油酸甲酯催化加氢制备生物烷烃的热力学分析

doi:10.11949/j.issn.0438-1157.20161808

化工学报 ›› 2017, Vol. 68 ›› Issue (6): 2258-2265.DOI: 10.11949/j.issn.0438-1157.20161808

油酸甲酯催化加氢制备生物烷烃的热力学分析

孙培永¹, 李梦晨², 刘森¹, 戚琪¹, 张胜红¹, 姚志龙¹

1. 北京石油化工学院化学工程学院, 恩泽生物质精细化工北京市重点实验室, 北京 102617;
2. 中国石油天然气集团公司石油化工研究院, 北京 102206

收稿日期:2016-12-26 修回日期:2017-03-10 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 张胜红
基金资助:
北京市属高等学校高层次人才引进与培养计划项目资助长城学者项目（20150316）

Thermodynamic analysis of catalytic hydrogenation of methyl oleate to produce bio-paraffins

SUN Peiyong¹, LI Mengchen², LIU Sen¹, QI Qi¹, ZHANG Shenghong¹, YAO Zhilong¹

1. Beijing Key Laboratory of Enze Biomass Fine Chemicals, College of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China;
2. Petrochemical Research Institute of CNPC, Beijing 102206, China

Received:2016-12-26 Revised:2017-03-10 Online:2017-06-05 Published:2017-06-05
Contact: 10.11949/j.issn.0438-1157.20161808
Supported by:
supported by the Changcheng Scholars Program of Beijing (CIT&TCD 20150316)

摘要/Abstract

摘要：

采用Benson基团贡献法对油酸甲酯加氢脱氧、加氢脱羰和加氢脱羧制备生物烷烃的热力学进行了分析，计算了613~653 K温度区间内油酸甲酯加氢体系的反应热、反应熵变、反应Gibbs自由能变和标准平衡常数，在此基础上采用PRO/Ⅱ软件中的平衡反应器模型分析了温度对油酸甲酯加氢产物分布的影响并和实验数据进行了对比验证。结果表明，油酸甲酯加氢脱氧、加氢脱羧和加氢脱羰制备生物烷烃的反应均为放热反应，放热量依次递减，各反应在613~653 K范围内均能够自发进行且反应完全。升高温度能够提高平衡产物中油酸甲酯加氢脱羰/羧产物的选择性，降低温度则有利于加氢脱氧产物的选择性，加氢脱氧与脱羰/羧产物选择性的比例随温度从613 K升高到653 K相应从1.92降低到0.56，与实验测得的反应数据变化趋势吻合。

关键词: 油酸甲酯, 加氢, 生物烷烃, 热力学, 基团贡献法, 模拟

Abstract:

The thermodynamic analysis of the hydrogenation of methyl oleate to bio-paraffins via hydrodeoxygenation (HDO), hydrodecarbonylation (HDCO) or hydrodecarboxylation (HDCO₂) routes was carried out by the Benson group-contribution method. Changes of enthalpy, entropy and Gibbs free energy, as well as the standard equilibrium constants, for each reaction were calculated in the temperature range of 613—653 K. The equilibrium distribution of products as a function of temperature was also simulated based on an equilibrium reactor of PRO/Ⅱ software and compared with the experimental data. The calculated thermodynamics indicates that HDO, HDCO and HDCO₂ of methyl oleate are exothermic processes, with the released heat decreasing in the order of HDO>HDCO₂>HDCO, and each reaction can take place spontaneously and proceed completely. Moreover, improving temperature prefers HDC to HDO products at equilibrium, results in a decreasing HDO/HDC ratio from 1.92 to 0.56 as the temperature rises from 613 K to 653 K, consisting well with the experimental data collected in the catalytic hydrogenation of methyl oleate.

Key words: methyl oleate, hydrogenation, bio-paraffins, thermodynamic, group-contribution method, simulation

中图分类号:

O642.1

孙培永, 李梦晨, 刘森, 戚琪, 张胜红, 姚志龙. 油酸甲酯催化加氢制备生物烷烃的热力学分析[J]. 化工学报, 2017, 68(6): 2258-2265.

SUN Peiyong, LI Mengchen, LIU Sen, QI Qi, ZHANG Shenghong, YAO Zhilong. Thermodynamic analysis of catalytic hydrogenation of methyl oleate to produce bio-paraffins[J]. CIESC Journal, 2017, 68(6): 2258-2265.

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油酸甲酯催化加氢制备生物烷烃的热力学分析

Thermodynamic analysis of catalytic hydrogenation of methyl oleate to produce bio-paraffins

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