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

doi:10.3969/j.issn.0253-2417.2020.05.010

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (5): 69-74.doi: 10.3969/j.issn.0253-2417.2020.05.010

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

魏琳珊^1,^2,³(),赵佳平²,叶俊^1,²,王奎^1,²,蒋剑春^1,^2,^3,*()

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

收稿日期:2020-04-23 出版日期:2020-10-28 发布日期:2020-10-31
通讯作者: 蒋剑春 E-mail:1076321913@qq.com;biomass2016@163.com
作者简介: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金(CAFYBB2016SY028)

Preparation of Levulinic Acid and Methyl Levulinate from Cellulose Catalyzed by Solid Iron Phosphate

Linshan WEI^1,^2,³(),Jiaping ZHAO²,Jun YE^1,²,Kui WANG^1,²,Jianchun JIANG^1,^2,^3,*()

1. Research Institute of Forestry New Technology, CAF, Beijing 100091, China
2. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
3. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2020-04-23 Online:2020-10-28 Published:2020-10-31
Contact: Jianchun JIANG E-mail:1076321913@qq.com;biomass2016@163.com

摘要/Abstract

摘要：

以纤维素为原料、固体FePO₄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，FePO₄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H₂SO₄、Al₂（SO₄）₃催化作用结果相当。其催化作用主要归结为固体FePO₄通过水解形成Brønsted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FePO₄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FePO₄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。

关键词: 纤维素, 乙酰丙酸/酯, 催化, 固体磷酸铁

Abstract:

Levulinic acid and methyl levulinate were synthesized from cellulose with using solid FePO₄ as catalyst in water/methanol medium. By comparing the catalytic results of liquid acid, metal chloride, metal sulfate and FePO₄, the results showed that FePO₄ 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 H₂SO₄ and Al₂(SO₄)₃.The catalytic effect of solid FePO₄ was mainly attributed to form Brønsted 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 FePO₄ 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 FePO₄.

Key words: cellulose, levulinic acid/levulinates, catalyze, solid iron phosphate

中图分类号:

TQ35

魏琳珊,赵佳平,叶俊,王奎,蒋剑春. 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[J]. 林产化学与工业, 2020, 40(5): 69-74.

Linshan WEI,Jiaping ZHAO,Jun YE,Kui WANG,Jianchun JIANG. Preparation of Levulinic Acid and Methyl Levulinate from Cellulose Catalyzed by Solid Iron Phosphate[J]. Chemistry and Industry of Forest Products, 2020, 40(5): 69-74.

图/表 5

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参考文献 24

1	MIKA L T , CSEFALVAY E , NEMETH A . Catalytic conversion of carbohydrates to initial platform chemicals:Chemistry and sustainability[J]. Chemical Review, 2018, 118 (2): 505- 613. doi: 10.1021/acs.chemrev.7b00395
2	BERNARDI M I B , ARAUJO V D , RIBEIRO C , et al. Microwave hydrothermal synthesis, characterisation, and catalytic performance of Zn_1-x Mn_xO in cellulose conversion[J]. Chemical Papers, 2014, 68 (9): 1213- 1218.
3	GUAN C Y , CHEN S S , LEE T H , et al. Valorization of biomass from plant microbial fuel cells into levulinic acid by using liquid/solid acids and green solvents[J]. Journal of Cleaner Production, 2020, 260, 121097. doi: 10.1016/j.jclepro.2020.121097
4	YU Z H , LU X B , XIONG J , et al. Heterogeneous catalytic hydrogenation of levulinic acid to gamma-valerolactone with formic acid as internal hydrogen source[J]. Chemsuschem, 2020, 13 (11): 2916- 2930. doi: 10.1002/cssc.202000175
5	ZHANG X Y , LI Y , XUE L F , et al. Catalyzing cascade production of methyl levulinate from polysaccharides using heteropolyacids H_nPW₁₁MO₃₉ with Brønsted/Lewis acidic sites[J]. ACS Sustainable & Chemical Engineering, 2018, 6 (1): 165- 176.
6	KANG S M , YU J . Effect of methanol on formation of levulinates from cellulosic biomass[J]. Industrial and Engineering Chemistry Research, 2015, 54 (46): 11552- 11559. doi: 10.1021/acs.iecr.5b03512
7	KANG S M , FU J X , ZHANG G . From lignocellulosic biomass to levulinic acid:A review on acid-catalyzed hydrolysis[J]. Renewable and Sustainable Energy Reviews, 2018, 94, 340- 362. doi: 10.1016/j.rser.2018.06.016
8	ZHOU S Q , YANG X M , ZHANG Y L , et al. Efficient conversion of cellulose to methyl levulinate over heteropoly acid promoted by Sn-Beta zeolite[J]. Cellulose, 2019, 26 (17): 9135- 9147. doi: 10.1007/s10570-019-02743-z
9	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 (6): 1323- 1334. doi: 10.1039/C7GC02883K
10	YE J , ZHOU M H , WANG K , et al. Catalytic conversion of bamboo meal to high-yield furfural with solid acid catalyst FePO₄·2H₂O[J]. ChemistrySelect, 2017, 2 (34): 11250- 11254. doi: 10.1002/slct.201702115
11	XIA H A , XU S Q , YAN X P , et al. High yield synthesis of 5-hydroxymethylfurfural from cellulose using FePO₄ as the catalyst[J]. Fuel Processing Technology, 2016, 152, 140- 146. doi: 10.1016/j.fuproc.2016.06.030
12	YANG L , YAN X P , XU S Q , et al. One-pot synthesis of 5-hydroxymethylfurfural from carbohydrates using an inexpensive FePO₄ catalyst[J]. RSC Advances, 2015, 5 (26): 19900- 19906. doi: 10.1039/C4RA16145A
13	ZHOU P , ZHANG Z H . One-pot catalytic conversion of carbohydrates into furfural and 5-hydroxymethylfurfural[J]. Catalysis Science & Technology, 2016, 6 (11): 3694- 3712.
14	RACHEL C , BRETT H , COREY T L , et al. X-ray computed tomography comparison of individual and parallel assembled commercial lithium iron phosphate batteries at end of life after high rate cycling[J]. Journal of Power Sources, 2018, 381, 46- 55. doi: 10.1016/j.jpowsour.2018.01.087
15	AVINASH H , VENKATA D , HOLGER B F . Effect of water and methanol in the production of methyl methacrylate over iron phosphate catalysts[J]. Reaction Kinetics Mechanisms and Catalysis, 2018, 124 (1): 265- 277. doi: 10.1007/s11144-017-1331-7
16	WANG K , YE J , ZHOU M H , et al. Selective conversion of cellulose to levulinic acid and furfural in sulfolane/water solvent[J]. Cellulose, 2017, 24 (3): 1383- 1394. doi: 10.1007/s10570-016-1184-7
17	CHEN X L , ZHANG Y X , HOU T , et al. Catalysis performance comparison of a Brønsted acid H₂SO₄ and a Lewis acid Al₂(SO₄)₃ in methyl levulinate production from biomass carbohydrates[J]. Journal of Energy Chemistry, 2018, 27 (2): 552- 558.
18	YANG Y , ABU-OMAR M M , HU C W . Heteropoly acid catalyzed conversion of fructose, sucrose, and inulin to 5-ethoxymethylfurfural, a liquid biofuel candidate[J]. Applied Energy, 2012, 99, 80- 84. doi: 10.1016/j.apenergy.2012.04.049
19	JIANG L Y , ZHOU L P , CHAO J Y , et al. Direct catalytic conversion of carbohydrates to methyl levulinate:Synergy of solid Brønsted acid and Lewis acid[J]. Applied Catalysis B:Environmental, 2018, 220, 589- 596. doi: 10.1016/j.apcatb.2017.08.072
20	DAI J , PENG L C , LI H . Intensified ethyl levulinate production from cellulose using a combination oflow loading H₂SO₄ and Al(OTf)₃[J]. Catalysis Communications, 2018, 103 (5): 116- 119.
21	ZHAO T , CHEN Z Z , LIN X R , et al. Preparation and characterization of microcrystalline cellulose (MCC) from tea waste[J]. Carbohydrate Polymers, 2018, 184, 164- 170. doi: 10.1016/j.carbpol.2017.12.024
22	LENG E W , ZHANG Y , PENG Y , et al. In situ structural changes of crystalline and amorphous cellulose during slow pyrolysis at low temperatures[J]. Fuel, 2018, 216, 313- 321. doi: 10.1016/j.fuel.2017.11.083
23	SONI B , HASSAN E B , MAHMOUD B . Chemical isolation and characterization of different cellulose nanofibers from cotton stalks[J]. Carbohydrate Polymers, 2015, 134, 581- 589. doi: 10.1016/j.carbpol.2015.08.031
24	YUE Y Y , ZHOU C J , FRENCH A D , et al. Comparative properties of cellulose nano-crystals from native and mercerized cotton fibers[J]. Cellulose, 2012, 19 (4): 1173- 1187. doi: 10.1007/s10570-012-9714-4

催化剂 catalyst	转化率/% conversion rate	产物产率yield of products/%
催化剂 catalyst	转化率/% conversion rate	糠醛 furfural	甲基葡萄糖苷 methylglucoside	乙酰丙酸 levulinic acid	乙酰丙酸甲酯 methyl levulinate
H₂SO₄	85.2	8.3	3.3	17.1	43.9
H₃PO₄	71.2	11.8	3.3	9.7	25.9
FeCl₃	68.2	1.3	0.3	3.8	13.4
CrCl₃	63.1	1.1	0.6	5.3	12.3
SnCl₄	64.3	1.9	0.7	4.6	14.2
InCl₃	61.5	1.7	0.4	3.8	13.5
Fe₂(SO₄)₃	80.3	8.3	2.8	5.3	42.3
CuSO₄	74.3	6.6	3.8	7.4	38.7
Al₂(SO₄)₃	82.6	8.6	4.4	7.6	58.3
FePO₄	82.5	7.6	5.8	9.3	52.9

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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

Preparation of Levulinic Acid and Methyl Levulinate from Cellulose Catalyzed by Solid Iron Phosphate

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