乳酸促进的仲钼酸铵催化氧化环己烷过程

doi:10.11944/j.issn.1000-0518.2015.01.140071

摘要/Abstract

摘要：

环己烷的催化氧化是重要的工业反应之一,为了寻找更高效廉价的催化剂,研究了仲钼酸铵(APM)对环己烷氧化的催化活性,并着重探讨了酸助剂的种类及添加量对APM催化活性的影响。与硝酸相比,乳酸对环己醇转化为环己酮的过程促进作用更强,且使反应物的有效利用率更高,并由此将APM对目标产物的总TON(turn over number)值由124提高到161。

关键词: 仲钼酸铵, 乳酸, 硝酸, 环己烷催化氧化, 机理

Abstract:

Cyclohexane oxidation is one of the most important industrial reactions. In order to find more efficient and cheap catalysts for this reaction, we studied the catalytic activity of ammonium paramolybdate(APM). By GC analysis, we focus on the effects of the species and the amount of the acids on the reactivity. Compared with nitric acid, lactic acid is more effective for the oxidation of cyclohexanol to cyclohexanone, and thus improve the TON(turn over number) value of the target products from 124 to 161. Furthermore, we propose a possible reaction mechanism of this new way for green oxidation of cyclohexane.

Key words: ammonium paramolybdate, lactic acid, nitric acid, cyclohexane oxidation, mechanism

中图分类号:

O643

吴琼, 邢娜, 马喜彤, 徐丽婷, 邢永恒. 乳酸促进的仲钼酸铵催化氧化环己烷过程[J]. 应用化学, 2015, 32(1): 85-92.

WU Qiong,XING Na,MA Xitong,XU Liting,XING Yongheng. Lactic Acid Promoted Cyclohexane Oxidation with Ammonium Paramolybdate[J]. Chinese Journal of Applied Chemistry, 2015, 32(1): 85-92.

参考文献

[1] Silva A R,Mourāo T,Rocha J. Oxidation of Cyclohexane by Transition-metal Complexes with Biomimetic Ligands[J]. Catal Today ,2013,203:81-86.
[2] ZHANG Yicheng,DAI Weili,WU Guangjun, et al . Cyclohexane Oxidation:Small Organic Molecules as Catalysts[J]. Chinese J Catal ,2014,35(3):279-285(in Chinese).
张义成,戴卫理,武光军,等. 环己烷氧化反应:有机小分子的催化作用[J]. 催化学报,2014,35(3):279-285.
[3] Xing N,Xu L T,Bai F Y, et al . Synthesis and Characterization of Novel Transition Metal Complexes with Indole Acetic Acid Ligands:Evaluation of Their Catalytic Activity for the Oxidation of Cyclohexane[J]. Inorg Chim Acta ,2014,409:360-366.
[4] Mac Leod T C O,Kopylovich M N,Guedes da Silva M F C, et al . Copper(Ⅱ) Complexes of Arylhydrazones of β -Diketones Immobilized on Zn-Al Layered Double Hydroxides as Effective Recyclable Catalysts for Peroxidative Oxidation of Alkanes[J]. Appl Catal ,2012,439/440:15-23.
[5] Martins L M D R S,Martins A,Alegria E C B A, et al . Efficient Cyclohexane Oxidation with Hydrogen Peroxide Catalysed by a C-scorpionate Iron(Ⅱ) Complex Immobilized on Desilicated MOR Zeolite[J]. Appl Catal A ,2013,464/465:43-50.
[6] SHEN Yang,YANG Xiaojie,SUN Wei, et al . Research Progress in Catalytic Oxidation of Cyclohexane by Metalloporphyrins[J]. Contemporary Chem Ind ,2011,40(9):936-939(in Chinese).
沈阳,杨晓杰,孙巍,等. 金属卟啉催化氧化环己烷反应的研究进展[J]. 当代化工,2011,40(9):936939.
[7] Huang G,Liu S Y,Wang A P, et al . Catalysis of Structure-like Macromolecules Supported Manganese Tetraphenylporphyrin for Cyclohexane Oxidation[J]. Catal Commun ,2007,8:1183-1186.
[8] Einaga H,Futamura S. Oxidation Behavior of Cyclohexane on Alumina-supported Manganese Oxides with Ozone[J]. Appl Catal B ,2005,60:49-55.
[9] Kopylovich M N,Mahmudov K T,Guedes da Silva M F C, et al . Ortho-hydroxyphenylhydrazo-beta-diketones:Tautomery, Coordination Ability, and Catalytic Activity of Their Copper(Ⅱ) Complexes Toward Oxidation of Cyclohexane and Benzylic Alcohols[J]. Inorg Chem ,2011,50:918-931.
[10] Kakiuchi F,Chatani N. Catalytic Methods for C—H Bond Functionalization:Application in Organic Synthesis[J]. Adv Synth Catal ,2003,345:10771101.
[11] Sun C J,Li B J,Shi Z J. Direct CH Transformation via Iron Catalysis[J]. Chem Rev ,2011,111:1293-1314.
[12] Carrasco C J,Montilla F, lvarez E, et al . Molybdenum-catalysed Oxidation of Cyclohexene with Hydrogen Peroxide in the Presence of Alcohols and X-ray Structures of Octamolybdate [C 4 mim] 4 [Mo 8 O 26 ] and Tetraperoxodimolybdate [Htmpy]₂[{MoO(O₂)₂}₂( μ O)] Complexes[J]. Polyhedron ,2013,54:123-130.
[13] Amini M,Haghdoost M M,Bagherzadeh M. Oxido-peroxido Molybdenum(Ⅵ) Complexes in Catalytic and Stoichiometric Oxidations[J]. Coord Chem Rev ,2013,257:1093-1121.
[14] Mahmudov K T,Kopylovich M N,Guedes da Silva M F C, et al . New Copper(Ⅱ) Dimer with 3-(2-Hydroxy-4-nitrophenylhydrazo)pentane-2,4-dione and Its Catalytic Activity in Cyclohexane and Benzyl Alcohol Oxidations[J]. J Mol Catal A Chem ,2010,318:44-50.
[15] Silva T F S,Guedes da Silva M F,Mishra G S, et al . Synthesis and Structural Characterization of Iron Complexes with 2,2,2-Tris(1-pyrazolyl)ethanol Ligands:Application in the Peroxidative Oxidation of Cyclohexane Under Mild Conditions[J]. Organomet Chem ,2011,696:1310-1318.
[16] Kopylovich M N,Kirillov A M,Baev A K, et al . Heteronuclear Iron(Ⅲ)-Chromium(Ⅳ) Hydroxo Complexes and Hydroxides, and Their Catalytic Activity Towards Peroxidative Oxidation of Alkanes[J]. J Mol Catal A Chem ,2003,206:163-178.
[17] Kopylovich M N,Mac Leod T C O,Haukka M, et al . Aquasoluble Iron(Ⅲ)-arylhydrazone- β -diketone Complexes:Structure and Catalytic Activity for the Peroxidative Oxidation of C 5 -C 8 Cycloalkanes[J]. J Inorg Biochem ,2012,115:72-77.
[18] Xing N,Shan H,Tian X, et al . Two New Scorpionate Oxomolybdenum(Ⅶ)-poly-(pyrazolyl)borate Complexes:Synthesis, Structure, and Catalytic Performance in the Oxidation of Cyclohexane[J]. Dalton Trans ,2013,42:359-363.
[19] Chavan S A,Srinivas D,Ratnasamy P. Oxidation of Cyclohexane, Cyclohexanone, and Cyclohexanol to Adipic Acid by a NonHNO 3 Route over Co/Mn Cluster Complexes[J]. J Catal ,2002,212:39-45.
[20] Kirillova M V,Kozlov Y N,Shul'pina L S, et al . Remarkably Fast Oxidation of Alkanes by Hydrogen Peroxide Catalyzed by a Tetracopper(Ⅱ) Triethanolaminate Complex: Promoting Effects of Acid Co-catalysts and Water, Kinetic and Mechanistic Features[J]. J Catal ,2009,268:26-38.
[21] Pokutsa A,Fliunt O,Kubaja Y, et al . Relationships Between the Efficiency of Cyclohexane Oxidation and the Electrochemical Parameters of the Reaction Solution[J]. J Mol Catal A-Chem ,2011,347:15-21.
[22] Weigold H. Behaviour of Co-Mo-Al₂O 3 Catalysts in the Hydrodeoxygenation of Phenols[J]. Fuel ,1982,10(61):1021-1026.
[23] Topsøe N Y,Topsøe H. Adsorption Studies on Hydrodesulfurization Catalysts:Ⅰ.Infrared and Volumetric Study of NO Adsorption on Alumina-supported Co, Mo, and Co-Mocatalysts in Their Calcined State[J]. J Catal ,1982,2(75):354-374.
[24] Li W T,Zuo F,Jia K, et al . Study of Catalytic Effect of Ammonium Molybdate on the Bisphthalonitrile Resins Curing Reaction with Aromatic Amine[J]. Chinese Chem Lett ,2009,20:348-351.
[25] Sun C Q,Zhang J D. Fabrication and Electrochemical Behavior of Multilayer Films Containing 1:12 Phosphomolybdic Anions and Their Electrocatalytic Oxidation of Ascorbic Acid[J]. Electrochim Acta ,1998,8(43):943-950.
[26] Ma X L,Schulzke C. Molybdenum and Tungsten Complexes of Bis(Phenolate) Ligands,O,X,O(X=S or Se):Synthesis, Characterization and Catalytic Oxygen Atom Transfer Properties[J]. Inorg Chim Acta ,2013,395:218-224.
[27] MIAO Yongxia,YANG Xinli,GUO Lihong. Synthesis of Mo-HMS and Its Catalytic Performance in Liquid Epoxidation of Propylene[J]. Chinese J Catal ,2012,33(4): 711-716(in Chinese).
苗永霞,杨新丽,郭丽红. Mo-HMS 的制备及其催化丙烯液相环氧化反应性能[J]. 催化学报,2012,33(4):711-716.
[28] Kirillov A M,Kirillova M V,Pombeiro A J L. Multicopper Complexes and Coordination Polymers for Mild Oxidative Functionalization of Alkanes[J]. Coord Chem Rev ,2012,256:2741-2759.