfural alcohol into alkyl levulinates catalyzed by metal salts[J]. Green Chemistry, 2016, 18 (6): 1516- 1523.
37	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.
38	TAN J , LIU Q , CHEN L , et al. Efficient production of ethyl levulinate from cassava over Al₂(SO₄)₃ catalyst in ethanol-water system[J]. Journal of Energy Chemistry, 2017, 26 (1): 115- 120.
39	EFREMOV A A , PERVYSHINA G G , KUZNETSOVB N . Production of levulinic acid from wood raw material in the presence of sulfuric acid and its salts[J]. Chemistry of Natural Compounds, 1998, 34 (2): 182- 185.
40	RASRENDRA C B , MAKERTIHARTHA I G B N , ADISASMITO S , et al. Green chemicals from D-glucose: Systematic studies on catalytic effects of inorganic salts on the chemo-selectivity and yield in aqueous solutions[J]. Topics in Catalysis, 2010, 53 (15/16/17/18): 1241- 1247.
41	DENG L , ZHAO Y , LI J , et al. Conversion of levulinic acid and formic acid into γ-valerolactone over heterogeneous catalysts[J]. ChemSusChem, 2010, 3, 1172- 1175.
42	DENG L , CHANG C , AN R , et al. Metal sulfates-catalyzed butanolysis of cellulose: Butyl levulinate production and optimization[J]. Cellulose, 2017, 24 (12): 1- 13.
43	CAO X , PENG X , SUN S , et al. Hydrothermal conversion of xylose, glucose, and cellulose under the catalysis of transition metal sulfates[J]. Carbohydrate Polymers, 2015, 118, 44- 51.
44	CHANG C , XU G Z , JIANG X X . Production of ethyl levulinate by direct conversion of wheat straw in ethanol media[J]. Bioresource Technology, 2012, 121, 93- 99.
45	HUANG Y , YANG T , CAI B , et al. Highly efficient metal salt catalyst for the esterification of biomass derived levulinic acid under microwave irradiation[J]. RSC Advances, 2016, 6, 2106- 2111.
46	TAO F , SONG H , CHOU L . Catalytic conversion of cellulose to chemicals in ionic liquid.[J]. Carbohydrate Research, 2011, 346 (1): 58- 63.
47	FRANCK R , NADINE E . 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): 799- 805.
48	PENG L , LIN L , LI H , et al. Conversion of carbohydrates biomass into levulinate esters using heterogeneous catalysts[J]. Applied Energy, 2011, 88 (12): 4590- 4596.
49	PENG L , LIN L , ZHANG J , et al. Solid acid catalyzed glucose conversion to ethyl levulinate[J]. Applied Catalysis A General, 2011, 397 (1): 259- 265.

化合物 chemical compound	相对分子质量 relative molecular weight	折射率 refractive index	密度/(kg·m^-3) density	熔点/℃ melting point	沸点/℃ boiling point
乙酰丙酸levulinic acid	116.12	1.4796/20 ℃	1140/20 ℃	33~35	245~246
乙酰丙酸甲酯methyl levulinate	130.14	1.422/20 ℃	1051/20 ℃	-24	196

溶剂 solvent	原料 substrate	时间/min time	温度/℃ temp.	产物(质量分数) product(mass fraction)	加热方式 heating mode	文献 ref.
甲醇/水methanol/water	纤维素cellulose	40	180	ML(70.6%)	微波加热microwave	[33]
甲醇/水methanol/water	纤维素cellulose	720	180	ML(60.8%)	油浴oil	[33]
甲醇/水methanol/water	纤维素cellulose	80	170	ML(68.4%)	微波microwave	[33]
甲醇methanol	葡萄糖glucose	150	160	ML(64%)	油浴oil	[35]
甲醇methanol	葡萄糖glucose	120	200	ML(54%)	油浴oil	[35]
甲醇methanol	果糖fructose	150	160	ML(49%)	油浴oil	[35]
甲醇methanol	纤维素cellulose	300	180	ML(44%)	油浴oil	[35]
乙醇ethanol	糠醇furfural alcohol	5	150	ML(80.6%)	微波microwave	[36]
正丁醇n-butanol	果糖fructose	120	200	BL(43.7%)	油浴oil	[37]
水water	木薯cassava	360	200	LA(14.53%)	油浴oil	[38]
乙醇/水ethanol/water	木薯cassava	360	200	EL(37.05%) LA(10.0%)*	油浴oil	[38]
水water	纤维素cellulose	120	250	LA(18.4%)	油浴oil	[39]
水water	纤维素cellulose	360	140	LA(5%)	油浴oil	[40]
水water	葡萄糖glucose	160	140	LA(5.0%)	油浴oil	[40]
甲醇methanol	小麦秸秆wheat straw	180	180	ML(10.2%)*	油浴oil	[41]
正丁醇n-butanol	纤维素cellulose	120	200	BL(13.6%)	油浴oil	[42]

催化剂 catalyst	溶剂 solvent	原料 substrate	时间/min time	温度/℃ temp.	产物 product	加热方式 heating mode	文献 ref.
Fe₂(SO₄)₃	甲醇/水methanol/water	纤维素cellulose	40	180	ML(48.2%)	微波microwave	[33]
Fe₂(SO₄)₃	水water	纤维素cellulose	30	200	LA(1.2 g/L)	油浴oil	[43]
Fe₂(SO₄)₃	甲醇methanol	葡萄糖glucose	150	160	ML(5.0%)	油浴oil	[35]
Fe₂(SO₄)₃	甲醇methanol	葡萄糖glucose	120	200	ML(43.0%)	油浴oil	[35]
FeSO₄	水water	纤维素cellulose	30	200	LA(0.1 g/L)	油浴oil	[43]
Fe₂(SO₄)₃	乙醇alcohol	糠醇furfural alcohol	5	150	ML(31.4%)	微波microwave	[36]
Fe₂(SO₄)₃	正丁醇n-butanol	果糖fructose	120	200	BL(59.2%)	油浴oil	[37]
Fe₂(SO₄)₃	水water	木薯cassava	360	200	LA(1.22%)	油浴oil	[38]
Fe₂(SO₄)₃	乙醇ethanol	木薯cassava	360	200	EL(9.28%) LA(4.01%)	油浴oil	[38]
Fe₂(SO₄)₃	水water	纤维素cellulose	120	250	LA(4.7%)	油浴oil	[39]
Fe₂(SO₄)₃	正丁醇n-butanol	纤维素cellulose	180	209	BL(37.2%)	油浴oil	[42]

溶剂 solvent	原料 substrate	时间/min time	温度/℃ temp.	产物 product	加热方式 heating mode	文献 ref.
甲醇/水methanol/water	纤维素cellulose	40	180	ML(4.4%)	微波microwave	[33]
甲醇methanol	葡萄糖glucose	150	160	ML(12%)	油浴oil	[34]
水water	纤维素cellulose	30	200	LA(3.2 g/L)	油浴oil	[43]
水water	葡萄糖glucose	30	200	LA(5.0 g/L)	油浴oil	[43]
正丁醇n-butanol	果糖fructose	120	200	BL(54.1%)	油浴oil	[37]
甲醇methanol	小麦秸秆wheat straw	234	183	ML(20.1%)	油浴oil	[44]
正丁醇n-butanol	纤维素cellulose	120	200	BL(29.1%)	油浴oil	[42]

溶剂 solvent	原料 substrate	时间/min time	温度/℃ temp.	产物 product	加热方式 heating mode	文献 ref.
甲醇/水methanol/water	纤维素cellulose	40	180	ML(4.4%)*	微波microwave	[33]
甲醇methanol	葡萄糖glucose	150	160	ML(2.0%)*	油浴oil	[34]
水water	葡萄糖glucose	30	200	LA(0.1 g/L)	油浴oil	[43]
水water	纤维素cellulose	30	200	LA(0.3 g/L)	油浴oil	[43]
乙醇alcohol	糠醇furfural alcohol	5	150	ML(9.7%)	微波microwave	[36]
正丁醇n-butanol	果糖fructose	120	200	BL(14.3%)*	油浴oil	[37]
水water	木薯cassava	360	200	LA(0.92%)	油浴oil	[38]
乙醇ethanol	木薯cassava	360	200	EL(0.16%) LA(0.25%)	油浴oil	[38]

硫酸盐催化转化木质纤维制备乙酰丙酸和乙酰丙酸酯的研究进展

Research Progress on Preparation of Levulinic Acid and Esters from Lignocellulose by Sulfate Catalyst

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