Directional conversion of lignocellulosic biomass to methyl levulinate over supported metal solid acid

doi:10.16085/j.issn.1000-6613.2023-0836

Abstract

Abstract:

Lignocellulosic biomass is an abundant and green resources. Preparation of high added-value liquid fuels and chemicals from lignocellulosic biomass can alleviate society's demand for fossil fuels and improve the ecological environment, and thus contribute to the "dual-carbon" objective. In this study, a variety of metal-supported solid acid catalysts were prepared for conversion of biomass carbohydrates to methyl levulinate. The prepared catalysts were characterized and were found to possess bifunctional properties(B- and L-acid active centers). The catalyst with AlCl₃ loaded on surface to provide L-acid showed the best catalytic performance. The effects of different factors such as reaction temperature and time on the simultaneous directional conversion of glucose and xylose to methyl levulinate were investigated in detail. A raw material conversion of 100% and levulinic acid/ester yield of 24.96% could be obtained with the co-solvent of dimethoxy-methane/methanol (1∶1 mass ratio) at 200℃ for 2h.

Key words: lignocellulosic biomass, catalyst, compounded solvent, biofuel, esterification

摘要：

木质纤维生物质是一种存量丰富、绿色的资源，通过利用木质纤维生物质制备高值化的液体燃料和化学品，不但可以缓解社会对化石燃料需求的压力，而且可以改善生态环境，助力“双碳”目标。本研究制备了多种金属负载型固体酸催化剂，用于催化生物质碳水化合物高效转化为乙酰丙酸甲酯。通过表征手段研究所制备催化剂的特性，发现其具备双功能特性（B酸和L酸活性中心）。其中，AlCl₃作为L酸供应体，负载到催化剂表面，催化性能最佳。研究反应温度和时间等因素对葡萄糖、木糖同步定向转化为乙酰丙酸甲酯的影响发现：在复合溶剂二甲氧基甲烷/甲醇的质量比1∶1、反应温度200℃、反应时间120min的条件下性能最好，原料的转化率达到了100%，乙酰丙酸/酯的最大收率达到了24.96%。

关键词: 木质纤维生物质, 催化剂, 复合溶剂, 生物燃料, 酯化

CLC Number:

TQ032

HE Shikun, ZHANG Wenhao, FENG Junfeng, PAN Hui. Directional conversion of lignocellulosic biomass to methyl levulinate over supported metal solid acid[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3042-3050.

何世坤, 张文豪, 冯君锋, 潘晖. 负载金属型固体酸催化木质纤维生物质定向转化为乙酰丙酸甲酯[J]. 化工进展, 2024, 43(6): 3042-3050.

Figures/Tables 17

References 31

1	TIAN Yijun, ZHANG Fangfang, WANG Jieni, et al. A review on solid acid catalysis for sustainable production of levulinic acid and levulinate esters from biomass derivatives[J]. Bioresource Technology, 2021,342: 125977.
2	PENG Qingpo, JIANG Yongjun, XU Beibei, et al. Zr oxo cluster for cascade conversion of furfural to alkyl levulinates[J]. ChemCatChem, 2023,15(5): e202201352.
3	BESSON Michèle, GALLEZOT Pierre, PINEL Catherine. Conversion of biomass into chemicals over metal catalysts[J]. Chemical Reviews, 2014, 114(3): 1827-1870.
4	王磊, 徐天晓, 韩燕絮, 等. Ru/有机改性蛭石催化乙酰丙酸甲酯加氢性能的研究[J]. 燃料化学学报, 2020, 48(1): 100-107.
	WANG Lei, XU Tianxiao, HAN Yanxu, et al. Study on the catalytic hydrogenation of methyl levulinate over Ru/organic modified vermiculite[J]. Journal of Fuel Chemistry and Technology, 2020, 48(1): 100-107.
5	徐漓, 吴玉锋, 张元甲, 等. “双碳”背景下广东农林废弃物综合利用技术进展[J]. 化工进展, 2023, 42(11): 5648-5660.
	XU Li, WU Yufeng, ZHANG Yuanjia, et al. The progress of comprehensive utilization technology of agricultural and forestry wastes in Guangdong under the background of “carbon peaking and carbon neutrality”[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5648-5660.
6	IMYEN Thidarat, SAENLUANG Kachaporn, DUGKHUNTOD Pannida, et al. Investigation of ZSM-12 nanocrystals evolution derived from aluminosilicate nanobeads for sustainable production of ethyl levulinate from levulinic acid esterification with ethanol[J]. Microporous and Mesoporous Materials, 2021, 312: 110768.
7	曾媛, 王允圃, 张淑梅, 等. 生物质微波热解制备液体燃料和化学品的研究进展[J]. 化工进展, 2021, 40(6): 3151-3162.
	ZENG Yuan, WANG Yunpu, ZHANG Shumei, et al. Research progress in preparation of liquid fuels and chemicals by microwave pyrolysis of biomass[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3151-3162.
8	JIANG Linyun, ZHOU Lipeng, CHAO Jinyun, 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.
9	CIPTONUGROHO Wirawan, MENSAH Joel B, Ghith AL-SHAAL, et al. WO _x /ZrO₂ catalysts for the conversion of α-angelica lactone with butanol to butyl levulinates[J]. Chemical Papers, 2023, 77(7): 3769-3778.
10	PENG Lincai, LIN Lu, LI Hui, et al. Conversion of carbohydrates biomass into levulinate esters using heterogeneous catalysts[J]. Applied Energy, 2011, 88(12): 4590-4596.
11	TANG Ge, DENG Kuaqian, LI Panyang, et al. One-pot method of recyclable lipase-nanocatalyst based on chitosan magnetic nanomaterial for ethyl levulinate synthesis[J]. Composites Science and Technology, 2023, 236: 110002.
12	Cristhian CAñON, SANCHEZ Nestor, COBO Martha. Sustainable production of ethyl levulinate by levulinic acid esterification obtained from Colombian rice straw[J]. Journal of Cleaner Production, 2022, 377: 134276.
13	徐杨杨, 祝慧敏, 李辰, 等. 竹材纤维定向醇解转化制备乙酰丙酸甲酯的研究[J]. 燃料化学学报, 2021, 49(12): 1889-1897.
	XU Yangyang, ZHU Huimin, LI Chen, et al. Study on preparation of methyl levulinate by directional alcoholysis of bamboo biomass[J]. Journal of Fuel Chemistry and Technology, 2021, 49(12): 1889-1897.
14	DU Xinyuan, LU Xuebin, BAI Hui, et al. Mesoporous molecular sieves solid superacid as a catalyst for alcoholysis of fructose into methyl levulinate[J]. Biomass and Bioenergy, 2022, 166: 106627.
15	ZHANG Luxin, TIAN Lu, XU Ziyuan, et al. Direct production of ethyl levulinate from carbohydrates and biomass waste catalyzed by modified porous silica with multiple acid sites[J]. Process Biochemistry, 2022, 121: 152-162.
16	TIWARI Manishkumar S, GAWADE Anil B, YADAV Ganapati D. Magnetically separable sulfated zirconia as highly active acidic catalysts for selective synthesis of ethyl levulinate from furfuryl alcohol[J]. Green Chemistry, 2017, 19(4): 963-976.
17	GAUTAM Priyanka, BARMAN Sanghamitra, Amjad ALI. A comparative study on the performance of acid catalysts in the synthesis of levulinate ester using biomass-derived levulinic acid: A review[J]. Biofuels, Bioproducts and Biorefining, 2022, 16(4): 1095-1115.
18	CHAOWAMALEE Supphathee, YAN Ning, NGAMCHARUSSRIVICHAI Chawalit. Propylsulfonic acid-functionalized mesostructured natural rubber/silica nanocomposites as promising hydrophobic solid catalysts for alkyl levulinate synthesis[J]. Nanomaterials, 2022, 12(4): 604.
19	CHHABRA Tripti, ROHILLA Jyoti, KRISHNAN Venkata. Nanoarchitectonics of phosphomolybdic acid supported on activated charcoal for selective conversion of furfuryl alcohol and levulinic acid to alkyl levulinates[J]. Molecular Catalysis, 2022, 519: 112135.
20	RUSSO Vincenzo, ROSSANO Carmelina, SALUCCI Emiliano, et al. Intraparticle diffusion model to determine the intrinsic kinetics of ethyl levulinate synthesis promoted by Amberlyst-15[J]. Chemical Engineering Science, 2020, 228: 115974.
21	BADGUJAR Kirtikumar C, BADGUJAR Vivek C, BHANAGE Bhalchandra. M. A review on catalytic synthesis of energy rich fuel additive levulinate compounds from biomass derived levulinic acid [J]. Fuel Processing Technology, 2020, 197: 106213.
22	MELFI Diego Trevisan, DOS SANTOS Kallynca Carvalho, RAMOS Luiz Pereira, et al. Supercritical CO₂ as solvent for fatty acids esterification with ethanol catalyzed by Amberlyst-15[J]. The Journal of Supercritical Fluids, 2020, 158: 104736.
23	WANG Zixin, XIE Chao, LI Xun, et al. Amberlyst-15 supported zirconium sulfonate as an efficient catalyst for Meerwein-Ponndorf-Verley reductions[J]. Chemical Communications, 2022, 58(25): 4067-4070.
24	XU Siquan, YIN Chunyu, PAN Donghui, et al. Efficient conversion of glucose into 5-hydroxymethylfurfural using a bifunctional Fe³⁺ modified Amberlyst-15 catalyst[J]. Sustainable Energy & Fuels, 2019, 3(2): 390-395.
25	周硕, 王辉, 王苏宁, 等. 硅铝比对Cu/SSZ-13分子筛低温催化性能的影响[J].化学工程, 2021, 49(7): 61-66.
	ZHOU Shuo, WANG Hui, WANG Suning, et al. Effect of Si/Al ratio on catalytic reduction performance of Cu/SSZ-13 zeolite for NH₃-SCR at low temperature[J]. Chemical Engineering, 2021, 49(7): 61-66.
26	ÖZGÜR Derya Öncel, Tayyibe ŞIMŞEK, Göksel ÖZKAN, et al. The Hydroloysis of ammonia borane by using Amberlyst-15 supported catalysts for hydrogen generation[J]. International Journal of Hydrogen Energy, 2018, 43(23): 10765-10772.
27	XING Xinyi, SHI Xian, HU Rui, et al. Hf-β zeolites as highly efficient catalysts for the production of 5-hydroxymethylfurfural from cellulose in biphasic system[J]. International Journal of Biological Macromolecules, 2022, 222: 3014-3023.
28	彭林才, 林鹿, 李辉. 生物质转化合成新能源化学品乙酰丙酸酯[J].化学进展, 2012, 24(5): 801-809.
	PENG Lincai, LIN Lu, LI Hui. Conversion of biomass into levulinate esters as novel energy chemicals[J]. Progress in Chemistry, 2012, 24(5): 801-809.
29	KASAR Gayatri B, DATE Nandan S, BHOSALE P N, et al. Steering the ester and γ-valerolactone selectivities in levulinic acid hydrogenation[J]. Energy & Fuels, 2018, 32(6): 6887-6900.
30	WU Xiaoyu, FU Jie, LU Xiuyang. One-pot preparation of methyl levulinate from catalytic alcoholysis of cellulose in near-critical methanol[J]. Carbohydrate Research 2012, 358: 37-39.
31	RAVASCO Joao M J M, COELHO Jaime A S, SIMEONOV Svilen P, et al. Bifunctional Cr³⁺ modified ion exchange resins as efficient reusable catalysts for the production and isolation of 5-hydroxymethylfurfural from glucose[J]. RSC Advances, 2017, 7(13): 7555-7559.

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/Å
A15	385.94	0.63	65.70
2%AlCl₃-A15	37.65	0.24	106.00
4%AlCl₃-A15	77.60	0.36	184.22
6%AlCl₃-A15	55.70	0.34	242.49

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/Å
A15	385.94	0.63	65.70
2%AlCl₃-A15	37.65	0.24	106.00
4%AlCl₃-A15	77.60	0.36	184.22
6%AlCl₃-A15	55.70	0.34	242.49

催化剂	B酸/mmol·g^-1	L酸/mmol·g^-1	L酸/B酸
2%AlCl₃-A15	0.037	0.047	1.27
4%AlCl₃-A15	0.058	0.068	1.17
6%AlCl₃-A15	0.049	0.051	1.04

催化剂	B酸/mmol·g^-1	L酸/mmol·g^-1	L酸/B酸
2%AlCl₃-A15	0.037	0.047	1.27
4%AlCl₃-A15	0.058	0.068	1.17
6%AlCl₃-A15	0.049	0.051	1.04

催化剂	原料转化率/%	糠醛得率/%	5-羟甲基糠醛得率/%	糖苷类得率/%	乙酰丙酸得率/%	乙酰丙酸甲酯得率/%	乙酰丙酸/酯得率/%
6%LiCl/乙醇-A15	100	0.08	1.90	1.09	3.62	14.35	17.97
6%LiCl/水-A15	100	0.10	3.02	0.79	8.36	15.20	23.56
6%LiCl/甲醇-A15	100	0.06	1.07	0.89	1.14	13.23	14.37