活性炭负载[Rh(COD)Cl]_2催化剂的制备及其催化性能
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摘要
以氧化活性炭(OAC)为载体、自制[Rh(COD)Cl]_2为活性组分,制备了负载型催化剂[Rh(COD)Cl]_2/OAC(COD为1,5-环辛二烯),用XPS、N2吸-脱附、FTIR等对其结构进行了表征与分析,以β-蒎烯加氢反应为探针反应,考察了载体种类、氧化剂HNO3浓度、[Rh(COD)Cl]_2与OAC质量比对负载型催化剂[Rh(COD)Cl]_2/OAC性能的影响,在此基础上优化了β-蒎烯加氢工艺条件,并测定了催化剂([Rh(COD)Cl]_2/OAC)的重复使用性。结果表明,催化剂的最佳制备条件为:氧化活性炭为较佳载体,HNO3浓度为7.23mol/L,[Rh(COD)Cl]_2与OAC质量比为1∶8.3,此时β-蒎烯转化率均值为99.94%;顺式蒎烷选择性(以只生成蒎烷计,下同)均值为88.64%;顺式蒎烷收率均值为88.59%;β-蒎烯加氢工艺的最佳条件为:反应温度50℃,反应压力3.5 MPa,催化剂用量为β-蒎烯质量的3.5%,反应时间4.0 h,此条件下β-蒎烯转化率均值为99.88%;顺式蒎烷选择性均值为89.00%;顺式蒎烷收率均值为88.90%,[Rh(COD)Cl]_2/OAC催化剂在β-蒎烯加氢反应中表现出较佳的催化活性。催化剂重复使用4次后,β-蒎烯转化率仍可达89.64%,活性组分Rh的流失是造成催化剂失活的主要原因。
Supported [Rh(COD)Cl]_2/OAC catalysts were prepared by using oxidized activated carbon as support and self made [Rh(COD)Cl]_2 as active component( COD = 1,5-cyclooctadiene). The resulting catalysts were characterized by means of XPS,N2 adsorption-desorption and FTIR.Hydrogenation reaction of beta-pinene was used as a probe reaction to investigate the effects of carrier type,oxidant nitric acid concentration and mass ratio of [Rh(COD)Cl]_2 to OAC on the catalytic properties. On this basis,the hydrogenation conditions of beta-pinene were optimized,and the reusability of [Rh(COD)Cl]_2/OAC was measured. The experimental results indicated that the optimum preparation conditions of catalyst were as follows: oxidized activated carbon was used as support,nitric acid concentration was 7. 23 mol/L,and the mass ratio of [Rh(COD)Cl]_2 to OAC was 1∶ 8. 3. Under these conditions,the catalyst showed excellent catalytic activities in the hydrogenation reaction of beta-pinene. The average conversion of beta-pinene was 99. 88%,and the average selectivity and yield of cis-pinane were 89. 00% and 88. 90%. Additively,the [Rh(COD)Cl]_2/OAC stillremained high activities with a conversion of 89. 64% after being used for four times. The cause of deactivation of [Rh(COD)Cl]_2/OAC was that active component Rh was easy to lose in the running process.
Supported [Rh(COD)Cl]_2/OAC catalysts were prepared by using oxidized activated carbon as support and self made [Rh(COD)Cl]_2 as active component( COD = 1,5-cyclooctadiene). The resulting catalysts were characterized by means of XPS,N2 adsorption-desorption and FTIR.Hydrogenation reaction of beta-pinene was used as a probe reaction to investigate the effects of carrier type,oxidant nitric acid concentration and mass ratio of [Rh(COD)Cl]_2 to OAC on the catalytic properties. On this basis,the hydrogenation conditions of beta-pinene were optimized,and the reusability of [Rh(COD)Cl]_2/OAC was measured. The experimental results indicated that the optimum preparation conditions of catalyst were as follows: oxidized activated carbon was used as support,nitric acid concentration was 7. 23 mol/L,and the mass ratio of [Rh(COD)Cl]_2 to OAC was 1∶ 8. 3. Under these conditions,the catalyst showed excellent catalytic activities in the hydrogenation reaction of beta-pinene. The average conversion of beta-pinene was 99. 88%,and the average selectivity and yield of cis-pinane were 89. 00% and 88. 90%. Additively,the [Rh(COD)Cl]_2/OAC stillremained high activities with a conversion of 89. 64% after being used for four times. The cause of deactivation of [Rh(COD)Cl]_2/OAC was that active component Rh was easy to lose in the running process.
引文
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[25]Díaz-Au1ón J A,Román-Martínez M C,de Lecea C S M.[Rh(μ-Cl)(COD)]2supported on activated carbons for the hydroformylation of 1-octene:effects of support surface chemistry and solvent[J].Journal of Molecular Catalysis A:Chemical,2001,170(1/2):81-93.
[26]Romn-Martínez M C,Díaz-Au1ón J A,de Lecea C S M,et al.Rhodium-diphosphine complex bound to activated carbon an effective catalyst for the hydroformylation of 1-octene[J].Journal of Molecular Catalysis A:Chemical,2004,213(2):177-182.
[2]Gao Hongyun(高红云),Ha Chengyong(哈成勇).Preparation of high-purityβ-pinene[J].Fine Chemicals(精细化工),2006,23(11):1134-1137.
[3]Smith H A,Fuzek J F.The Influence of certain additives on the rate of catalytic hydrogenation of terpenes on nickel[J].Journal of the American Chemical Society,1950,72(8):3454-3458.
[4]Deliy I V,Simakova I L.Catalytic activity of theⅧgroup metals in the hydrogenation and isomerization ofα-andβ-pinenes[J].Russian Chemical Bulletin,2008,57(10):2056-2064.
[5]Tanielyan S,Biunno N,Bhagat R,et al.Anchored Wilkinson catalyst:hydrogenation ofβ-pinene[J].Topics in Catalysis,2014,57(17-20):1564-1569.
[6]He Xiangwen(贺香文),Zheng Fuping(郑福平),Xu Cuicui(徐翠翠),et al.Synthesis of 2,10-epoxypinane by epoxidation ofβ-pinene with hydrogen peroxide[J].Fine Chemicals(精细化工),2011,28(10):978-981.
[7]Liu Bing(刘兵),Ao Wangwei(敖汪伟),Yang Yang(杨杨),等.Synthesis of(+)-nopinone from(-)-β-pinene by selective oxidation[J].Journal of Nanjing Forestry University(Natural Science Edition)(南京林业大学学报:自然科学版),2010,34(2):89-94.
[8]Ou Yang Yuzhu(欧阳玉祝),Li Hui(李辉),Yin Dulin(尹笃林),等.Preparation of myrtenal fromβ-pinene by photo-sensitized oxidation[J].Chemistry and Industry of Forest Products(林产化学与工业),2004,24(04):45-48.
[9]Barros H J V,Ospina M L,Arguello E,et al.Rhodium catalyzed hydroformylation ofβ-pinene and camphene:effect of phosphorous ligands and reaction conditions on diastereoselectivity[J].Journal of organometallic chemistry,2003,671(1):150-157.
[10]GuinéR P F,Castro J A A M.Polymerization ofβ-pinene with ethylaluminum dichloride(C2H5Al Cl2)[J].Journal of Applied Polymer Science,2001,82(10):2558-2565.
[11]Huang Zengfang(黄增芳),Gao Haiyang(高海洋),Wu Qing(伍青).Copolymerization ofβ-pinene and norbornene with 2-aminopyridine nickel(Ⅱ)complexes/MAO catalysts[J].Chemical Journal of Chinese Universities(高等学校化学学报),2010,31(6):1257-1262.
[12]Liu Zuguang(刘祖广),Zhu Hualong(朱华龙),Zeng Wei(曾巍),等.Cationic polymerization ofβ-pinene using Keggin phosphotungstic acid as catalyst[J].CIESC Journal(化工学报),2011,62(4):962-969.
[13]Duan Wengui(段文贵).Progress in catalytic hydrogenation of turpentine[J].Chemical World,2003,44(5):274-276.
[14]Lauterbach G,Pritzkow W.Kinetic studies of the liquid-phase oxidation of cis-pinane and of adamantane with molecular oxygen[J].Journal Fur Praktische Chemie/Chemiker-Zeitung,1995,337(1):416-417.
[15]Bain J P.Preparation of 2,6-dimethyl-2,7-octadiene:US19650471989[P].1966-10-04.
[16]Yang Yiqin(杨益琴),Wang Shifa(王石发),Li Yanping(李艳苹),等.Synthesis of nitrogen-containing derivatives fromα-pinene and their nematieidal activity against pinewood nematode[J].Acta Chimica Sinica(化学学报),2009,67(21):2463-2474.
[17]Semikolenov V A,Ilyna I I,Simakova I L.Linalool synthesis fromα-pinene:kinetic peculiarities of catalytic steps[J].Applied Catalysis A:General,2001,211(1):91-107.
[18]Mao Liqiu(毛丽秋),Yin Dulin(尹笃林),Li Qianhe(李谦和),等.New technology of catalytic synthesis of dihydromyrcenol from pinane[J].Chemistry and Industry of Forest Products(林产化学与工业),2000,20(4):20-24.
[19]Jiang Ru(姜茹),Nan Pengjuan(南鹏娟),Liu Wei(柳巍),等.Synthesis of new chiral diphosphine-borane complex and its application to the catalytic asymmetric hydrogenation[J].Chemical Journal of Chinese Universities(高等学校化学学报),2001,22(6):936-938.
[20]Silbernagel R,Díaz A,Steffensmeier E,et al.Wilkinson-type hydrogenation catalysts immobilized on zirconium phosphate nanoplatelets[J].Journal of Molecular Catalysis A:Chemical,2014,394(10):217-223.
[21]Pérez-Cadenas M,Lemus-Yegres L J,Román-Martínez M C,et al.Immobilization of a Rh complex derived from the Wilkinson's catalyst on activated carbon and carbon nanotubes[J].Applied Catalysis A:General,2011,402(1):132-138.
[22]Wang D W,Lu S M,Zhou Y G.A simple and highly effective method for hydrogenation of arenes by[Rh(COD)Cl]2[J].Tetrahedron Letters,2009,50(12):1282-1285.
[23]Chatt J,Venanzi L M.Olefin co-ordination compounds.Part VI.diene complexes of rhodium(I)[J].Journal of the Chemical Society,1957,12(0),4735-4741.
[24]An N,Dai Y S,Tang C,et al.Design and preparation of a simple and effective palladium catalyst and the hydrogenation performance toward dibenzylbiotinmethylester[J].J.Colloid Interface Sci,2016,470(5):56-61.
[25]Díaz-Au1ón J A,Román-Martínez M C,de Lecea C S M.[Rh(μ-Cl)(COD)]2supported on activated carbons for the hydroformylation of 1-octene:effects of support surface chemistry and solvent[J].Journal of Molecular Catalysis A:Chemical,2001,170(1/2):81-93.
[26]Romn-Martínez M C,Díaz-Au1ón J A,de Lecea C S M,et al.Rhodium-diphosphine complex bound to activated carbon an effective catalyst for the hydroformylation of 1-octene[J].Journal of Molecular Catalysis A:Chemical,2004,213(2):177-182.