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苯酚羟基化合成苯二酚反应产物分离过程酚焦油的形成原因
引用本文:张信芳,张敬畅,张光明,张天巧. 苯酚羟基化合成苯二酚反应产物分离过程酚焦油的形成原因[J]. 石油化工, 2004, 33(11): 1036-1040
作者姓名:张信芳  张敬畅  张光明  张天巧
作者单位:1. 清华大学,深圳研究生院,广东,深圳,518055;中国石化股份有限公司,北京燕山分公司研究院,北京,102500
2. 北京化工大学,理学院,北京,100029
3. 清华大学,深圳研究生院,广东,深圳,518055
4. 中国石化股份有限公司,北京燕山分公司研究院,北京,102500
基金项目:国家自然科学基金(20076004)中国石化股份有限公司燕山分公司资助项目。
摘    要:对苯酚羟基化合成苯二酚产物分离过程酚焦油的形成原因进行了研究。模拟研究表明,在含有邻苯二酚和对苯二酚的混合溶液中,邻苯二酚比对苯二酚更易氧化缩合生成酚焦油。苯酚羟基化反应液中催化剂残留和催化剂被溶解形成的金属离子对酚焦油的形成具有促进作用;对苯醌的存在对酚焦油的生成具有促进作用;泄漏进入的氧或空气可加速苯二酚的氧化缩合反应;酚焦油生成量随常压脱水和减压精馏过程操作温度的升高、操作时间的延长而增加。醋酸能溶解催化剂活性组分,存在醋酸和金属离子残留问题,从而增加了羟基化反应产物分离过程酚焦油的生成量。在羟基化反应产物中加入Na2HSO3,使羟基化反应产物中的对苯醌还原,同时减少羟基化反应产物中的溶解氧含量,从而起到了抑制脱水和精馏过程中酚焦油生成的作用。

关 键 词:苯酚  苯二酚  产物分离  酚焦油  形成原因
文章编号:1000-8144(2004)11-1036-05
修稿时间:2004-06-20

Phenolic Tar Formation during Products Separation of Diphenols Synthesis by Phenol Hydroxylation
Zhang Xinfang,Zhang Jingchang,Zhang Guangming,Zhang TianqiaoShenzhen Graduate School of Tsinghua University,Shenzhen Guangdong ,China,Faculty of Science,Beijing University of Chemical Technology,Beijing ,China, Research Institute of Beijing Yansan Petrochemical Co.,SINOPEC,Beijing ,China). Phenolic Tar Formation during Products Separation of Diphenols Synthesis by Phenol Hydroxylation[J]. Petrochemical Technology, 2004, 33(11): 1036-1040
Authors:Zhang Xinfang  Zhang Jingchang  Zhang Guangming  Zhang TianqiaoShenzhen Graduate School of Tsinghua University  Shenzhen Guangdong   China  Faculty of Science  Beijing University of Chemical Technology  Beijing   China   Research Institute of Beijing Yansan Petrochemical Co.  SINOPEC  Beijing   China)
Affiliation:Zhang Xinfang,Zhang Jingchang,Zhang Guangming,Zhang TianqiaoShenzhen Graduate School of Tsinghua University,Shenzhen Guangdong 518055,China,Faculty of Science,Beijing University of Chemical Technology,Beijing 100029,China, Research Institute of Beijing Yansan Petrochemical Co.,SINOPEC,Beijing 102550,China)
Abstract:Formation of phenolic tar during separation of products from diphenols synthesis by phenol hydroxylation was studied. Phenolic tar was formed when dehydration of products under atmospheric pressure and successive vacuum distillation. In mixed solution of catechol and hydroquinone, the former condensated to phenolic tar more easily than hydroquinone. Residue of catalyst,presence of dissolved metal ions,leaked in oxygen and benzoquinone, would all accelerate formation of phenolic tar in hydroxylated liquid. High temperature and long operation time would also favoured amount of phenolic tar produced. Active components of composite oxides catalysts could be partly dissolved by acetic acid in hydroxylation system and increased amount of phenolic tar. Residual acetic acid and metallic ions could be avoided by modification of composite oxides catalyst, using solid acid instead of acetic acid as assistant catalyst. Na2HSO3 could inhibit formation of phenolic tar during dehydration and distillation of hydroxylated products.
Keywords:phenol  diphenol  product separation  phenolic tar  formation reason
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