共查询到18条相似文献,搜索用时 62 毫秒
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将钌基配合物催化剂固载于氯甲基化后的交联聚苯乙烯树脂上,催化超临界二氧化碳加氢反应。结果表明,多种类型的膦配体均能够与过渡金属钌原子配位催化二氧化碳加氢反应,但由于各种膦配体物化性质的差异,形成的活性物种具有不同的结构和催化性能。双齿膦配体形成的钌基配合物的加氢活性均高于单齿膦配体。 相似文献
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报道了螯合型正方平面羰基铑配合物催化甲醇羰基化反应的机理研究。通过含有两种与铑具有不同配位能力的授体的配体,与四羰基二氯二铑形成螯合型正方平面阳离子配合物。研究证明,该类配合物在催化甲醇羰基化反应过程中,其活性物种区别于文献报道的[Rh(CO)2I2]-阴离子。配合物中铑与吡啶环上共轭N形成的N→Rh配键,在羰基化反应过程中并非通常认为的断裂而是形成新的活性物种,即配体与铑作为整体参与了CH3I的氧化加成及CH3COI的生成过程。通过对相应的聚合物配体铑催化剂的研究,进一步证实了这个反应机理。这一结果,对该类催化剂分子设计,以及克服其工业使用中的催化剂沉淀失活等现象均有重要意义。 相似文献
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SiO_2负载高分子钯配合物催化剂的制备及其加氢性能研究 总被引:1,自引:0,他引:1
以SiO2为载体,三聚氰胺与甲醛的缩聚物为高分子配体,制备出一类新的SiO2负载含氮杂环的高分子配体配合钯催化剂,并用XPS对其进行了结构表征,结果表明高分子配体与活性中心钯进行了配位作用;并以硝基苯的加氢反应为研究对象,考察了其对硝基苯的催化加氢活性。在复合载体中,较佳的氮含量为1.49%;在氮气保护下,用乙醇还原时制备的催化剂具有较高的催化活性;并考察了反应温度及催化剂用量对反应的影响。在0.3g(0.00523mmolPd/0.1g催化剂)催化剂作用下,1mL硝基苯在乙醇溶剂中于313K的反应温度下,在0.1MPa压力下加氢2h,可使硝基苯的转化率达98%,而产物仅有苯胺。 相似文献
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氢甲酰化反应是目前生产醛醇化合物最重要的反应之一,高碳烯烃氢甲酰化工艺改进是研究的难点和热点之一。探索了一种C10烯烃氢甲酰化反应的工艺,以三苯基膦(Ph3P)和亚磷酸三(2-叔丁基-4-甲氧基苯基)酯(LA)混合物为配体,与乙酰丙酮二羰基铑原位合成的催化体系催化1-癸烯氢甲酰化反应。系统考察了反应温度、反应压力、铑浓度、膦铑比、无机盐添加剂对反应的影响。结果表明,在n(Ph3P)/n(LA)=10、铑质量分数为280 mg/kg,1-癸烯用量(相对于甲苯)为0.3 g/mL,n(膦)/n(铑)=45、反应温度为90 ℃、反应压力为2.0 MPa、n(一氧化碳)/n(氢气)=1条件下反应4 h,1-癸烯转化率为98.1%、醛收率为93.2%、正异比为7.5。研究还发现,在减压蒸馏产物与催化剂分离时,加入无机盐添加剂能够提高催化剂的稳定性,减少铑损失。 相似文献
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合成了水溶性配体三苯基膦间单磺酸(TPPMS)、三苯基膦间三磺酸(TPPTS)、2,2'-联毗啶-5-磺酸及相应的铑系列水溶性金属有机化合物, 并用相关体系进行了常压环己烯催化加氢反应。结果表明在常压下Rh-EDTA、RH-TPPMS、Rh-TPPTS、RH-联吡啶-5-磺酸等对催化环己烯加氢具有一定的活性, 在水/有机两相反应体系中, 由于催化剂在水中有相当的溶解度, 使反应后催化剂分离简单、快捷, 产物中催化剂残留少。由于烯烃的催化加氢反应可能是在水相中进行, 共溶剂及快速搅拌是必需的。 相似文献
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壳聚糖铁(Ⅲ)配合物的合成及其对苯酚羟基化的催化性能研究 总被引:4,自引:0,他引:4
以Fe3+溶液与壳聚糖合成了壳聚糖铁(Ⅲ)配合物,考察了反应时间、反应温度、pH值、Fe3+含量对反应的影响,确定壳聚糖铁(Ⅲ)配合物的优化合成条件为:pH值为1.8的3% Fe3+溶液和1.0 g壳聚糖在65℃下反应6 h,此时壳聚糖对Fe3+的吸附量达75 mg·g-1.通过X-射线粉末衍射(XRD)、红外光谱(FTIR)、扫描电镜(SEM)对其结构进行了表征.将制备的壳聚糖铁(Ⅲ)配合物作为催化剂用于苯酚羟基化反应中,在催化剂与苯酚的质量比为1∶100、苯酚与H2O2的摩尔比为1∶2、反应温度为60℃、反应时间为4 h的条件下,苯酚的转化率最高达22.88%,选择性最高达99.67%. 相似文献
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Catalysts prepared by a condensation reaction of Rh(CO)2(acac) within the supercages of zeolite Y made basic by treatment with NaN3 are active for CO hydrogenation and selective for low-molecular-weight olefins and methanol. High partial pressures of CO (or CO + H2) stabilize the catalyst. The predominant species in the catalyst are suggested to be rhodium carbonyl clusters trapped in the zeolite cages. 相似文献
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The catalytic performances of rhodium complexes with three new amphiphilic phosphine ligands, bis-(3-sodium sulfonatophenyl)-(4-tert-butylphenyl)-phosphine (3), phenyl-(3-sodium sulfonatophenyl)-(4-tert-butyl-phenyl)-phosphine (4) and bis-(4-tert-butylphenyl)-(3-sodium sulfonatophenyl) phosphine (5), in hydroformylation of 1-hexene, 1-octene and 1-dodecene have been studied. The steric attributes of free ligands are investigated by Tolman's cone angle method through geometric optimizations. The results reveal that the new phosphines are surface-active as the typical surfactants and the corresponding rhodium complexes show significant enhancements in the reaction rate and higher selectivities toward the normal aldehydes in comparison with those obtained by triphenylphosphine trisulfonate (TPPTS)- and triphenylphosphine disulfonate (TPPDS) rhodium complexes under identical conditions. 相似文献
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Pekka Suomalainen Helena Riihimäki Sirpa Jääskeläinen Matti Haukka Jouni T. Pursiainen Tapani A. Pakkanen 《Catalysis Letters》2001,77(1-3):125-130
The influence of the alkyl-substituted phosphanes (o-methylphenyl)diphenylphosphane (o-MeP), (o-ethylphenyl)diphenylphosphane (o-EtP), bis(o-methylphenyl)phenylphosphane (o-Me2P), bis(o-ethylphenyl)phenylphosphane (o-Et2P), and (2,4,5-trimethylphenyl)diphenylphosphane (2,4,5-MeP) was screened in model reaction of rhodium-catalyzed 1-hexene hydroformylation. Compared with PPh3, the prepared phosphanes afforded lower chemoselectivity towards aldehydes, but increased the normal to branched ratio. Catalyst results are discussed in relation to stereoelectronic properties of the phosphane ligands. Electron donor capacity of the ligands was studied in terms of spectroscopic data of the trans-RhCl(CO)P2 species, formed in reaction between Rh2(-Cl)2(CO)4 and the ligands (P). Furthermore, steric attributes of free and bound phosphanes were investigated by Tolmans cone angle method. Crystal structures for ligands o-EtP, o-Me2P, o-Et2P, and complexes trans-Rh(CO)Cl(o-MeP)2 and trans-Rh(CO)Cl(o-Et2P) were solved as well. 相似文献
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报道新型固体复合盐催化剂(Ⅱ)的制备,应用5种催化剂分别进行催化乙酸和乙醇合成乙酸丁酯的对比试验,选出优良催化剂(Ⅱ)并进行催化酯化合成了18种酯的研究工作。通过实验证明催化剂(Ⅱ)酯化性能优良(优于固体超强酸Fe2O3/SO4^2-),操作简单,污染小。在18种酯中乙酸丁酯的产率高达97.9%。 相似文献
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采用自由配体法制备了系列M(Salen)/Y(M=Ni,Pd and Ru)和RuL/Y[L=phenanthroline(phen),2,2′-bipyridyl(bpy) and N,N′-ethylenebis (salicylidene-aminato) (Salen)]催化剂,分别考察了金属元素性质和不同配体性质对所制催化剂催化加氢性能的影响,结果表明Ru(Salen)/Y的催化加氢活性优于Pd(Salen)/Y和Ni(Salen)/Y;不同性质与结构的配体对所制催化剂的催化加氢性能也有很大的影响,以Salen希夫碱为配体所制备的RuL/Y催化活性高于以二联吡啶(bpy)和邻菲咯啉(phen)为配体所制备的催化剂. 相似文献
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In this work, we describe how addition of alkylpolyglycol ether type nonionic surfactant affects the hydroformylation of 1-octene
in the presence of phosphine modified rhodium catalyst. Influence of different process parameters such as ligand excess and
amount of surfactant on the reaction rate and selectivity were discussed. Direct comparison of microemulsion systems with
classic processes was achieved by performing the reactions under comparable homogeneous and biphasic conditions. Thus, the
experiments were carried out using catalysts such as unmodified rhodium carbonyl HRh(CO)4 and HRh(CO)(PPh3)3 in homogeneous system, Rh–TPPTS complex in two-phase system and in association with co-solvent. 相似文献