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松节油催化异构-分子间氢转移反应的研究 被引量:6

Catalytic Isomerization-Intermolecular Hydrogen Transfer of Turpentine
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摘要 以马尾松松节油为原料进行直接催化异构-分子间氢转移反应的研究,探讨了Pd/C-H2SO4协同催化反应的机理。采用500r·min^-1的搅拌转速与10-20μm的催化剂粒径,以气相色谱-质谱联用(GC-MS)和气相色谱(GC)定性、定量分析了反应产物,考察了催化剂种类、酸种类、温度、催化剂含量、酸浓度及时间等条件对反应的影响,测定不同搅拌转速下的液-液-固非均相反应效果,结果表明,在Pd/C-H2SO4复合催化剂上,反应温度为120℃、催化剂用量为占松节油质量的0.2%,20%H2SO4溶液及反应时间为8h的最优反应条件下,蒎烯的转化率为99.13%,对伞花烃的收率为61.56%,并认为在Pd/C-H2SO4复合催化剂上松节油异构-分子间氢转移反应机理是酸性中心作用的正碳离子历程与金属中心作用的氢转移历程共同组成,其主要成分双环单萜蒎烯的异构及分子间氢转移歧化反应为主反应,实现异构-分子间氢转移平行连串反应的耦合,使反应时间从原来两步法的14h降低为8h。 Direct catalytic isomerization-intermolecular hydrogen transfer of turpentine was studied, and the synergetic catalytic reaction mechanism over Pd/C-H2SO4 catalyst was discussed. During the experiments, the rotation speed of 500 r.min^-1 and the catalyst diameter of 10-20 μm were used, and the reaction products were qualitatively and quantitatively analyzed respectively by gas chromatography/mass spectrometry-data system (GC-MS) and chromatography (GC). The effects of the species of catalyst and used acid, catalyst content, acid concentration, reaction temperature and time, and the ratio of acid to oil on the reaction were investigated. The results show that under the optimal conditions, (i.e., reaction temperature of 120℃, catalyst content of 0.2% based on turpentine weight, H2SO4 concentration of 20%(vol) and reaction time of 8 h), the conversion of pinene is 99.13% and the yield of p-cymene is 61.56% over Pd/C-H2SO4 catalyst. It was found that the synergetic catalytic reaction mechanism of isomerization-intermolecular hydrogen transfer reaction of turpentine over Pd/C-H2SO4 catalyst is made up of carbonium mechanism of acidity center and hydrogen transfer mechanism of metal center. The isomerization and intermolecular hydrogen transfer disproportionation of bicyclic terpene pinene (the main composition of turpentine) is the main reaction, and the coupling of parallel-consecutive reaction (isomerization-intermolecular hydrogen transfer) is carried out. As a result, the reaction time was decreased from 14 h for the generally used two-step method to 8 h.
出处 《高校化学工程学报》 EI CAS CSCD 北大核心 2008年第5期809-815,共7页 Journal of Chemical Engineering of Chinese Universities
基金 国家自然科学基金资助项目(30560119) 教育部高等学校博士学科点专项科研基金项目(20070593004) 广西青年基金资助项目(0640001) 广西教育厅资助项目(桂教科研[2006]26号)
关键词 松节油 催化 异构 分子间氢转移 对伞花烃 turpentine catalytic isomerization intermolecular hydrogen transfer p-cymene
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