Merox and Related Metal Phthalocyanine Catalyzed Oxidation Processes

Alkyl and aromatic mercaptans are among important organic sulfur compounds distributed in petroleum products. The mercaptans cause foul odor and are corrosive toward metals. In addition, mercaptans may cause oxidative deterioration as well as inhibit the performance of various additives (TEL, antioxidants) in finished products. Therefore, it is necessary to remove them, either by extractive processes or by converting them into innocuous disulfides. Such processes are usually referred to as “sweetening.”     

金属酞菁催化氧化含硫化合物的实验研究

采用浸渍法将1,4,8,11,15,18,22,25-(异戊氧基)酞菁钴(铜,镍)分别负载到介孔分子筛MCM-41上,形成MCM-41-Co Pc,MCM-41-Ni Pc,MCM-41-Cu Pc组装体。在(20±1)℃,p H=7氧气气氛下,以各组装体为催化剂,研究了其对Na2SO3溶液的催化氧化活性。实验结果表明:各组装体具有良好的催化氧化性能,不同金属酞菁组装体表现出不同的催化活性,MCM-41-Co Pc催化剂的催化氧化性能最好。同种催化剂在不同浓度Na2SO3溶液中的催化活性也有所不同,此类催化剂可重复利用5次。负载型金属酞菁对硫化物的催化氧化作用,可以应用到油气田开发中的污水处理方面,对环保贡献了一定力量。     

Advances in Merox? Process and Catalysis for Thiol Oxidation

The UOP Merox? process is an efficient and economical catalytic process developed for the treatment of petroleum fractions to remove sulfur present as thiols or to directly convert thiols to less-objectionable disulfides. The key to this oxidation process is a metal-chelate redox catalyst which selectively catalyzes the oxidation of thiols with oxygen as the oxidant without causing undesirable oxidation of hydrocarbons. In this paper, we discuss the Merox? process and mechanisms by which the catalyst selectively oxidizes thiols. Additionally, we discuss the development of promoted thiol oxidation catalyst systems which eliminate the use of caustic media in the oxidation process.     

过渡金属催化烃类液相氧化反应的研究进展

作为新型、廉价的烃类氧化反应催化剂,铜、铁络合物表现出良好的应用潜力。本文总结了烃类催化氧化反应的条件,对铜、铁在烃类氧化反应中的应用进行介绍,并讨论其反应机理。     

金属席夫碱催化分子氧氧化环己烷的研究

采用两步法合成了两类共18种金属席夫碱配合物,将其用于催化环己烷的氧化反应。结果表明:金属席夫碱配合物在温和条件下能有效催化环己烷的反应,生成目的产物;双核金属席夫碱催化效果较单核好。     

金属酞菁的固相法合成

以苯酐、尿素、金属盐、钼酸铵为原料，用固相法合成出一系列金属酞菁配合物，并用元素分析、红外光谱对它们进行了表征。铜、镍、钴、钒等金属酞菁产率较高，镁、锰酞菁产率不高；不同的金属酞菁的理想反应温度为200℃-280℃之间，尿素与苯酐的摩尔比为1：5时产率最高，适量加入碳酸钠和氯化铵有利于产率的提高。本法具有工艺简单、生产稳定、质量好、成本低等优点。     

金属酞菁类复合光催化剂研究进展

金属酞菁具有优异的物理、化学性能,其复合光催化剂是研究的热点之一.综述了金属酞菁类复合光催化剂的制备方法,介绍了金属酞菁类复合光催化剂的应用,分析了制备和应用中存在的问题,对未来的研究方向进行了展望.     

Efficient Allylic Oxidation of Olefins Catalyzed by Polymer Supported Metal Schiff Base Complexes with Peroxides

Three homogeneous Cu(II), Co(II) and Ni(II) complexes of a Schiff base ligand and their heterogeneous complexes supported on poly(4-aminostyrene) were prepared and characterized by using elemental analysis, fourier transform infrared spectroscopy, UV–Vis diffuse reflectance spectroscopy, thermogravimetric analysis and scanning electron microscopy. The catalytic performance of both homogeneous and heterogeneous complexes was evaluated in the liquid phase oxidation of cyclohexene, styrene and trans-stilbene in acetonitrile with tert-butylhydroperoxide or hydrogen peroxide as the oxidant. All types of catalyst were active in oxidation; and, the complexes produce allylic oxidation products in all cases. Immobilized complexes are slightly more active than their homogeneous complexes. The polymer-supported Cu(II) complex shows a higher catalytic activity than the other metal species. The activities of the immobilized catalysts remained nearly the same after five cycles, suggesting the true heterogeneous nature of the catalyst.     

金属酞菁及助催化剂存在下对乙苯的液相催化氧化

在常压氧、100℃反应条件下,研究了不同金属酞菁及助催化剂K2Cr2O7存在时对乙苯液相催化氧化的活性,同时考察了高价金属氧化物V2O5、MnO5、MoO3在钴酞菁液相催化氧经乙苯中的协同效应。反应时间6h,无助催化剂K2Cr2O7存在时,钴酞菁具有较高的活性,铁酞菁具有最高的转化率。     

浅述高级氧化法处理水体中有机污染物

利用高级氧化法处理水体中有机污染物,尤其是难降解的有机污染物是当前国内外水处理领域的研究热点。文章综述了高级氧化技术在处理水体中有机污染物的研究状况,包括高级氧化技术的发展史、技术特点、分类、反应动力学、各种高级氧化体系及其反应机理和研究进展。     

金属酞菁配合物的合成及其三阶非线性光学性能研究

合成了酞菁铝(AlClPc)、酞菁亚铁(Ⅱ)(FePc)、酞菁钴(Ⅱ)(CoPc)、酞菁镍(Ⅱ)(NiPc)以及酞菁铜(Ⅱ)(CuPc)等金属酞菁配合物.使用四波混频技术测量了它们在硫酸溶液中的三阶非线性光学系数x(3)值,发现四种过渡金属酞菁配合物的x(3)值随着金属的原子系数的增加而上升.而酞菁铝的x(3)值则大于酞菁亚铁(Ⅱ)和酞菁钴(Ⅱ)的x(3)值、小于酞菁镍(Ⅱ)和酞菁铜(Ⅱ)的x(3)值.文中初步讨论了金属离子的d电子以及与酞菁构成的空间结构对紫外吸收和三阶非线性光学性质的影响机理.     

Sustainable Desulfurization Processes Catalyzed by Titanium-Polyoxometalate@TM-SBA-15

A titanium-polyoxometalate with a µ-hydroxo dimeric structure [(PW₁₁O₃₉Ti)₂OH]^7? ((PW₁₁Ti)₂OH) was used efficiently for the desulfurization of a model diesel containing a mixture of various refractory sulfur compounds present in real fuels. The catalytic performance of the µ-hydroxo dimeric compound was compared in its homogeneous form and also when immobilized in the trimethylammonium-functionalized SBA-15 ((PW₁₁Ti)₂OH@TM-SBA-15). An optimization study was performed using the homogeneous and heterogeneous catalysts to obtain high catalytic efficiency, sustainability and cost-effectiveness of the system. Different optimized conditions were found using the homogeneous and heterogeneous catalysts. Lower amounts of solvent extraction (MeCN, 175 µL), catalyst (0.5 µmol of active center) and oxidant (50 µL) were used to produce sulfur-free model diesel after 2 h at 70?°C, using the heterogeneous (PW₁₁Ti)₂OH@TM-SBA-15 catalyst. On the other hand, complete desulfurization was achieved with homogeneous (PW₁₁Ti)₂OH catalyst after only 40 min, although higher amounts of MeCN (750 µL), catalyst (1.5 µmol) and oxidant (75 µL) were used. Both systems combined liquid–liquid extraction and catalytic oxidation. Using the heterogeneous catalyst, adsorption of oxidized-sulfur compound was also observed. Both homogeneous and heterogeneous desulfurization systems presented a high capacity to be reused/recycled for consecutive desulfurization cycles.     

NHPI和磺化酞菁钴催化的环己烷氧化反应

以N-羟基邻苯二甲酰亚胺(NHPI)和磺化酞菁钴(CoSPc)组成的催化体系对环己烷的氧化反应进行了研究,通过对反应时间、温度、NHPI用量、磺化酞菁钴用量的考察,得出环己烷氧化的最优反应条件为:反应时间2h,反应温度80℃,n(环己烷)∶n(NHPI)=10∶1,n(NHPI)∶n(CoSPc)=6∶1。在气相色谱上用内标法进行氧化反应产物的组成分析,产物除了环己酮和环己醇外,还发现了乙酸环己酯。在最优反应条件下,环己酮、环己醇、乙酸环己酯的产率及总产率为10.5%、1.1%、0.4%和12.0%。     

双核酞菁铁催化t-BHP氧化环己烷性能研究

考察了实验室自制的酰亚胺基取代双核酞菁铁(FeBPcN)催化氧化环己烷的性能,所用氧化剂为叔丁基过氧化氢,探讨了反应时间、反应温度、催化剂用量、溶剂、氧化剂用量及加入方式对该催化反应的影响。得出实验室自制的双核酞菁铁催化氧化环己烷的最优化条件为:反应压力:常压;反应温度:25℃;反应时间:20h;环己烷用量:2mL;催化剂用量:0.02g;氧化剂用量:10mLt-BHP;氧化剂加入方式:1.25mL/h滴加。自制酰亚胺基取代双核酞菁铁与卟啉铁、酞菁铁相比,催化性能无明显差别且容易回收,回收一次和回收两次后酮醇产率分别为17.0和17.1,仍能保持原有的催化氧化性能。     

有机废水处理的高级氧化技术研究

综述了近年来有机废水处理的高级氧化技术，主要包括Fenton氧化、臭氧氧化、超声声化学氧化、湿式氧化、超临界水氧化及光催化氧化技术等，并介绍了各种处理技术的基本原理、特点及研究进展。     

活性炭催化氧化制备草甘膦工艺

研究活性炭催化下,氧气氧化双甘膦（PMIDA）制备草甘膦（PMG）工艺条件,在1．4MPa、90℃时,20g／100mLH2O浓度的PMIDA中,加入0．44mol／L的碱,PMG收率达到83％,原液浓度达12g／100mLH2O。     

Bromate Formation in Ozone and Advanced Oxidation Processes

Both the direct ozone reaction and the indirect hydroxyl radical reaction are important in ozonation of drinking water. This article investigates the effectiveness of ozone versus the advanced oxidation process of ozone coupled with hydrogen peroxide in the formation of bromate. The investigation was conducted on a pilot scale at various H₂O₂:O₃ dose ratios of 0.1, 0.2, and 0.35 at different times of the year. The results of this study show a reduction in bromate with the addition of hydrogen peroxide to an ozone system versus ozone alone. It was also observed that bromate increased with increased H₂O₂:O₃ ratios; however, concentrations were still lower than those in the ozone only system.     

微囊型铁卟啉的制备及催化氧化环己烷研究

将四苯基铁(Ⅲ)卟啉包埋在苯乙烯和二乙烯苯的共聚物中制备微囊型催化剂。研究了苯乙烯和二乙烯苯摩尔比和搅拌速度对微囊型催化剂制备的影响,结果表明,苯乙烯和二乙烯苯摩尔比为1∶1,搅拌速度为800r/m in时,催化剂的粒子表面光滑、圆整。通过红外、扫描电镜对其进行了表征。用所制备的微囊型催化剂催化环己烷氧化,比游离的铁卟啉催化活性高,当其粒径在30~50μm时,环己醇产率为73.5%。该催化剂回收使用5次后,环己醇的产率仍可达到63.1%。