色谱 ›› 2019, Vol. 37 ›› Issue (4): 454-461.DOI: 10.3724/SP.J.1123.2018.10032

• 技术与应用 • 上一篇    

Cu-Ce/γ-Al2O3对硬脂酸催化水热脱氧产生烷烃的效果

于琪1, 张祖浩1, 尹昭森1, 孔圣艳1, 杨滋恒1, 陈佳毅2, 张景来1   

  1. 1. 中国人民大学, 北京 100872;
    2. 大唐环境产业集团股份有限公司, 北京 100098
  • 收稿日期:2018-10-22 出版日期:2019-04-08 发布日期:2015-02-14
  • 通讯作者: 张景来.Tel:(010)82502695,E-mail:zhangjl@ruc.edu.cn
  • 基金资助:

    中国人民大学"中央高校建设世界一流大学(学科)和特色发展引导专项资金".

Effect of Cu-Ce/γ-Al2O3 catalyst on bio-oil production by hydrothermal deoxygenation of stearic acid

YU Qi1, ZHANG Zuhao1, YIN Zhaosen1, KONG Shengyan1, YANG Ziheng1, CHEN Jiayi2, ZHANG Jinglai1   

  1. 1. Renmin University of China, Beijing 100872, China;
    2. Datang Environment Industry Group Co. Ltd., Beijing 100098, China
  • Received:2018-10-22 Online:2019-04-08 Published:2015-02-14
  • Supported by:

    Fund for Building World-Class Universities (Disciplines) of Renmin University of China.

摘要:

利用等体积浸渍法制备Cu-Ce/γ-Al2O3催化剂,并在无H2存在的条件下对硬脂酸进行催化水热液化。对催化剂进行BET比表面积分析和X射线衍射(XRD)分析可知,Cu-Ce/γ-Al2O3催化剂中存在CuO和CeO2两种晶型,在300℃条件下水热反应12 h后具有更好的热稳定性。通过对硬脂酸进行水热液化实验和对生物油进行气相色谱-质谱(GC-MS)分析发现,加入Cu-Ce/γ-Al2O3催化剂能够获得最高的硬脂酸转化率(94.71%)和总烃产率(81.41%),水热液化脱氧效果最好。分析正烷烃的产率,结果发现硬脂酸在高温水热条件下主要发生脱羧反应。Cu-Ce/γ-Al2O3催化剂的加入能够同时促进反应过程中脱羧反应、加氢脱氧反应和裂化反应。此外,Cu-Ce/γ-Al2O3还能够促进羰基基团的脱除,有效减少产物中的醛和酮类物质。

关键词: -Al2O3催化剂, Cu-Ce/&gamma, 气相色谱-质谱, 生物油, 水热液化, 脱氧, 硬脂酸

Abstract:

In order to improve the hydrothermal deoxygenation of organic acids as well as to reduce the cost, we prepared a Cu-Ce/γ-Al2O3 catalyst to study the hydrothermal deoxygenation of stearic acid in the absence of H2. The Brunauer-Emmett-Teller surface area and X-ray diffraction pattern suggest that both CuO and CeO2 exist in the Cu-Ce/γ-Al2O3 catalyst. The crystals of Cu-Ce/γ-Al2O3 were more stable compared with those of the Cu/γ-Al2O3 catalyst after 12 h of hydrothermal liquefaction at 300℃, thereby indicating a better thermal stability of the former. The presence of Cu-Ce/γ-Al2O3 catalyst could greatly improve the conversion of stearic acid (94.71%) and the yield of hydrocarbon (81.41%). A preliminary analysis of the mechanism suggests that decarboxylation is the main step in the deoxygenation during the hydrothermal liquefaction of stearic acid. The addition of Cu/γ-Al2O3 and Cu-Ce/γ-Al2O3 decreased the yield of n-heptadecane and increased the yield of n-octadecane. Besides, the yields of n-paraffins increased drastically from 0.45% to 49.72% along the series from n-nonane to n-hexadecane. Thus, the cracking reactions could be improved in the presence of Cu-Ce/γ-Al2O3, suggesting that it is an efficient deoxygenation catalyst in the hydrothermal liquefaction of organic acid. In addition, the Cu-Ce/γ-Al2O3 catalyst could help in removing the carbonyl groups, and this effectively reduced the amounts of aldehydes and ketones in the bio-oil.

Key words: bio-oil, Cu-Ce/γ-Al2O3 catalyst, deoxygenation, gas chromatography-mass spectrometry (GC-MS), hydrothermal liquefaction, stearic acid

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