纳米γ-Al2O3与Ru/CMK-3混合催化转化纤维素制备山梨醇

摘要

高选择性一步转化纤维素制山梨醇,是实现纤维素制备高附加值化学品的一个重要途径。催化剂的酸水解性能及加氢性能直接影响纤维素一步转化的反应结果。筛选了一系列纳米酸性金属氧化物与Ru/CMK-3组合催化剂,结果表明纳米γ-Al₂O₃-Ru/CMK-3组合催化剂可高选择性催化纤维素转化为山梨醇,在适宜的反应条件下,纤维素转化率为49.8%,山梨醇选择性可高达91.3%。并讨论了各组合催化剂的酸性位、加氢活性位的组合特点及反应产物的分布特征,结果表明催化剂的酸性位和加氢活性位的合理匹配是提高山梨醇选择性的重要因素。当酸性位占主导时,纤维素水解生成的葡萄糖不能快速加氢转化,会降解生成5-羟甲基糠醛等副产物,从而降低山梨醇选择性。

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	郑丹
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关键词：纤维素；山梨醇；酸性位；加氢活性位；纳米酸性金属氧化物

Abstract：

The effective one-pot conversion of cellulose to sorbitol is an important way to prepare high value-added chemicals from cellulose. The one-pot conversion of cellulose is affected by the acid hydrolysis and the hydrogenation of catalyst simultaneously. In this article, catalysts with the combination of various nanosized acid metallic oxides and Ru/CMK-3 were used in the hydrolytic hydrogenation of cellulose to sorbitol. The combination of nanosized γ-Al₂O₃ and Ru/CMK-3 catalyst showed a relatively higher conversion of cellulose and better sorbitol selectivity. A cellulose conversion of 49.8% and a sorbitol selectivity of 91.3% were obtained under the optimum conditions. The acid sites and the hydrogenation sites of various combination catalysts and the distribution characteristics of the reaction products were also discussed. The result shows that the match between the acid sites and the hydrogenation sites is crucial to obtain the high selectivity of sorbitol. When the acid function is too dominant, glucose formed by hydrolysis of cellulose can not be quickly hydrogenated. This free glucose will start to degrade into byproducts (5-HMF), which leads to the low selectivity of sorbitol.

Keywords： cellulose； sorbitol； acid sites； hydrogenation sites； nanosized acid metallic oxides

Received 2014-05-10;

Fund:

国家自然科学基金(21076152,21276191);教育部博士点基金(2100032110018)。

Corresponding Authors: 王华,E-mail:tjuwanghua@tju.edu.cn。 Email: tjuwanghua@tju.edu.cn

About author: 郑丹(1989-),女,硕士研究生,现从事生物质转化的研究。

引用本文:

郑丹, 韩金玉, 王华, 吕结.纳米γ-Al₂O₃与Ru/CMK-3混合催化转化纤维素制备山梨醇[J]. 化学工业与工程, 2016,33(3): 13-18,49

Zheng Dan, Han Jinyu, Wang Hua, Lv Jie.Conversion of Cellulose into Sorbitol over Nanosized γ-Al₂O₃ and Ru/CMK-3 Combination Catalyst[J]. Chemcial Industry and Engineering, 2016,33(3): 13-18,49

[1] Ruppert A M, Weinberg K, Palkovits R. Hydrogenolysis goes bio:From carbohydrates and sugar alcohols to platform chemicals[J]. Angewandte Chemie International Edition, 2012, 51(11):2 564-2 601
[2] Klemm D, Heublein B, Fink H P, et al. Cellulose:Fascinating biopolymer and sustainable raw material[J]. Angewandte Chemie International Edition, 2005, 44(22):3 358-3 393
[3] Fleming K, Gray D G, Matthews S. Cellulose crystallites[J]. Chemistry-A European Journal, 2001, 7(9):1 831-1 836
[4] Fukuoka A, Dhepe P L. Catalytic conversion of cellulose into sugar alcohols[J]. Angewandte Chemie International Edition, 2006, 45(31):5 161-5 163
[5] Lee H, Han J W. Direct conversion of cellulose into sorbitols using dual-functionalized catalysts in neutral aqueous solution[J]. Catalysis Communications, 2012, 19:115-118
[6] Geboers J, Van de Vyver S, Ooms R, et al. Chemocatalytic conversion of cellulose:Opportunities, advances and pitfalls[J]. Catalysis Science & Technology, 2011, 1(5):714-726
[7] Ding L, Wang A, Zheng M, et al. Selective transformation of cellulose into sorbitol by using a bifunctional nickel phosphide catalyst[J]. Chem Sus Chem, 2010, 3(7):818-821
[8] Baek I G, You S J, Park E D. Direct conversion of cellulose into polyols over Ni/W/SiO₂-Al₂O₃[J]. Bioresource Technology, 2012, 114: 684-690
[9] You S J, Baek I G, Kim Y T, et al. Direct conversion of cellulose into polyols or H₂ over Pt/Na(H)-ZSM-5[J]. Korean Journal of Chemical Engineering, 2011, 28(3):744-750
[10] Geboers J, Van de Vyver S, Carpentier K, et al. Efficient catalytic conversion of concentrated cellulose feeds to hexitols with heteropoly acids and Ru on carbon[J]. Chemical Communications, 2010, 46(20):3 577-3 579
[11] Geboers J, Van de Vyver S, Carpentier K, et al. Efficient hydrolytic hydrogenation of cellulose in the presence of Ru-loaded zeolites and trace amounts of mineral acid[J]. Chemical Communications, 2011, 47(19):5 590-5 592
[12] 刘佳欣, 黄玉东. 纳米材料在纤维素催化转化中的应用[J]. 纤维素科学与技术, 2011, 19(4):74-79 Liu Jiaxin, Huang Yudong. Nanosized materials in the application of the catalytic conversion of cellulose[J]. Journal of Cellulose Science and Technology, 2011, 19(4):74-79 (in Chinese)
[13] Luo C, Wang S, Liu H. Cellulose conversion into polyols catalyzed by reversibly formed acids and supported ruthenium clusters in hot water[J]. Angewandte Chemie International Edition, 2007, 46(40):7 636-7 639
[14] Chambon F, Rataboul F, Pinel C, et al. Cellulose conversion with tungstated-alumina-based catalysts:Influence of the presence of platinum and mechanistic studies[J]. Chem Sus Chem, 2013, 6(3):500-507
[15] Zheng M, Wang A, Ji N, et al. Transition metal-tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol[J]. Chem Sus Chem, 2010, 3(1):63-66
[16] Kobayashi H, Komanoya T, Hara K, et al. Water-Tolerant mesoporous-carbon-supported ruthenium catalysts for the hydrolysis of cellulose to glucose[J]. Chem Sus Chem, 2010, 3(4):440-443
[17] 聂仁峰, 王军华, 费金华, 等. 介孔氧化铝的制备及其在甲醇脱水制二甲醚反应中的应用[J]. 催化学报, 2011, 32 (2):379-384 Nie Renfeng, Wang Junhua, Fei Jinhua, et al. Preparation of mesoporous alumina and its application in dehydration of methanol to dimethyl ether[J]. Chinese Journal of Catalysis, 2011, 32 (2):379-384 (in Chinese)
[18] Jun S, Joo S H, Ryoo R, et al. Synthesis of new, nanoporous carbon with hexagonally ordered mesostructure[J]. Journal of American Chemistry Society, 2000, 122(43):10 712-10 713
[19] Chambon F, Rataboul F, Pinel C, et al. Cellulose hydrothermal conversion promoted by heterogeneous Brønsted and Lewis acids:Remarkable efficiency of solid Lewis acids to produce lactic acid[J]. Applied Catalysis B:Environmental, 2011, 105(1/2):171-181