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过程工程学报 ›› 2019, Vol. 19 ›› Issue (6): 1101-1110.DOI: 10.12034/j.issn.1009-606X.219155

• 反应与分离 • 上一篇    下一篇

混配组分对基于KH2PO4/Al2O3催化剂的酚油醚化的影响

袁 博1,2,3, 王 泽1,2,3*, 宋文立1,2, 李松庚1,2   

  1. 1. 中国科学院过程工程研究所多相复杂系统国家重点实验室,北京 100190 2. 中国科学院大学中丹学院,北京 100049 3. 中国丹麦科研教育中心,北京 100049
  • 收稿日期:2019-03-12 修回日期:2019-03-28 出版日期:2019-12-22 发布日期:2019-12-22
  • 通讯作者: 王泽
  • 基金资助:
    原位供氢条件下生物质水热转化制备液体燃料基础研究

Effect of blending component on etherification of phenolic-oil over KH2PO4/Al2O3

Bo YUAN1,2,3, Ze WANG1,2,3*, Wenli SONG1,2, Songgeng LI1,2   

  1. 1. State Key Laboratory of Multi-Phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 2. Sino-Danish College, University of Chinese Academy of Sciences, Beijing 100049, China 3. Sino-Danish Center for Education and Research, Beijing 100049, China
  • Received:2019-03-12 Revised:2019-03-28 Online:2019-12-22 Published:2019-12-22

摘要: 以KH2PO4/Al2O3为催化剂,针对以甲醇为烷基化试剂的酚油醚化体系,研究了5种混配组分(乙酸、甲酸、丙酮、呋喃、乙酸乙酯)对酚油醚化反应规律的影响。结果表明,丙酮对促进烷基酚转化为芳醚的作用效果最强。基于丙酮混配组分,500℃下探究了丙酮质量配比的影响,基于最佳丙酮添加量(50wt%),进一步考察了温度对反应体系的影响,并进行机理分析。结果表明,丙酮含量不高于70wt%时,液体收率随丙酮含量升高而降低,进一步提高丙酮含量时液体收率基本稳定。各丙酮含量下,液体产物中均未检出邻甲氧基苯酚或其它任何烷氧基酚。较高丙酮含量时烷基酚含量显著降低。丙酮含量为50wt %时,芳醚含量出现极大值(29.06area%),进一步提高丙酮含量,芳烃及其它组分显著增加,导致产物中芳醚含量降低。随反应温度升高,产物中的芳醚和芳烃含量分别在500和450℃时出现极大值。综合考虑液体收率和产物极性两方面因素,确定该反应体系的最佳反应温度为450℃,丙酮添加量为50wt%,最佳条件下产物中芳醚与芳烃总量达52.90area%。丙酮分子中的羰基与酚系物中的羟基发生作用,分解产生CO2,同时烷基酚与烷氧基酚脱羟基后分别得到芳烃和芳醚两类主要液相产物。

关键词: 酚油, 醚化, 添加剂, 丙酮, 甲醇, 催化

Abstract: The polarity of phenolic-oil can decrease with improved miscibility in gasoline or diesel, if the phenolic mixture can be converted to aryl ethers. As the following work of early-stage studies, in this work, based on the prior well-estimated catalyst of KH2PO4/Al2O3, a novel process with addition of blending component was put forward and the effects of blending components on the vapor-phase etherification of phenols with methanol were investigated systematically, using phenolic-oil as research object. Five blending components (acetic acid, formic acid, acetone, furan and ethyl acetate) were screened and the effect of acetone was found to be the best in promoting the conversion of alkylphenols to aryl ethers. The effect of acetone dosage was examined at a constant temperature of 500℃. It was found that the liquid recovery deceased with increasing dosage of acetone before 70wt%, and then turned to a stable trend at even higher dosages. Guaiacol or any other alkoxyphenol was not detected in all cases. Alkylphenols decreased remarkably at higher acetone dosages compared with that without blending component. Aryl ethers were most generated at the acetone dosage of 50wt%. With even higher dosage of acetone, aromatics and other compounds were more generated, leading to a remarkable decrease of aryl ethers. Furthermore, with the optimized acetone percentage of 50wt%, the influence of temperature on the alkylation reaction was investigated. It was found that the liquid recovery deceased with increasing of the temperature, and decreased even faster in the range from 500 to 550℃. The content of aryl ethers reached to a maximum value (29.06area%) at 500℃ and aromatics were most generated (26.01area%) at 450℃ Considering the both factors of liquid recovery and polarity of liquid product, the optimized conditions were determined as 450℃ with 50wt% of acetone dosage, with summary content of aromatics and aryl ethers (52.90area%). It was speculated that the carbonyl group of acetone interacted with the hydroxyl group of phenols, leading to the release of CO2, and meanwhile aromatics and arylethers were generated from alkylphenols and alkoxyphenols respectively.

Key words: phenolic-oil, etherification, additive, acetone, methanol, catalysis