Ru催化加氢选择性脱除F-T合成水相中的含氧化合物

doi:10.3969/j.issn.0438-1157.2014.11.019

化工学报 ›› 2014, Vol. 65 ›› Issue (11): 4347-4355.DOI: 10.3969/j.issn.0438-1157.2014.11.019

• 催化、动力学与反应器 • 上一篇下一篇

Ru催化加氢选择性脱除F-T合成水相中的含氧化合物

陈伦刚¹, 刘勇^1,2, 定明月¹, 张兴华¹, 李宇萍¹, 张琦¹, 王铁军¹, 马隆龙¹

1. 中国科学院广州能源研究所, 中国科学院可再生能源重点实验室, 广东广州 510640;
2. 中国科学院大学, 北京 100049

收稿日期:2014-03-26 修回日期:2014-08-18 出版日期:2014-11-05 发布日期:2014-11-05
通讯作者: 陈伦刚
基金资助:
广东省-中国科学院全面战略合作项目(2012B090400042);中国科学院重点部署项目(KGZD-EW-304-2);广东省自然科学基金项目 (S2013040016417).

Removal of oxygenates in aqueous phase product of F-T process by catalytic hydrogenation over Ru catalyst

CHEN Lungang¹, LIU Yong^1,2, DING Mingyue¹, ZHANG Xinghua¹, LI Yuping¹, ZHANG Qi¹, WANG Tiejun¹, MA Longlong¹

1. Chinese Academy of Sciences Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2014-03-26 Revised:2014-08-18 Online:2014-11-05 Published:2014-11-05
Supported by:
supported by the Guangdong Province-Chinese Academy of Comprehensive Strategic Cooperation Project (2012B090400042), the Key Program of Chinese Academy of Sciences (KGZD-EW-304-2), and the Natural Science Foundation of Guangdong Province (S2013040016417).

摘要/Abstract

摘要： 采用催化加氢技术脱除F-T合成水相中羧酸、醛、醇、酮、酯含氧化合物,考察了Ru/ZrO₂、Ru/TiO₂、Ru/SiO₂和Ru/Al₂O₃ 4种Ru催化剂的反应性能.相对于酸、醇,水中的醛、酮、酯更易被转化.其中Ru/ZrO₂和Ru/TiO₂具有良好的加氢脱羰活性,在200℃、9.8 MPa、3.0 h^-1空速下,酸、醛、醇、酮、酯均转化为C₁～C₆的烷烃,总转化率达92%.同条件下,虽然Ru/Al₂O₃对酸、醛、酮、酯的转化活性较高(>87%),但对醇的转化不到30%,具有选择性转化特点.H₂-TPR和NH₃-TPD结果表明,Ru/Al₂O₃催化剂的金属活性位与载体酸性位的协同作用有利于羧酸的加氢反应,能抑制醇的加氢脱羰活性;而金属-载体相互作用较弱和酸度较低的催化剂有利于羧酸、醇发生加氢脱羰反应.Ru/Al₂O₃催化剂运行500 h后失活,XRD、SEM和N₂-物理吸附表明,载体结构物相和织构性质的改变以及活性组分的流失是导致催化剂失活的主要因素.

关键词: 催化加氢, 费托水, 催化剂, 羧酸, 醇, 载体

Abstract: Removal of oxygenates in aqueous phase product of Fischer-Tropsch (F-T) process was studied by the catalytic hydrogenation over supported Ru catalysts. The catalytic performance of several Ru catalysts supported on different metal oxides such as ZrO₂, TiO₂, SiO₂ and γ-Al₂O₃ was investigated. In the catalytic hydrogenation processes, aldehydes, ketones and esters are more readily to be transformed than carboxylic acid and alcohol. The Ru/ZrO₂ and Ru/TiO₂ catalysts exhibited excellent hydrogenation activity, and under the conditions of 200℃, 9.8 MPa pressure and 3.0 h^-¹ WHSV, the carboxylic acids, aldehydes, alcohols, ketones and esters all are transformed to C₁—C₆ alkanes with overall conversion of above 92%. However, the Ru/Al₂O₃ catalyst displays the lowest activity towards alcohols with below 30% of conversion at the same conditions, although other oxygenates, including carboxylic acids, aldehydes, ketones and esters, are transformed with considerable conversion of above 87%, indicating that the Ru/Al₂O₃ catalyst was of selectivity for the conversion of oxygenates and the most of alcohols can not be transformed. The results from H₂-TPR and NH₃-TPD reveal that the synergy between metal and alumina is conductive to the hydrogenation of carboxylic acids and inhibits the hydrogenation-decarbonylation of alcohols. On the contrary, the catalysts with weak metal-support interaction and low acidity improve the hydrogenation activity for carboxylic acids and alcohols. However, there was a good stability of 400 h for Ru/Al₂O₃ catalyst, although the degeneration of catalytic activity was also observed after running 400 h. The results from X-ray diffraction (XRD), scanning electron microscopy (SEM) and N₂ physisorption show that the change of textural and structural properties is the key factors for activity degeneration of Ru/Al₂O₃ catalyst, because of the transformation of γ-alumina to boehmite and of the great decrease of surface area from 197 m²·g^-¹ to 21 m²·g^-¹ and loss of porosity.

Key words: catalytic hydrogenation, F-T water, catalyst, carboxylic acid, alcohol, support

中图分类号:

陈伦刚, 刘勇, 定明月, 张兴华, 李宇萍, 张琦, 王铁军, 马隆龙. Ru催化加氢选择性脱除F-T合成水相中的含氧化合物[J]. 化工学报, 2014, 65(11): 4347-4355.

CHEN Lungang, LIU Yong, DING Mingyue, ZHANG Xinghua, LI Yuping, ZHANG Qi, WANG Tiejun, MA Longlong. Removal of oxygenates in aqueous phase product of F-T process by catalytic hydrogenation over Ru catalyst[J]. CIESC Journal, 2014, 65(11): 4347-4355.

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Ru催化加氢选择性脱除F-T合成水相中的含氧化合物

Removal of oxygenates in aqueous phase product of F-T process by catalytic hydrogenation over Ru catalyst

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