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石化资源的开发与利用极大的丰富了人们的生活水平,仅在能源消费中,石化资源就占80%以上,除此之外,它还是重要有机化工的原料,可以用来生产合成树脂、合成橡胶以及多种精细化学品,然而随着它们储量的不断减少以及全球气候变暖的影响,寻找可替换石化资源的可再生资源是势在必行的。目前,人们已经开发了多种可再生资源:如生物质,风能,太阳能和潮汐能等。与其他资源相比,生物质不仅可转化为其他可再生资源,而且还能直接制备成燃油,平台化合物和生物基材料等产品,除此之外,其含量丰富,仅我国一年的生物质可利用资源量就相当于4.11亿吨标准煤 [1],这些都为生物质的可持续转化提供了坚实的基础[2]。
目前生物质资源的转化方法主要有以下几类:直接利用法、酶解法和化学催化法。直接利用法是将生物质直接燃烧转化为热量,存在能量利用形式单一,能源利用度低和环境污染等问题,因此发展前景受限。酶解法是利用微生物或生物酶发酵将生物质转化为沼气和生物乙醇,该法生产成本高[3],转化时间长和产物单一。化学催化法是通过控制反应体系中加入的催化剂和辅料生产出各种化学产品,如5-羟甲基糠醛[4],戊二醇[5],异山梨醇[6]和2,5-呋喃二羧酸[7]等,生产速度快,因此具有广阔的发展前景。
化学催化法研究的首要的任务是制备出适宜的催化剂[8],常用的均相催化剂如硫酸,盐酸和磷酸等对生物质的转化具有良好的催化效果[9],但在大规模化的应用中存在着废水量大,催化剂难以回收和设备容易被腐蚀等诸多问题[10]。非均相催化剂如固体酸具有安全性高,存储方便、副产物少、易于分离与能重复利用等特点[11],因此,利用固体酸催化生物质转化具有广阔的发展前景 [12]。
本文从以下两个方面对近年来固体酸催化生物质转化的研究进行综述:(1)用于生物质催化转化的固体酸种类;(2)固体酸在催化生物质转化成各类产品中的应用。同时在文章最后对这个领域进行展望,以期为固体酸催化生物质转化提供一些参考。
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目前固体酸的种类有沸石,金属氧化物,硫酸化金属氧化物,杂多化合物,碳基固体酸、阳离子交换树脂、固载化液体酸和天然黏土等,这些固体酸由于自身带有酸性基团或具有吸收电子的能力,因此表现出酸性,而常用于催化生物质转化的固体酸主要有以下几类(见表1)。
表 1 常用于生物质催化转化固体酸催化剂的种类
Table 1. Types of solid acid catalysts commonly used in biomass catalytic conversion
序号 类型 实例 1 沸石 H-ZMS-5 2 金属氧化物 Al2O3,SiO2,ZnO 3 硫酸化金属氧化物 SO42−/SnO2,SO42−/ZrO2 4 杂多化合物 [TEA-PS]1.5H1.5PW12O40,H3PW12O40 5 阳离子交换树脂 Amberlyst 15, Amberlyst 31 6 碳基固体酸
Research Progress on Biomass Conversion Catalyzed by Solid Acids
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摘要: 受能源危机和环境污染的影响,绿色环保的固体酸催化剂在催化生物质转化为各类化学品方面的研究已成为近期的热点。本文综述了固体酸在生物质催化转化上的研究进展,首先列举可用于生物质转化的固体酸种类,接着介绍了固体酸催化剂在催化生物质转化生成生物质燃料、生物质平台化合物和生物基材料的研究状况,然后总结了在应用中存在的问题,最后展望解决这一问题的建议和思路。Abstract: Due to the impact of energy crisis and environmental pollution, the research of green solid acid catalysts in catalyzing the conversion of renewable biomass into various chemicals has become a hot spot in recent years. In this paper, the research progress of solid acid in biomass catalytic conversion was reviewed. Firstly, types of solid acids that could be used for biomass conversion were listed. Secondly, the research status of solid acid catalysts in catalyzing the biomass conversion to produce biomass fuels, biomass platform compounds and bio-based materials was introduced. Finally, the existing problems in the application were summarized, and then the suggestions and ideas for solving these problems were recommended.
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Key words:
- Solid acid;
- Biomass;
- Biomass fuel;
- Biomass platform compounds;
- Bio-based materials
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图 1 木质纤维素热解制备燃油的简要转化过程[19]
Fig. 1 Brief conversion process of lignocellulose pyrolysis to prepare fuel oil
图 2 木质纤维素热解制备燃气的简要转化过程[24]
Fig. 2 Brief conversion process of lignocellulose pyrolysis to prepare gas
图 4 糠醛(FUR)和HMF的制备路径[39]
Fig. 4 Preparation path of FUR and HMF
表 1 常用于生物质催化转化固体酸催化剂的种类
Tab. 1 Types of solid acid catalysts commonly used in biomass catalytic conversion
序号 类型 实例 1 沸石 H-ZMS-5 2 金属氧化物 Al2O3,SiO2,ZnO 3 硫酸化金属氧化物 SO42−/SnO2,SO42−/ZrO2 4 杂多化合物 [TEA-PS]1.5H1.5PW12O40,H3PW12O40 5 阳离子交换树脂 Amberlyst 15, Amberlyst 31 6 碳基固体酸 -
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