王琳琳,徐徐,陈小鹏,李大燕,韦彩妙,童张法

• 1:广西大学化学化工学院

摘要(Abstract)：

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。

关键词(KeyWords)： 松节油;催化;异构;分子间氢转移;对伞花烃

Abstract:

Keywords:

基金项目(Foundation): 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)

作者(Author): 王琳琳,徐徐,陈小鹏,李大燕,韦彩妙,童张法

参考文献(References)：

• [1]CHENG Zhi(程芝).Production Technology of Natural Resins.(2nd Ed)(天然树脂生产工艺学)(第2版)[M].Beijing(北京):China Forestry Press(中国林业出版社),1996.
• [2]Rashmi K,Kad G L.Juvenile hormone analogues active on mosquitoes:synthesis and juvenile hormonal activity of newly synthesized juvenoid ethers withα-pinene and substituted cyclohexene ring[J].J India Chem Soc,2001,78(4):197-201.
• [3]Robles-Dutenhefner P,Da Silva M J,Sales L S et al.Solvent-free liquid-phase autoxidation of monoterpenes catalyzed by sol-gel Co/SiO2[J].Appl Catal A:Gen,2004,217(1):139-144.
• [4]Buhl D,Roberge D M,Holderich W F.Production of p-cymene fromα-limonene over silica supported Pd/C catalysts[J].Appl Catal A:Gen,1999,188(1-2):287-299.
• [5]Hoelderich W,Fischer R,Mross W D et al.Preparation of alkyl benzenes[P].USP:4,665,252,1987-05-12.
• [6]HU Gui-Xian(胡贵贤);LIU Xian-Zhang(刘先章).Study on utilization of dipentene(双戊烯加工利用的研究)[J].Chem Ind Forest Prod(林产化学与工业),1993,13(4):305-310.
• [7]Grau R J,Zgolicz P D,Gutierrez C et al.Liquid phase hydrogenation,isomerization and dehydrogenation of limonene and derivatives with supported palladium catalysts[J].J Mol Catal A:Chem,1999,148(1-2):203-214.
• [8]LIU De-chen(刘德臣),SUN Zhi-Qiang(孙志强),GUO Qing-hua(郭清华).Study on preparation process of p-pymene with gas-phase catalytic dehydrogenation of industrial dipentene(工业双戊烯气相催化脱氢制对伞花烃的研究)[J].Fine Chemicals(精细化工),1998,15(6):42-45.
• [9]Stanislaus A,Yeddanapalli L M.Vapor phase catalytic transformations of terpene hydrocarbons in the C10H16series.Ⅱaromatization ofα-pinene over chromia-alumina[J].Can J Chem,1972,50(1):113-118.
• [10]LI Ning(李凝).Study of trial production for synthesis of glyoxylic acid by oxygen method(以松节油为原料合成对异丙基甲苯)[J].Fine Chemicals(精细化工),2002,19(8):477-478,481.
• [11]Tike M A,Mahajani V V.Studies in catalytic transfer hydrogenation of soybean oil using ammonium formate as donor over5%Pd/C catalyst[J].Chem Eng J,2006,123(1-2):31-41.
• [12]ZHU Yuan-jiao(祝远姣),CHEN Xiao-peng(陈小鹏),WANG Lin-lin(王琳琳)et al.Measurement and correlation for saturated vapor pressure of pinane(蒎烷饱和蒸汽压的测定与关联)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2003,17(5):564-568.
• [13]CONG Pu-zhu(丛浦珠).The Application of Mass Spectroscopy in Natural Organic Chemistry(质谱学在天然有机化学中的应用)[M].Beijing(北京):Science Press(科学出版社),1987.
• [14]Heller S R,Milne G W A.EPA/NIH Mass Spectral Data Base[M].Washington:US Government Printing Office,1978.
• [15]Shah N,Pattanaik S,Huggins F E et al.XAFS and Mossbauer spectroscopy characterization of supported binary catalysts for nonoxidative dehydrogenation of methane[J].Fuel Process Technol,2003,83(1-2):163-173.
• [16]Feng Z T,Liu L J,Anthony R G.Reactions of propane on modified metal oxides[J].J Catal,1992,136(2),423-431.
• [17]WANG Liao-sha(王廖沙).Determination of liquid phase reaction conditions and selection of catalyst for the preparation of p-cymene fromα-pinene(由α-蒎烯制取对伞花烃液相反应条件的确定及催化剂的选择)[J].Chemistry Word(化学世界),2001,39(3):131-133,165.
• [18]LIU Chun-xue(刘春雪),MI Zhen-tao(米镇涛),WANG Li(王莅).Intrinsic kinetic study on hydrogenation of2-amylanthraquinone(2-戊基蒽醌氢化本征动力学研究)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2007,21(6):530-533.
• [19]Fogler H S.LI Shu-yuan(李术元),ZHU Jian-hua(朱建华)Transl.(译).Chemical Reaction Engineering.(3nd Ed)(化学反应工程)(原著第三版)[M].Beijin(北京):Chem Ind Press(化学工业出版社),2005.