石油化工高等学校学报

石油化工高等学校学报 ›› 2010, Vol. 23 ›› Issue (2): 16-20.

• 石油化工 • 上一篇    下一篇

碳基固体酸催化剂上的酯化反应动力学研究

冷冬梅1,石采静1,周长行1,余济伟2,任立国1*   

  1. 1.辽宁石油化工大学化学与材料科学学院, 辽宁抚顺113001; 2.抚顺石化公司催化剂厂, 辽宁抚顺113001
  • 收稿日期:2000-11-26 出版日期:2010-06-25 发布日期:2010-06-25
  • 作者简介:冷冬梅(1984 -), 女, 辽宁锦州市, 在读硕士
  • 基金资助:
    辽宁省教育厅资助项目(05L299)

The Kinetics Study of the Esterification on the Carbon-Based Solid Acid Catalys

  1. 1. School of Chemistry and Material Science,Liaoning Shihua University,Fushun  Liaoning 113001, P. R. China; 
    2. Catalysts Factory of Fushun Petrochemical Company,Fushun Liaoning 113001,P.R.China
  • Received:2000-11-26 Published:2010-06-25 Online:2010-06-25

摘要: 通过膨化淀粉和十二烷基苯磺酸混合物的部分碳化制备新型碳基固体强酸催化剂, 研究了碳基固体
酸催化剂在油酸与乙醇的酯化反应中的催化性能, 考察了乙醇与油酸物质的量比、催化剂与油酸的质量比、反应温
度和反应时间等因素对油酸转化率的影响。XRD 和酸碱电位滴定结果表明, 膨化淀粉和十二烷基苯磺酸混合物的
部分碳化生成含高密度— SO3H 的芳香碳薄层组成的无定形碳。新型碳基固体强酸催化剂在油酸与乙醇的酯化反
应中具有较好的催化活性。在乙醇与油酸物质的量比为8 、催化剂质量为1 g 、回流反应6 .0 h 的条件下, 油酸转化率
达83 .88%。并且发现在50 ~ 70 ℃, 随温度升高油酸的转化率也随之升高, 油酸和乙醇在碳基固体酸催化剂上的酯
化反应服从准一级反应动力学方程, 表观活化能和指前因子分别为35.78 kJ/ mol 和5 .70 ×104 h -1

关键词: 碳基固体酸 , 酯化 , 生物柴油 , 拟均相模型 , 动力学

Abstract:

Novel solid acid catalysts for esterification have been described that were made by incomplete carbonization of expanded starch and dodecylbenzene sulfonic acid. The effects of the molar ratio of alcohol to oleic acid, the mass ration of catalyst to oleic acid,reaction temperatures and reaction time were discussed. The kinetics of esterification of oleic acid with ethanol in the liquid phase catalyzed by carbon-based solid acid was studied under atmospheric pressure. The results of XRD and acid-base titration indicate the incompletely carbonization of the mixtures of expanded starch and p-toluene sulfonic acid results in amorphous carbon consisting of small polycyclic aromatic carbon sheets with high density of —SO3H groups. The remarkable catalytic activity of this material is attributable to the incorporation of reactants into the bulk structure and the high density of strongly acidic —SO3H sites. The experimental results show that the conversion of oleic acid is 83.88% by following conditions:molar ratio of ethanol to oleic acid is 8∶1,catalyst mass 1.0 g, refluxe reaction time 6.0 h.It was also found that the reaction depended on temperature. The conversion of oleic acid was found to increase with the temperature increasing from 50 ℃ to 70 ℃. The experimental data were correlated with a first-order pseudohomogeneous kinetic model. The activation energy and pre-exponential factor of this reaction are calculated to be 35.78 kJ/mol and 5.70×104  h-1, respectively. 

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引用本文

冷冬梅,石采静,周长行. 碳基固体酸催化剂上的酯化反应动力学研究[J]. 石油化工高等学校学报, 2010, 23(2): 16-20.

LENG Dong-mei,SHI Cai-jing,ZHOU Chang-xing,et al. The Kinetics Study of the Esterification on the Carbon-Based Solid Acid Catalys[J]. Journal of Petrochemical Universities, 2010, 23(2): 16-20.

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