| 油酸甲酯催化加氢制备生物烷烃的热力学分析 |
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| 引用本文： | 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. DOI: 10.11949/j.issn.0438-1157.20161808 |
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| 作者姓名： | 孙培永 李梦晨 刘森 戚琪 张胜红 姚志龙 |
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| 作者单位： | 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 |
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| 基金项目： | 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） |
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| 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。
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| 关 键 词： | 油酸甲酯 加氢 生物烷烃 热力学 基团贡献法 模拟 |
| 收稿时间： | 2016-12-26 |
| 修稿时间： | 2017-03-10 |
Thermodynamic analysis of catalytic hydrogenation of methyl oleate to produce bio-paraffins |
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| 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]. Journal of Chemical Industry and Engineering(China), 2017, 68(6): 2258-2265. DOI: 10.11949/j.issn.0438-1157.20161808 |
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| Authors: | SUN Peiyong LI Mengchen LIU Sen QI Qi ZHANG Shenghong YAO Zhilong |
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| Affiliation: | 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 |
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| 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. |
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| Keywords: | methyl oleate hydrogenation bio-paraffins thermodynamic group-contribution method simulation |
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