水滑石负载CuMn氧化物的硫醇氧化催化剂制备及其催化性能
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摘要
采用无溶剂球磨法制备出水滑石(HT)负载型CuMn氧化物催化剂CuMn/HT,利用X射线衍射、原子吸收光谱,X射线光电子能谱,透射电子显微镜、扫描电子显微镜等分析方法测定了催化剂的组成及结构;并在常温条件下,以空气为氧化剂,乙醇为溶剂,考察了催化剂CuMn/HT在硫醇氧化反应中的催化性能。结果表明:CuMn/HT催化剂有效负载金属组分Cu和Mn的质量分数分别为7.1%,1.9%,其表面吸附氧中不饱和氧占比为84.9%,吸附的晶格氧只占15.1%;热过滤实验表明,硫醇氧化反应的催化作用来源于催化剂CuMn/HT而非溶液中存在的金属,且该催化剂至少可重复使用5次,二硫化物的收率不低于94%;以催化裂化汽油轻质馏分为原料,使用该催化剂在常温下进行硫醇氧化反应5 h后,FCC汽油产品中不含硫醇。
The hydrotalcite( HT)-supported CuMn oxide catalyst( CuMn/HT) was prepared by the solvent-free ball milling method,the composition and structure of the catalyst were characterized by X-ray diffraction( XRD),atomic absorption spectroscopy( ICP-AES),X-ray photoelectron spectroscopy( XPS),transmission electron microscopy( TEM) and scanning electron microscopy( SEM),etc,and the catalytic performance of the catalyst CuMn/HT in mercaptan oxidation reaction was investigated at room temperature with air as oxidant and ethanol as solvent. The results showed that the mass fraction of loaded Cu and Mn on the catalyst CuMn/HT was 7. 1% and 1. 9%,respectively,and in the surface saturated oxygen,the unsaturated oxygen accounted for 84. 9%,saturated lattice oxygen 15. 1%; the hot-filtration results showed that the catalytic reaction of mercaptan oxidation reaction derived from the catalyst CuMn/HT instead of the metal in the solution,the catalyst could be reused at least five times,the yield of disulfide was not less than 94%; the product did not contain mercaptan in the oxidation reaction for 5 h at room temperature with light fraction of fluid catalytic cracking gasoline as raw material.
The hydrotalcite( HT)-supported CuMn oxide catalyst( CuMn/HT) was prepared by the solvent-free ball milling method,the composition and structure of the catalyst were characterized by X-ray diffraction( XRD),atomic absorption spectroscopy( ICP-AES),X-ray photoelectron spectroscopy( XPS),transmission electron microscopy( TEM) and scanning electron microscopy( SEM),etc,and the catalytic performance of the catalyst CuMn/HT in mercaptan oxidation reaction was investigated at room temperature with air as oxidant and ethanol as solvent. The results showed that the mass fraction of loaded Cu and Mn on the catalyst CuMn/HT was 7. 1% and 1. 9%,respectively,and in the surface saturated oxygen,the unsaturated oxygen accounted for 84. 9%,saturated lattice oxygen 15. 1%; the hot-filtration results showed that the catalytic reaction of mercaptan oxidation reaction derived from the catalyst CuMn/HT instead of the metal in the solution,the catalyst could be reused at least five times,the yield of disulfide was not less than 94%; the product did not contain mercaptan in the oxidation reaction for 5 h at room temperature with light fraction of fluid catalytic cracking gasoline as raw material.
引文
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[2]蒋锋,齐邦峰,赵彬,等.汽油氧化脱硫醇研究[J].精细石油化工进展,2008,9(3):32-35.
[3]Bricker J C.Advances in MeroxTMprocess and catalysis for thiol oxidation[J].Topics in Catalysis,2012,55(19/20):1315-1323.
[4]胡震.汽油脱臭工艺的研究进展[J].石油与天然气化工,2007,36(4):302-305.
[5]Hajipour A R,Mallakpour S E,Adibi H.Selective and efficient oxidation of sulfides and thiols with benzyltriphenylphosphonium peroxymonosulfate in aprotic solvent[J].J Org Chem,2002,67(24):8666-8668.
[6]Mandal B,Basu B.Recent advances in S-S bond formation[J].Rsc Advances,2014,4(27):13854-13881.
[7]Dharmarathna S,King O C K,Pahalagedara L,et al.Manganese octahedral molecular sieve(OMS-2)catalysts for selective aerobic oxidation of thiols to disulfides[J].Applied Catalysis B Environmental,2014(147):124-131.
[8]Paul S,Islam S M.Oxidative dehydrogenation of thiols to disulfides at room temperature using silica supported iron oxide as an efficient solid catalyst[J].Rsc Advances,2016,6(98):95753-95759.
[9]Rajabi F,Kakeshpour T,Saidi M R.Supported iron oxide nanoparticles:Recoverable and efficient catalyst for oxidative S-Scoupling of thiols to disulfides[J].Catalysis Communications,2013,40(40):13-17.
[10]Dhakshinamoorthy A,Alvaro M,Garcia H.Chem Inform Abstract:Aerobic oxidation of thiols to disulfides using iron metal-organic frameworks as solid redox catalysts[J].Chemical Communications,2010,46(35):6476-6478.
[11]Chatterjee T,Ranu B C.Aerobic oxidation of thiols to disulfides under ball-milling in the absence of any catalyst,solvent,or base[J].Rsc Advances,2013,3(27):10680-10686.
[12]Menini L,Pereira M C,Ferreira A C,et al.Cobalt-iron magnetic composites as heterogeneous catalysts for the aerobic oxidation of thiols under alkali free conditions[J].Applied Catalysis A General,2011,392(1/2):151-157.
[13]Yang Y,Zhang S,Wang S,et al.Ball milling synthesized MnOxas highly active catalyst for gaseous POPs removal:Significance of mechanochemically induced oxygen vacancies[J].Environmental Science&Technology,2015,49(7):4473-4480.
[14]Carlos G,David R,Pablo A,et al.Back cover:Few-layer antimonene by liquid-phase exfoliation[J].Angew Chem Int Ed Engl,2016,55(46):14470.
[15]Xu M,Bi X R,Yu C Y,et al.Ball-milling synthesized hydrotalcite supported Cu-Mn mixed oxide under solventfree conditions:An active catalyst for aerobic oxidative synthesis of 2-acylbenzothiazoles and quinoxalines[J].Green Chemistry,2018(20):4638-4644.
[16]Meng X,Wang Y G,Wang Y M,et al.OMS-2-supported Cu hydroxide-catalyzed benzoxazoles synthesis from catechols and amines via domino oxidation process at room temperature[J].Journal of Organic Chemistry,2017,82(13):6922-6931.
[17]Nakai S,Uematsu T,Ogasawara Y,et al.Aerobic oxygenation of alkylarenes over ultrafine transition-metal-containing manganese-based oxides[J].Chem Cat Chem,2018,10(5):1096-1106.
[18]Uematsu T,Miyamoto Y,Ogasawara Y,et al.Molybdenumdopedα-MnO2as an efficient reusable heterogeneous catalyst for aerobic sulfide oxygenation[J].Catal Sci Technol,2015,6(1):222-233.