摘要
顺酐选择性加氢可以产生多种重要化学原料,且产物分布受温度影响显著。热力学分析在研究反应过程和产物选择性中起着重要作用。本文基于热力学分析方法研究了反应温度对顺酐加氢网络中不同反应路径及产物选择性的影响。首先采用Benson基团贡献法,估算了顺酐、丁二酸酐和1,4-丁二醇在标准状态下的摩尔生成焓、熵和等压热容等数据。进而计算了顺酐加氢反应体系中各反应的摩尔焓变、Gibbs自由能变以及平衡常数。最后,以工业上典型的Cu/SiO_(2)催化剂为研究对象,探究了温度对不同产物选择性的影响规律,实验结果与热力学计算结果相吻合。本工作为探究顺酐加氢网络中产物分布规律以及调控生产工艺参数提供了理论指导。
The selective hydrogenation of maleic anhydride(MA)could yield a variety of important chemical feedstocks,and the product distribution is greatly affected by reaction temperature.Thermodynamic analysis plays an important role in linking the chemical process and product selectivity.In this work,the effect of reaction temperature on different reaction pathways and product selectivity in maleic anhydride hydrogenation was investigated by thermodynamic analysis.Firstly,the molar enthalpy,entropy and heat capacity of MA,succinic anhydride,and 1,4-butanediol were estimated by using Benson group contribution method.Then,the reaction enthalpy,Gibbs free energy change and equilibrium constant for different reactions were calculated and analyzed.Finally,a typical Cu/SiO_(2) catalyst in industry was used to verify the influence of temperature on product selectivity.The experimental result was consistent with the thermodynamic calculation.This work provides theoretical guidance for exploring the product distribution and regulating the process parameters in maleic anhydride hydrogenation network.
作者
杨有为
陈梁锋
王健
郭凯
王黎敏
王万民
朱俊华
YANG Youwei;CHEN Liangfeng;WANG Jian;GUO Kai;WANG Limin;WANG Wanmin;ZHU Junhua(State Key Laboratory of Green Chemical Engineering and Industrial Catalysis,SINOPEC Shanghai Research Institute of Petrochemical Technology Company Limited,Shanghai 201208,China)
出处
《化学反应工程与工艺》
2025年第3期382-389,425,共9页
Chemical Reaction Engineering and Technology
