生物油加氢精制工艺研究进展.pdf

第 30 卷 第 9 期 农 业 工 程 学 报 Vol.30 No.9 2014年 5月 Transactions of the Chinese Society of Agricultural Engineering May 2014 183 生物油加氢精制工艺研究进展 李雁斌1,2，徐 莹 1,3，马隆龙1,2,3，陈冠益2，王铁军1,3，张 琦1,3 （1. 中国科学院广州能源研究所,广州 510640；2. 天津大学环境学院生物质能研究中心/内燃机燃烧学国家重点实验室，天 津 300072；3. 中国科学院广州能源研究所可再生能源重点实验室，广州 510640） 摘 要：该文针对近年来生物油加氢精制方面的研究进行了探讨，介绍了加氢精制原理，总结了国内外生物油加 氢精制工艺研究取得的进展，包括催化剂性能，反应机理和工艺路线的创新与研究。详细说明了分段加氢、加氢 酯化、原位加氢等工艺流程的创新和缺点；传统加氢催化剂：如 NiMo、CoMo 催化剂，以及 Ru、Pt、Pd、Rh 等 贵金属催化剂，在加氢工艺中的特点，前者价格便宜但效果较差，失活现象更严重；后者具有更强的反应活性， 但价格昂贵且须在反应后回收。同时，该文对模型化合物、生物油部分相以及生物油真实体系的加氢试验分别进 行了详述。最后，针对目前研究中遇到的无法长时间连续运行，成本过高工艺复杂以及缺乏合适催化剂等问题， 预测了该技术未来加强催化剂抗结焦能力和低温活性，简化工艺流程并降低成本的研究方向。 关键词：生物质；燃料；催化剂；生物油；加氢；原位加氢；加氢酯化；分段加氢 doi：10.3969/j.issn.1002-6819.2014.09.023 中图分类号：TE665.6 文献标志码：A 文章编号：1002-6819(2014)-09-0183-09 李雁斌，徐 莹，马隆龙，等. 生物油加氢精制工艺研究进展J. 农业工程学报，2014，30(9)：183191. Li Yanbin, Xu Ying, Ma Longlong, et al. Development in hydrotreating process of bio-oilJ. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2014, 30(9): 183191. (in Chinese with English abstract) 0 引 言 近年来，随着原油价格的不断攀升，以及国际 社会对温室效应的担忧，各国纷纷加紧寻找可再生 的新能源。而生物油被认为是一种重要的化石燃料 替代品，也是近年来国内外研究的重点之一。但是 无论是热解生物油还是由各类植物制成的植物油， 都存在着高黏度、高腐蚀性1、高含水率2、对设 备损耗大等问题，导致生产出来的生物油无法作为 普通燃料直接使用，所以生物油必须经过精制转化 为更优质的燃料油3。生物油精制的方法很多，包 括催化裂化、催化加氢、乳化、分子蒸馏等方法。 加氢工艺是生物油精制工艺中比较成熟的一 种，国内外也普遍认为4加氢工艺是传统生物油精 制工艺中比较高效的工艺。对这种工艺的研究已经 进行了超过 25 a 5。国内外许多研究者都针对生物 油的理化特性，对生物油加氢精制反应进行过研 收稿日期：2013-11-15 修订日期：2014-01-03 基金项目：国家自然科学基金资助项目（51036006 2009. 25 Xiong W M, Fu Y, Zeng F X, et al. An in situ reduction approach for bio-oil hydroprocessingJ. Fuel Processing Technology, 2011, 92(8): 15991605. 26 Fisk CA, Morgan T, Ji Y, et al. Bio-oil upgrading over platinum catalysts using in situ generated hydrogenJ. Applied Catalysis A: General, 2009, 358(2): 150156. 27 Popov A, Kondratieva E, Goupil J M, et al. 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Applied Catalysis A: General, 2012, 449: 121130. Development in hydrotreating process of bio-oil Li Yanbin1,2, Xu Ying1,3, Ma Longlong1,2,3 , Chen Guanyi2, Wang Tiejun1,3, Zhang Qi1,3 (1. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China; 2. Faculty of Environmental Science and Engineering/State Key Lab of international Combustion Engine, Tianjin University, Tianjin 300072, China; 3. Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China) Abstract: This paper reviews catalytic the hydrotreatment upgrading technology of biomass-derived oil. It provides an overview of the reaction mechanism and the condition of the operation, then summarizes the process of bio-oil hydrogenation at home and abroad. Detailed comparison of various technological processes such as multi-stage hydrogenation, hydrogenation-esterification, in-situ hydrogenation, etc. are made. Multi-stage hydrogenation, which separates the hydroprocessing into two stages (mild hydrotreating and deep hydrotreating), can improve the selectivity of products, moreover avoiding an economic penalty by using less hydrogen. Hydrogenation-esterification combines hydrogenation and esterfication to establish a new upgrading method. Through the method, unstable compounds of biomass-derived oil can be converted more effectively. In-situ hydrogenation, which leads to reducing the cost and enhancing the safety, uses other reagents as resources of hydrogen, simultaneously generating hydrogen and hydrotreating in one reaction system to replace transporting hydrogen from outside. The reasonable optimization of the process routes benefits improving product quality. Research in this area is expected to become a main research direction for bio-oil hydrotreatment. Experimental data were collected about various model compounds including cresol, phenol, guaiacol, acetone, aldehyde, etc. and bio-oil from the literature in the field of this study. Also, a test is reviewed about a range of catalysts including the conventional and novel types of supported noble metal and transition metal catalytic materials and their performance in bio-oil hydroprocessing. Conventional catalysts, such as NiMo and CoMo, have economic advantages; the reaction using noble metal catalysts have better reactivity; amorphous catalysts