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催化木质素增值转化工艺生产芳烃化学品和氢气。

Catalytic lignin valorization process for the production of aromatic chemicals and hydrogen.

机构信息

Utrecht University, Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.

出版信息

ChemSusChem. 2012 Aug;5(8):1602-9. doi: 10.1002/cssc.201100699. Epub 2012 Jun 27.

DOI:10.1002/cssc.201100699
PMID:22740175
Abstract

With dwindling reserves of fossil feedstock as a resource for chemicals production, the fraction of chemicals and energy supplied by alternative, renewable resources, such as lignin, can be expected to increase in the foreseeable future. Here, we demonstrate a catalytic process to valorize lignin (exemplified with kraft, organosolv, and sugarcane bagasse lignin) using a mixture of cheap, bio-renewable ethanol and water as solvent. Ethanol/water mixtures readily solubilize lignin under moderate temperatures and pressures with little residual solids. The molecular weight of the dissolved lignins was shown to be reduced by gel permeation chromatography and quantitative HSQC NMR methods. The use of liquid-phase reforming of the solubilized lignin over a Pt/Al(2)O(3) catalyst at 498 K and 58 bar is introduced to yield up to 17 % combined yield of monomeric aromatic oxygenates such as guaiacol and substituted guaiacols generating hydrogen as a useful by-product. Reduction of the lignin dissolved in ethanol/water using a supported transition metal catalyst at 473 K and 30 bar hydrogen yields up to 6 % of cyclic hydrocarbons and aromatics.

摘要

随着化石原料储备的减少,作为化学品生产资源,替代的可再生资源(如木质素)提供的化学品和能源的比例预计将在可预见的未来增加。在这里,我们展示了一种使用廉价的生物可再生乙醇和水的混合物作为溶剂来增值木质素(以 kraft、有机溶剂和甘蔗渣木质素为例)的催化过程。在温和的温度和压力下,乙醇/水混合物很容易溶解木质素,几乎没有残留的固体。通过凝胶渗透色谱和定量 HSQC NMR 方法表明,溶解的木质素的分子量降低。通过在 498 K 和 58 巴下在 Pt/Al(2)O(3)催化剂上对溶解的木质素进行液相重整,可得到高达 17%的单体芳香族含氧化合物(如愈创木酚和取代的愈创木酚)的总收率,同时生成氢气作为有用的副产物。在 473 K 和 30 巴氢气下,使用负载过渡金属催化剂还原溶解在乙醇/水中的木质素,可得到高达 6%的环状烃类和芳烃。

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