加压碱浸处理氰化浸出法回收汽车废催化剂中的贵金属

为提高铂族金属的浸出回收率,针对前期研究提出的汽车废催化剂先经加压碱浸处理而后再加压氰化浸出铂族金属的新工艺,变动预处理反应过程各种工艺参数,考察了对后续铂族金属氰化浸出指标的影响。结果表明:预处理可打开汽车废催化剂载体对铂族金属的包裹,有利于其氰化浸出;但物料粒度过细或反应碱用量过大、温度过高、时间过长均容易形成新相重新包裹,不利于氰化试剂与铂族金属有效接触;预处理渣进一步湿磨,可消除包裹,提高氰化浸出率;在实验最佳条件下,铂族金属氰化浸出率分别可达到:Pt 96%、Pd 98%、Rh92%。     

铂族金属配合物的光化学研究概论

概述铂族金属配合物的光化学研究包括激发去活和光化学反应，重点讨论光配体取代反应，光异构化反应和光氧化还原反应，举例说明了铂族金属配合物光化学的实际应用。     

铂族金属催化剂回收技术及发展动态

铂族金属失效催化剂是铂族金属二次资源的重要来源,综述了失效的汽车尾气催化剂和石化催化剂的回收技术现状,以及各种回收技术的优缺点,并对铂族金属失效催化剂提取冶金技术发展动态趋势进行介绍.     

汽车催化剂的回收

用于净化汽车尾气的催化剂含有铂族金属(PGM)铂(Pt)、钯(Pd)、铑(Rh),1980～2006年全世界用于汽车催化剂的铂族金属总量为3 500吨,其中钯1 600吨,铂1 500吨,铑330吨.同期世界上这三种金属的总产量约为8 300吨,这就是说,汽车催化剂消费了铂族金属总产量的大约40%,是铂族金属最重要的消费部门.本文评述了汽车催化剂的回收链,特别是催化剂中铂族金属的精炼技术.     

负载型铂族金属催化剂研究进展

负载型铂族金属催化剂具有优良的催化性能,对化工、环保、生物等领域发展影响显著。综述了适用于负载型铂族金属催化剂的各种载体材料(金属氧化物、沸石分子筛、炭材料、其他材料)及其优点,对催化剂制备工艺的发展趋势(单金属→双金属→复杂工艺)进行介绍,并对回收技术(分离载体、分离铂族金属、整体处理)进行讨论,着力提高催化剂的效率和铂族金属的利用率。     

从石油化工废催化剂中回收铂族金属的研究进展

贵金属催化剂是石油化工的核心技术之一,随着石油化工工业的发展,贵金属催化剂的用量也变得越来越大,从石油化工废催化剂中回收贵金属具有十分重要的意义。文章介绍了铂族金属的资源及石油化工领域用量较大的贵金属催化剂,并详细介绍了从石油化工废催化剂中回收铂族金属的工艺和产业化应用情况。     

汽车催化剂的回收

用于净化汽车尾气的催化剂含有铂族金属（PGM）铂（Pt）、钯（Pd）、铑（Rh），1980～2006年全世界用于汽车催化剂的铂族金属总量为3500吨，其中钯1600吨，铂1500吨，铑330吨。同期世界上这三种金属的总产量约为8300吨，这就是说，汽车催化剂消费了铂族金属总产量的大约40％，是铂族金属最重要的消费部门。本文评述了汽车催化剂的回收链，特别是催化剂中铂族金属的精炼技术。     

国外简讯

用作回收铂族金属的网催化反应时,从催化剂逸出的金属铂(尤其当氨氧化时用一贵金属网回收Pt),例如氧化NH_3时,设置贵金属Pd-Au合金网在催化网后面反应物流经的路上,该网由粗度不同的丝织成.其改进是这样,作无压力操作时线的粗度是从30~40%变动;作中     

铂族金属的资源,应用与开发

本文介绍铂族金属的特性以及矿藏资源在世界各国的分布情况。此外，对三种主要铂族金属在汽车工业、珠宝首饰、生物医学、燃料电池、航空航天、航海、信息、激光、能源、催化剂、新材料以及体育运动等方面的应用现状进行了详细的叙述。预测了铂族金属到２０００年的开发和展望。     

硝酸氧化炉尘中回收贵金属试验——湿法流程小试及扩试小结

一、前言氨氧化催化剂——铂铑钯三元合金网在使用过程中逐渐损耗减重。其中相当部分损耗金属沉积于氧化炉的管道中与炉中其它灰尘一起称为氧化炉尘。炉尘中铂族金属含量一般在千分之几到百分之几,视各厂对网的生产负荷,管理情况及炉尘收集情况而定。我们遵照毛主席的教导:要勤俭办一切事业,从炉尘中回收铂族金属,再重新使用是必要的和有重大意义的。本部分为湿法冶炼小型试验和30公斤扩大试验工作小结。     

Synthesis of functionally substituted metalloporphyrin receptor and study of their supramolecular properties

The ways of supramolecular self-assembly of metalloporphyrins containing peripheral ligand groups with metal cations and exobidentate ligands are studied.     

铑催化剂在NBR加氢领域的应用及回收方法

研究了铑催化剂在丁腈橡胶(NBR)均相加氢领域的应用,并开发了一种新的水相萃取回收铑的方法,首次以氯化亚锡为络合剂,2mol/L盐酸为萃取剂,可以很容易从氢化丁腈橡胶(HNBR)胶液中脱除铑催化剂。主要研究反应温度、时间、络合剂用量及萃取剂用量等条件对脱除铑催化剂的影响,在得到铑络合催化剂的最佳脱除条件下,铑催化剂的脱除率可达99%以上。IR以及1HNMR表征表明这种脱除铑催化剂工艺对HNBR的结构无影响,且不影响耐油的CN基团。     

Recent progress in structural modulation of metal nanomaterials for electrocatalytic CO_2 reduction

The electrochemical CO_2 reduction(ECR) into value-added products presents an appealing approach to mitigate CO_2 emission caused by excess consumption of fossil fuels.To obtain high catalytic activity and selectivity toward target product in ECR,designing and developing a stable and efficient electrocatalyst is of significant importance.To date,metal nanomaterials have been widely applied as electrocatalysts for ECR due to their unique physicochemical properties.The structural modulation of metal nanomaterials is an attractive strategy to improve the catalytic performance.In this review,the recent progress of structural modulation,including size,facet,grain boundary,composition,interface,ligand modification,and crystal phase,is systematically summarized from both theoretical and experimental aspects.Finally,the opportunities and perspectives of structural modulation of metal nanomaterials for ECR are proposed.     

一种新的铽发光配合物的合成、晶体结构及表征

在水热合成条件下合成一个新的吡啶-3,5-二羧酸的稀土铽配合物[Tb2(pydc-3,5)3(H2O)9]n3nH2O，通过X射线单晶衍射、元素分析和红外等手段的表征确定该化合物的组成和晶体结构。结果表明，吡啶-3,5-二羧酸(pydc-3,5)配体与稀土金属Tb形成了一维链状配位聚合物，中心稀土金属有两种配位形式，每个金属均与氧原子形成九配位的结构。配体中的羧酸根采用两种配位方式，即单齿配位和双齿配位。同时配合物能发出三价铽离子的特征绿色荧光，荧光光谱的研究表明，配合物表现出很好的荧光性能。     

Peculiarities of electroless deposition of Ni-W-P alloy on aluminum

A method of producing compact Ni-W-P films on aluminum from citrate-hypophosphite solution containing glycine as a ligand is proposed. The deposition rate and elemental and phase compositions of Ni-W-P films are shown to depend on the nature of the substrate. It is found that tungstate ions are reduced by hydrogen, which is formed either under catalytic oxidation of hypophosphite ions or upon dissolution of the substrate metal (aluminum) accompanied by hydrogen evolution from water.     

Design and electropolymerization of new chiral thiophene–salen complexes

New chiral thiophene-containing salen ligands have been synthesized. The corresponding metal complexes (Co, Cu, Cr and Ni) were prepared and electropolymerized at a platinum electrode by cyclic voltammetry. The resulting polymers exhibited stable and quasi-reversible redox processes when submitted to voltammetric repeated scans, whatever the nature of the metal or the structure of the ligand. Preliminary catalytic tests have been performed to examine the efficiency of these new chiral polymeric complexes as asymmetric heterogeneous catalysts.     

Preparation and electrical conduction properties of polymeric transition metal complexes of 1,1,2,2-ethenetetrathiolate ligand

The preparation and electrical conduction properties of a series of polymers based on transition metal complexes of the 1,1,2,2,-ethenetetrathiolate ligand (TT) of stoichiometry M₂-TT are described. The nickel, copper and platinum complexes exhibit high electrical conductivities (5, 5 and 3 S cm⁻¹, respectively); the cobalt and palladium polymers have conductivities many orders of magnitude lower. Partial oxidation of the copper-containing polymer can result in a ten-fold increase in the conductivity.     

Synthesis,photo- and electroluminescent properties of norbornene based platinum-containing copolymers

Norbornene based monomers containing the 2-phenylpyridinato–N,C²′ platinum(II) complex bonded by acetylacetonate or pyrazolonate anchor groups were synthesized and copolymerized with a carbazole-containing norbornene comonomer by ring-opening metathesis polymerization (ROMP). The photo- and electroluminescence spectra of the resulting Pt-copolymers are similar. They consist of broad bands with maxima at 495, 530 and 565 nm which arise from the mixed ligand centered (LC) and metal to ligand charge transfer (MLCT) transitions. The copolymer with the cyclometalated platinum(II) complex bonded to the polymer chain via the pyrazolonate anchor group revealed the highest brightness of electroluminescence (260 cd/m² at 21 V).     

一种离子型铱磷光配合物的合成及表征

以2-苯基吡啶(ppy)为环金属配体、4,4''-二叔丁基-2,2''-二吡啶(Dtbbpy)为N^N辅助配体,PF6^-为对阴离子,合成了一种离子型磷光配合物[Ir(ppy)2(Dtbbpy)]⁺PF6^-,产率为91.0%。通过元素分析(EA)、红外光谱(IR)、核磁共振谱(¹H-NMR和¹³C-NMR)和质谱(MS)对其组成和化学结构进行了确认和表征。采用紫外可见光谱(UV-Vis)和光致发光光谱(PL)研究了其光物理性能,该配合物在二氯甲烷中的最大发射波长为557 nm,属于黄绿光发射离子型铱磷光配合物。     

Preparation,characterization, electrochemistry and in situ spectroelectrochemistry of novel α-tetra[7-oxo-3-(2-chloro-4-fluorophenyl)coumarin]-substituted metal-free,cobalt and zinc phthalocyanines

In this study, a novel ligand, 7-(2,3-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin was synthesized by the reaction of 3-(2-chloro-4-fluorophenyl)-7-hydroxycoumarin with 1,2-dicyano-3-nitrobenzen in dry DMF as the solvent in the presence of K₂CO₃ as the base. The preparation of the corresponding phthalocyanines H₂Pc, CoPc and ZnPc, substituted with 7-oxo-3-(2-chloro-4-fluorophenyl)coumarin functional groups at α positions of the Pc ring, was achieved by the cyclotetramerization of the coumarin ligand without any metal salts or with the relevant metal(II) acetates in 2-N,N-dimethylaminoethanol. The structures of the compounds were confirmed by elemental analysis, UV–vis, IR, MALDI-TOF mass and ¹H NMR spectra. In addition, aggregation and redox properties of the novel phthalocyanines with four halogenated coumarinoxy substituents at α positions of the phthalocyanine ring were compared with those of previously reported corresponding ones with β-substitution, by UV–vis spectroscopy, in situ spectroelectrochemistry and voltammetry. Remarkable differences in these properties between α- and β-substituted compounds were detected, and discussed in detail.