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公开(公告)号：US4543348A
公开(公告)日：1985-09-24
申请号：US467157
申请日：1983-02-16
摘要： An electrode having a lead base and a catalyst is manufactured by (a) compressing titanium sponge particles so as to consolidate them to a coherent porous layer, (b) applying the catalyst to the titanium sponge particles, and (c) fixing the layer of consolidated sponge particles to the lead base. The catalyst is formed on the titanium sponge particles before or after their consolidation to a coherent layer. This layer may be produced and fixed to the base in a single compressing and fixing step combining (a) and (c). Oxygen is anodically evolved at a reduced, stable potential by means of this electrode, so that it can be usefully applied as an anode in processes for electrowinning metals from acid electrolytes.
摘要翻译： 通过以下方法制造具有铅基和催化剂的电极：（a）压缩钛海绵颗粒以将其固结在粘着多孔层上，（b）将该催化剂施加到钛海绵颗粒上，和（c）将 固结海绵颗粒到铅基。 催化剂在固化到相干层之前或之后在钛海绵颗粒上形成。 可以在组合（a）和（c）的单个压缩和固定步骤中生产并固定该层。 氧气通过该电极在降低的稳定电位下阳极放电，使得其可以有用地用作阳极，用于从酸性电解质中电解提取金属。
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2.发明授权Composite catalytic material particularly for electrolysis electrodes and method of manufacture 失效复合催化材料特别适用于电解电极及其制造方法
公开(公告)号：US4585540A
公开(公告)日：1986-04-29
申请号：US689134
申请日：1985-01-07
申请人： Henri B. Beer , Frans A. M. Van den Keybus , Jeries I. Bishara , William A. Kovatch , Jean M. Hinden
发明人： Henri B. Beer , Frans A. M. Van den Keybus , Jeries I. Bishara , William A. Kovatch , Jean M. Hinden
CPC分类号： C25B11/0484
摘要： A porous high surface area composite electroconductive catalytic material, particularly as electrocatalyst for electrolysis electrodes, comprises a porous pre-formed matrix which is a catalytic mixed crystal material of at least one platinum group metal oxide and at least one valve metal oxide throughout which a subsequently-added additional catalyst preferably consisting of at least one platinum group metal and/or oxide is dispersed by chemideposition in an oxidizing or reducing atmosphere preferably followed by an annealing post heat treatment. The porous matrix may be ruthenium-titanium oxide and the additional catalyst advantageously comprises at least two oxides of ruthenium, rhodium, palladium and iridium, other combinations being possible.
摘要翻译： 多孔高表面积复合导电催化材料，特别是作为电解电极的电催化剂，包括多孔预形成基体，其是至少一种铂族金属氧化物和至少一种阀金属氧化物的催化混合晶体材料，其中随后 优选由至少一种铂族金属和/或氧化物组成的附加催化剂通过化学沉积分散在氧化或还原气氛中，优选随后进行热处理退火。 多孔基质可以是钌 - 氧化钛，另外的催化剂有利地包括钌，铑，钯和铱的至少两种氧化物，其它组合也是可能的。
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公开(公告)号：US5827411A
公开(公告)日：1998-10-27
申请号：US716821
申请日：1996-09-10
CPC分类号： C25D21/16 , C25D21/20 , Y10S204/13
摘要： Methods, and various apparatus therefor, are disclosed for the electrolytic treatment of an acidic solution. Generally the method comprises: (a) providing an electrolytic cell, the cell comprising: (i) an anode chamber and an anode therein; (ii) a cathode chamber and a cathode therein; and (iii) a diaphragm. Usually the diaphragm is of a non-isotropic fibrous mat comprising 5-70 weight percent organic halocarbon polymer fiber in adherent combination with about 30-95 weight percent of finely divided inorganic particulate impacted into said fiber during fiber formation, the diaphragm having a weight per unit of surface area of about 3-12 kilograms per square meter. The method can continue by (b) introducing the acidic solution into the cell; (c) impressing a current on the anode and the cathode causing the migration of ions through the diaphragm; and (d) recovering a product of the electrolytic treatment from the anode chamber, or the cathode chamber, or from both chambers. In one method, the acidic solution is a cell bath circulated to the anode chamber, while rinse solution downstream of the cell bath is circulated to the cathode chamber. The method, and apparatus therefor, are particularly applicable to the recovery of hexavalent chromium from a dilute chromium electroplating rinse solution.
摘要翻译： 公开了用于电解处理酸性溶液的方法及其各种设备。 通常，该方法包括：（a）提供电解池，所述电池包括：（i）阳极室和阳极; （ii）阴极室和阴极; 和（iii）隔膜。 通常，隔膜是非均质纤维垫，其包含5-70重量％的有机卤化碳聚合物纤维，其粘合组合与约30-95重量％的在纤维形成期间冲击到所述纤维中的细碎无机颗粒，隔膜具有重量 单位面积约3-12公斤每平方米。 该方法可以通过（b）将酸性溶液引入细胞中来继续进行; （c）在阳极和阴极上施加电流，导致离子迁移通过隔膜; 和（d）从阳极室或阴极室或从两个室回收电解处理的产物。 在一种方法中，酸性溶液是循环到阳极室的细胞浴，而细胞浴下游的漂洗溶液循环到阴极室。 该方法及其装置特别适用于从稀镀铬电镀冲洗溶液中回收六价铬。
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公开(公告)号：US5593627A
公开(公告)日：1997-01-14
申请号：US534683
申请日：1995-09-27
CPC分类号： C25D21/16 , C25D21/20 , Y10S204/13
摘要： Methods, and various apparatus therefor, are disclosed for the electrolytic treatment of an acidic solution. Generally the method comprises: (a) providing an electrolytic cell, the cell comprising: (i) an anode chamber and an anode therein; (ii) a cathode chamber and a cathode therein; and (iii) a diaphragm. Usually the diaphragm is of a non-isotropic fibrous mat comprising 5-70 weight percent organic halocarbon polymer fiber in adherent combination with about 30-95 weight percent of finely divided inorganic particulate impacted into said fiber during fiber formation, the diaphragm having a weight per unit of surface area of about 3-12 kilograms per square meter. The method can continue by (b) introducing the acidic solution into the cell; (c) impressing a current on the anode and the cathode causing the migration of ions through the diaphragm; and (d) recovering a product of the electrolytic treatment from the anode chamber, or the cathode chamber, or from both chambers. In one method, the acidic solution is a cell bath circulated to the anode chamber, while rinse solution downstream of the cell bath is circulated to the cathode chamber. The method, and apparatus therefor, are particularly applicable to the recovery of hexavalent chromium from a dilute chromium electroplating rinse solution.
摘要翻译： 公开了用于电解处理酸性溶液的方法及其各种设备。 通常，该方法包括：（a）提供电解池，所述电池包括：（i）阳极室和阳极; （ii）阴极室和阴极; 和（iii）隔膜。 通常，隔膜是非均质纤维垫，其包含5-70重量％的有机卤化碳聚合物纤维，其粘合组合与约30-95重量％的在纤维形成期间冲击到所述纤维中的细碎无机颗粒，隔膜具有重量 单位面积约3-12公斤每平方米。 该方法可以通过（b）将酸性溶液引入细胞中来继续进行; （c）在阳极和阴极上施加电流，导致离子迁移通过隔膜; 和（d）从阳极室或阴极室或从两个室回收电解处理的产物。 在一种方法中，酸性溶液是循环到阳极室的细胞浴，而细胞浴下游的漂洗溶液循环到阴极室。 该方法及其装置特别适用于从稀镀铬电镀冲洗溶液中回收六价铬。
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公开(公告)号：US5405507A
公开(公告)日：1995-04-11
申请号：US67918
申请日：1993-05-27
CPC分类号： C25D21/16 , C25D21/20 , Y10S204/13
摘要： Methods, and various apparatus therefor, are disclosed for the electrolytic treatment of an acidic solution. Generally the method comprises: (a) providing an electrolytic cell, the cell comprising: (i) an anode chamber and an anode therein; (ii) a cathode chamber and a cathode therein; and (iii) a diaphragm. Usually the diaphragm is of a non-isotropic fibrous mat comprising 5-70 weight percent organic halocarbon polymer fiber in adherent combination with about 30-95 weight percent of finely divided inorganic particulate impacted into said fiber during fiber formation, the diaphragm having a weight per unit of surface area of about 3-12 kilograms per square meter. The method can continue by (b) introducing the acidic solution into the cell; (c) impressing a current on the anode and the cathode causing the migration of ions through the diaphragm; and (d) recovering a product of the electrolytic treatment from the anode chamber, or the cathode chamber, or from both chambers. In one method, the acidic solution is a cell bath circulated to the anode chamber, while rinse solution downstream of the cell bath is circulated to the cathode chamber. The method, and apparatus therefor, are particularly applicable to the recovery of hexavalent chromium from a dilute chromium electroplating rinse solution.
摘要翻译： 公开了用于电解处理酸性溶液的方法及其各种设备。 通常，该方法包括：（a）提供电解池，所述电池包括：（i）阳极室和阳极; （ii）阴极室和阴极; 和（iii）隔膜。 通常，隔膜是非均质纤维垫，其包含5-70重量％的有机卤化碳聚合物纤维，其粘合组合与约30-95重量％的在纤维形成期间冲击到所述纤维中的细碎无机颗粒，隔膜具有重量 单位面积约3-12公斤每平方米。 该方法可以通过（b）将酸性溶液引入细胞中来继续进行; （c）在阳极和阴极上施加电流，导致离子迁移通过隔膜; 和（d）从阳极室或阴极室或从两个室回收电解处理的产物。 在一种方法中，酸性溶液是循环到阳极室的细胞浴，而细胞浴下游的漂洗溶液循环到阴极室。 该方法及其装置特别适用于从稀镀铬电镀冲洗溶液中回收六价铬。
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公开(公告)号：US4543174A
公开(公告)日：1985-09-24
申请号：US628533
申请日：1984-07-06
申请人： Henri B. Beer , Michael Katz , Jean M. Hinden
发明人： Henri B. Beer , Michael Katz , Jean M. Hinden
CPC分类号： C25B11/0484 , C25C7/02
摘要： A method of making a catalytic lead-based oxygen-evolving anode comprises catalytically activating titanium sponge particles larger than 300 microns by impregnating with a solution containing Mn and Ru compounds, in amounts corresponding to Mn/Ru in an atomic ratio between 70/30 and 90/10, and thermally converting the compounds to an electrocatalyst comprising Mn and Ru in oxide form. Catalytic Ti sponge particles with up to 3 wt % Ru are thus produced, which are then uniformly distributed on the surface of a lead anode base in an amount greater than 400 g/m.sup.2, pressed, and partly embedded, thereby firmly anchoring and electrically connecting them to the lead anode base. The catalytic lead-based anode thus produced operates with oxygen evolution on the catalytic particles at a reduced potential at which the lead base remains electrochemically inactive. It thereby operates with significant energy savings over an extended service life.
摘要翻译： 制备催化铅基放氧阳极的方法包括通过用含有Mn和Ru化合物的溶液浸渍而以大于300微米的钛海绵颗粒催化活化，其量相当于Mn / Ru，原子比为70/30和 90/10，并且将化合物热转化成包含氧化物形式的包含Mn和Ru的电催化剂。 因此产生具有高达3重量％Ru的催化钛海绵颗粒，然后将其均匀分布在铅阳极基底的表面上，其量大于400g / m 2，压制和部分嵌入，由此牢固地锚固和电连接 他们到铅阳极基地。 如此生产的催化性铅基阳极在催化剂颗粒上以降低的电位产生氧气而导致铅基保持电化学活性。 从而在延长的使用寿命期间显着节省能源。
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公开(公告)号：US4528084A
公开(公告)日：1985-07-09
申请号：US507937
申请日：1983-06-23
申请人： Henri B. Beer , Jean M. Hinden
发明人： Henri B. Beer , Jean M. Hinden
CPC分类号： C25B11/0484 , C25C7/02
摘要： An electrode for use in electrolytic processes comprises a base of film-forming metal such as titanium with an operative outer electrocatalytic surface which is an integral surface film of a compound of the titanium base, usually the oxide, incorporating a platinum-group metal electrocatalyst, preferably iridium, rhodium, palladium and/or ruthenium as metal or oxide. The surface film is formed by the application of a dilute solution of a thermodecomposable iridium, rhodium and/or ruthenium compound containing an agent such as HCl which attacks the titanium base and converts metal from the base into ions which are converted to the compound in a subsequent heating step. The concentrations of this agent and of the thermodecomposable compound and the number of applied layers are such that during heating the electrocatalyst formed from the decomposed compound is incorporated fully in the surface film formed from the base. The base is usually in sheet form, but may also be a powder.
摘要翻译： 用于电解方法的电极包括钛的成膜金属的基底，其具有可操作的外部电催化表面，所述外部电催化表面是钛基的化合物的整体表面膜，通常是掺入铂族金属电催化剂的氧化物， 优选铱，铑，钯和/或钌作为金属或氧化物。 表面膜是通过使用含有诸如HCl的试剂（例如HCl）的可热分解的铱，铑和/或钌化合物的稀释溶液形成的，所述试剂可以将金属从碱中转化为离子，将其转化为化合物 后续加热步骤。 该试剂和热可分解化合物的浓度和施加层的数量使得在加热期间，由分解的化合物形成的电催化剂完全并入从由碱形成的表面膜中。 基底通常是片状，但也可以是粉末。
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8.发明授权Dimensionally stable coated electrode for electrolytic process, comprising protective oxide interface on valve metal base, and process for its manufacture 失效用于电解工艺的尺寸稳定的涂层电极，包括阀金属基底上的保护性氧化物界面及其制造方法
公开(公告)号：US4444642A
公开(公告)日：1984-04-24
申请号：US293382
申请日：1981-08-17
申请人： Jean M. Hinden , Henri B. Beer
发明人： Jean M. Hinden , Henri B. Beer
CPC分类号： C25C7/02 , C25B11/0484 , C25B11/16
摘要： An electrode for use in an electrolytic process is provided with a mixed oxide interface between a titanium base and an outer coating. The mixed oxide is formed at said interface by means of titanium from the base and noble metal from a solution containing a predetermined amount of HCl which attacks the titanium base surface. Slow drying provides a metal chloride mixture which is thermally converted to said mixed oxide of titanium and noble metal in a given ratio, whereby to protect the titanium base from oxidation.An outer coating of manganese dioxide or lead dioxide is electroplated on the mixed oxide layer so as to provide an inexpensive electrode with improved resistance to oxidation.This electrode can be used for various processes where a high resistance to oxidation is required, e.g. as a manganese dioxide anode in a metal electrowinning process or as a lead dioxide anode for electroflotation or organic oxidation reactions.
摘要翻译： 用于电解工艺的电极在钛基和外涂层之间设置有混合的氧化物界面。 混合氧化物通过来自碱的钛和贵金属在所述界面处由含有预定量的HCl的钛溶液表面形成。 缓慢干燥提供金属氯化物混合物，其以给定的比率热转化为钛和贵金属的所述混合氧化物，由此保护钛碱免受氧化。 在混合氧化物层上电镀二氧化锰或二氧化铅的外涂层，以便提供具有改善的抗氧化性能的廉价电极。 该电极可用于需要高抗氧化性的各种工艺，例如， 作为金属电解提取工艺中的二氧化锰阳极或用于电浮选或有机氧化反应的二氧化铅阳极。
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公开(公告)号：US4331528A
公开(公告)日：1982-05-25
申请号：US194071
申请日：1980-10-06
申请人： Henri B. Beer , Jean M. Hinden
发明人： Henri B. Beer , Jean M. Hinden
CPC分类号： C25B11/0478 , C25B11/0484
摘要： An electrode for use in electrolytic processes comprises a substrate of film-forming metal such as titanium having a porous electrocatalytic coating comprising at least one platinum-group metal and/or oxide thereof possibly mixed with other metal oxides, in an amount of at least about 2 g/m.sup.2 of the platinum-group metal(s) per projected surface area of the substrate. Below the coating is a preformed barrier layer constituted by a surface oxide film grown up from the substrate. This preformed barrier layer has rhodium and/or iridium as metal or compound incorporated in the surface oxide film during formation thereof in an amount of up to 1 g/m.sup.2 (as metal) per projected surface area of the substrate.
摘要翻译： 用于电解方法的电极包括诸如钛的成膜金属的基底，其具有多孔电催化涂层，该多孔电催化涂层包含至少一种与其它金属氧化物混合的铂族金属和/或氧化物，其量至少约为 基板的每个投影表面积为2g / m 2的铂族金属。 涂层下面是由从基材生长的表面氧化膜构成的预制阻挡层。 该预成型阻挡层在其形成期间具有以表面氧化膜形成的金属或化合物的铑和/或铱，其量为基板每投影表面积高达1g / m 2（作为金属）。
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10.发明授权Electrode with outer coating for effecting an electrolytic process and protective intermediate coating on a conductive base, and method of making same 失效具有外部涂层的电极，用于在导电性基底上进行电解处理和保护性中间涂层及其制造方法
公开(公告)号：US4435313A
公开(公告)日：1984-03-06
申请号：US293381
申请日：1981-08-17
申请人： Michael Katz , Jean M. Hinden , Jurgen F. Gauger
发明人： Michael Katz , Jean M. Hinden , Jurgen F. Gauger
CPC分类号： C25B11/16 , C25B11/0489 , C25C7/02
摘要： An electrode with an outer coating for effecting an electrolytic process is provided with a protective intermediate coating consisting of a conducting insoluble polymer network formed in situ on a titanium base and containing a small amount of finely dispersed platinum group metal catalyst.A method of manufacturing the electrode comprises applying to the titanium base several layers of a solution containing a polymer precursor and a platinum metal compound which are thermally converted to the protective polymer coating, on which the outer coating is formed, more particularly by electrodepositing manganese dioxide or lead dioxide.The polymeric intermediate coating serves to protect the titanium base from oxidation, and to more particularly provide stable electrode performance with economical use of precious metal.
摘要翻译： 具有用于进行电解处理的外涂层的电极具有由在钛基上原位形成并含有少量微细分散的铂族金属催化剂的导电不溶性聚合物网络组成的保护性中间涂层。 制造电极的方法包括向钛基底施加几层含有聚合物前体和铂金属化合物的溶液，其被热转化成形成外涂层的保护性聚合物涂层，更特别地通过电沉积二氧化锰 或二氧化铅。 聚合物中间涂层用于保护钛基免受氧化，并且更具体地提供经济使用贵金属的稳定的电极性能。
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