Cu-Ce/γ-Al2O3对硬脂酸催化水热脱氧产生烷烃的效果

引用本文: 于琪, 张祖浩, 尹昭森, 孔圣艳, 杨滋恒, 陈佳毅, 张景来. Cu-Ce/γ-Al₂O₃对硬脂酸催化水热脱氧产生烷烃的效果[J]. 色谱, 2019, 37(4): 454-461. doi: 10.3724/SP.J.1123.2018.10032 shu

Citation: YU Qi, ZHANG Zuhao, YIN Zhaosen, KONG Shengyan, YANG Ziheng, CHEN Jiayi, ZHANG Jinglai. Effect of Cu-Ce/γ-Al₂O₃ catalyst on bio-oil production by hydrothermal deoxygenation of stearic acid[J]. Chinese Journal of Chromatography, 2019, 37(4): 454-461. doi: 10.3724/SP.J.1123.2018.10032 shu

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.
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
基金项目:
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".

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:

English

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

1.
Renmin University of China, Beijing 100872, China;
2.
Datang Environment Industry Group Co. Ltd., Beijing 100098, China
Received Date: 22 October 2018
Fund Project:
Fund for Building World-Class Universities (Disciplines) of Renmin University of China.

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:

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

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Cu-Ce/γ-Al₂O₃对硬脂酸催化水热脱氧产生烷烃的效果

English

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

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