双酚F合成体系热力学和动力学分析  

Thermodynamic and kinetic analysis of bisphenol F synthesis

作　　者：邓玉媛 乔凯[1] 霍稳周[1] 李花伊[1] DENG Yu-yuan QIAO Kai HUO Wen-zhou LI Hua-yi(Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001, Liaoning Province, China)

机构地区：[1]中国石油化工股份有限公司抚顺石油化工研究院,辽宁抚顺113001

出　　处：《化学工程》2017年第3期46-51,共6页Chemical Engineering(China)

摘　　要：对苯酚与甲醛反应合成双酚F体系进行了热力学分析,通过等键反应设计、G-C基团贡献法和分子模拟等多种方法计算了双酚F合成体系中各物质液态的生成焓和标准熵,计算涉及反应的焓变、熵变、Gibbs自由能变及平衡常数。结果表明:在298—363 K之间,苯酚与甲醛合成双酚F的主、副反应均为放热反应,Gibbs自由能变均为绝对值较大的负值,反应可自发进行,需要开发高选择性的催化剂和适宜的反应条件以控制副反应;各步反应平衡常数很高,反应进行得较完全。此外,通过动力学分析讨论了苯酚/甲醛摩尔比对双酚F选择性的影响,随着苯酚/甲醛摩尔比增加,选择性提高,酚醛摩尔比高于10后变化不明显。Thermodynamics of bisphenol F synthesis from phenol and formalin was analyzed. Enthalpies of formaldehyde and standard entropies of the components in liquid phase were estimated by methods of designed isodesmic reaction, G-C group contribution method and molecular simulation etc. , and enthalpy changes, entropy changes, Gibbs free energy changes and equilibrium constants were calculated. Main and side reactions were all exothermic and spontaneous processes in the range of 298-363 K, which meaned that high-selectivity catalyst and proper reaction condition needed to avoid side reactions. The equilibrium constants of each step were high, so the reactions should run completely. Influence of molar ratio of phenol to formaldehyde on selectivity of bisphenol F was discussed through kinetic analysis. The selectivity was improved with increasing the molar ratio of phenol to formaldehyde.

关 键 词：双酚F合成 反应焓变 Gibbs自由能变 酚醛比 双酚F选择性 

分 类 号：O625.14[理学—有机化学]