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ZnO 改性 Ni-W/β-沸石催化剂用于纤维素氢解制备 C/C 二醇的反应路径选择。

Reaction Route Selection for Cellulose Hydrogenolysis into C/C Glycols by ZnO-Modified Ni-W/β-zeolite Catalysts.

机构信息

State Key Laboratory of Pollution Control and Resources Reuse, Key Laboratory of Yangtze River Water Environment of MOE, National Engineering Research Center of Protected Agriculture, Shanghai Engineering Research Center of Protected Agriculture, Tongji University, Shanghai, 200092, China.

College of Quality and Safety Engineering, China Jiliang University, Hangzhou, 310018, China.

出版信息

Sci Rep. 2019 Aug 16;9(1):11938. doi: 10.1038/s41598-019-48103-6.

Abstract

A β-zeolite-supported nickel and tungsten catalyst (Ni-W/β) was employed to generate C/C glycols (ethylene and propylene glycols) in a satisfactory yield from cellulose. After optimizing the acidity of the support, the Ni-W synergy and the co-catalyst, the yield of C/C glycols reached 70.1% (C %), with propylene glycol accounting for 51.1% of the product. This performance was attributed to the effective control of the major reaction steps, namely, hydrolysis, isomerization, retro-aldol condensation and hydrogenation, by the tailored Ni-W-ZnO/β catalyst. The characterization and reaction results indicated that the cellulose hydrolysis step was promoted by the appropriate acidic sites of the β-zeolite, and the reaction routes to C/C glycols were influenced by the mass loading of Ni-W through the synergy of nickel and tungsten oxide, in which Ni is effective in the hydrogenation while W facilitates bond cleavage via a retro-aldol condensation (C to C/C). Moreover, with the leaching of metal during four cycles of reuse, the catalytic performance was also influenced by the synergy of Ni and W. In addition, the isomerization of glucose to fructose was promoted by ZnO and afforded a high yield of propylene glycol.

摘要

一种负载于 β-沸石上的镍和钨催化剂(Ni-W/β)被用于从纤维素中以较高产率生成 C/C 二醇(乙二醇和丙二醇)。在优化了载体的酸度、Ni-W 协同作用和共催化剂之后,C/C 二醇的产率达到了 70.1%(以碳计),其中丙二醇占产物的 51.1%。这一性能归因于通过定制的 Ni-W-ZnO/β催化剂有效控制了主要反应步骤,即水解、异构化、逆醛缩合和加氢。表征和反应结果表明,纤维素的水解步骤是由β-沸石的适当酸性位促进的,而 Ni-W 的质量负载通过镍和氧化钨的协同作用影响 C/C 二醇的反应途径,其中 Ni 在加氢中有效,而 W 通过逆醛缩合(C 到 C/C)促进键的断裂。此外,在四次重复使用过程中金属的浸出也会影响 Ni 和 W 的协同作用。此外,ZnO 促进了葡萄糖向果糖的异构化,从而获得了丙二醇的高产率。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7698/6697703/8623f465078e/41598_2019_48103_Fig1_HTML.jpg

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