第41卷第5期 2013年5月
文章编号：0253-2409(2013)05-0571-08
燃料化学学报
Journal of Fuel Chemistry and Technology
小球藻热裂解油催化加氢精制研究
仲卫成，郭庆杰，王许云，张亮
（青岛科技大学化工学院，清洁化工过程山东省高校重点实验室，山东青岛266042）
Vol. 41 No.5 May 2013
摘要：以Ni-Co-Pd/-Al,O,为催化剂，在固定床反应器中研究了小球藻热裂解油的催化加氢精制。在较低加氢压力（2x 10°Pa)下考察了加氢温度和氢油比（体积比)对精制生物油的含水率、热值、运动黏度和十六烷值等参数的影响，并对加氢前后油品进行了元素分析和GC-MS分析。结果表明，在2x10°Pa压力下，氢油比为120：1，温度为300℃时，精制油收率达 89.6%，热值和十六烷值较加氢前分别增加了17.94%和71.2%，黏度下降66.32%。元素分析和GC-MS分析表明，精制生物油的H/C原子比由1.55提高至1.97，氧、氮、硫含量明显降低，脱氧率达到80.46%。精制油中的有机酸、酯、酮、醛的含量明显降低，烷烃和醇醚含量明显增加。
关键词：小球藻热裂解油；催化加氢；Ni-Co-Pd/-Al,O,催化剂；反应机理中图分类号：TK6
5文献标识码：A
Catalytichydroprocessingofthefastpyrolysisbio-oilofChlorella
ZHONG Wei-cheng, GUO Qing-jie, WANG Xu-yun, ZHANG Liang
(Key Laboratory of Clean Chemical Processing of Shandong Province,
College of Chemical Engineering, Qingdao University of Science & Technology, Qingdao2
266042,China)
Abstract : Catalytic hydroprocessing of the bio-oil obtained through fast pyrolysis of Chlorella was carried out in a bench-scale continuous-flow fixed-bed reactor equipped with a Ni-Co-Pd/y-Al,O, catalyst. The effects of the hydrogenation temperature and the H/oil molar ratio on the moisture content, calorific value, viscosity and cetane number of the refined bio-oils were investigated at the pressure of 2x1o° Pa, It was shown that the yield of the refined oil reached 86. 1% , and the calorific value and cetane number were increased by 17.94% and 71. 2% respectively, while the viscosity was decreased by 66.32% at the temperature of 300 C, the pressure of 2x10° Pa and the H/oil mol ratio of 120. The elemental analysis and GC-MS analysis results of the bio-oil before and after hydrogenation show that the H/C mol ratio was increased from 1. 55 to 1.97, while the oxygen, nitrogen and sulfur contents were significantly decreased. The deoxidation degree reached 80. 46%. The amounts of organic acids, esters, ketones and aldehyde in the refined oils were obviously decreased, while those of alcohols and alkanes were markedly increased.
Key words : chlorella pyrolysis oil; catalytic hydroprocessing; Ni-Co-Pd/y-Al, O, catalyst; reaction mechanism
生物质油[1]是通过快速加热的方式使生物质中的高分子物质裂解成低分子有机蒸气，并采用骤冷的方法得到液体。未精制的油品含氧量高，导致其稳定性差、热值低、黏度大，尤其是酸性含氧化合物还会造成设备的腐蚀，给生物质油的运输与储存带来难度。生物质油精制技术的核心是去除其中的氧，提高H/C比，使其有是够高的燃烧热值和十六烷值、适宜的黏度和pH值2]。
近年来，有关生物质油加氢提质的研究报道较多，主要集中于纤维素和木质素类（如玉米秸秆、松树枝、锯末等)生物质热解油3,4}，且一般是在高压(5×10°~1.5×10°Pa）和中高温度（150~450℃）下对模型含氧化合物进行考察。Douglas等3]在
收稿日期：2012-12-31；修回日期：2013-02-21。
6×10°~1×10°Pa压力和170~450℃对松木屑快速热裂解油进行了催化加氢精制，研究了适于芬兰松树生物油加氢精制的工艺过程。Gandarias等16用催化剂Ni-W/y-Al,O,和Ni-Mo/-Al,O，研究了酚类化合物的加氢脱氧(HDO)反应。研究发现，在预硫化和预还原两种状态下，Ni-Mo催化剂均比Ni-W 催化剂有更高的活性，加氢脱氧的主要产物为苯、环已烯、环已烷以及甲基环戊烷。杨骏等7在反应温度240~320℃、氢油比700、液体空速1.5h-、压力 4x10°Pa条件下，考察了Mo-Ni/Al,O，系列催化剂对模型含氧化合物醇和酸的加氢脱氧反应性能。结果表明,Mo-Ni/Al,O，催化剂对醇和酸具有高的加氢脱氧活性。其中，Mo16Ni6/Al,O，催化剂在
基金项目：海洋可再生能源专项资金（GHME2001SW02）；山东省科技攻关项目（2008GG10006010，2009GG10007001）。联系作者：郭庆杰，Tel;0532-84022757，Fax;0532-84022757，E-mail;qi.guo@yahoo.com。
本文的英文电子版由Elsevier出版社在ScienceDirect_上出版（http：//www.sciencedirect.com/science/joumal/18725813）。