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1. 发明授权

US4330378A Electrolysis cell and method for electrolytic production of hydrogen 失效
标题翻译：电解槽和氢电解生产方法
公开(公告)号：US4330378A
公开(公告)日：1982-05-18
申请号：US208933
申请日：1980-11-21
申请人： Dagmar Boltersdorf , Robert Junginger , Bernd D. Struck , Herbert Neumeister
发明人： Dagmar Boltersdorf , Robert Junginger , Bernd D. Struck , Herbert Neumeister
IPC分类号： C25B1/02 , C25B1/22 , C25B9/00 , C25B9/08
CPC分类号： C25B9/08 , C25B1/02 , C25B1/22
摘要： The production of hydrogen by electrolysis in a cell, in which the anode electrolyte contains sulfur dioxide as well as sulfuric acid and an intermediate chamber separated from the anode and cathode chambers by cation-exchanger membranes is provided through which an electrolyte flows in order to prevent sulfur dioxide from reaching the cathode chamber is greatly improved by using as the anode side membrane a cation-exchanger in which a polyvinyl chloride skeleton is combined with a polymer of styrol and divinyl benzol to which sulfonic acid groups have been attached, such a membrane having a very low resistivity, thus reducing the necessary electrolysis voltage. Such a membrane also loses conductivity with increasing sulfuric acid concentration at a lower rate than membranes previously used in such an electrolysis process and permits a higher sulfuric acid concentration in the anode electrolyte. The improvement on the anode side makes possible the operation of the cathode at low sulfuric acid electrolyte concentration, below 20 or even 10% by weight. Through-flow electrodes of porous graphite encased except on the membrane side by impermeable graphite further improve the operation of the process, especially if they fill the electrolyte chamber right up to the membrane.
摘要翻译：通过在电池中电解生产氢，其中阳极电解质含有二氧化硫以及硫酸，以及通过阳离子交换膜从阳极室和阴极室分离的中间室，通过电解液流过以防止通过将聚氯乙烯骨架与其中已经连接有磺酸基团的苯乙烯和二乙烯基苯酚的聚合物组合的阳离子交换剂用作阳极侧膜，可以大大改善到达阴极室的二氧化硫，这样的膜具有电阻率非常低，从而减少必要的电解电压。这样的膜也会随着硫酸浓度的增加而以比先前在这种电解方法中使用的膜低的速率降低导电性并允许阳极电解质中的较高的硫酸浓度。在阳极侧的改进使阴极在低硫酸电解质浓度下的操作成为可能，低于20甚至10重量％。通过不渗透石墨在膜侧除外的多孔石墨的通流电极进一步改善了该方法的操作，特别是如果它们将电解液室填充到膜上。

2. 发明授权

US4391682A Method for electrolytic production of hydrogen 失效
标题翻译：电解生产氢的方法
公开(公告)号：US4391682A
公开(公告)日：1983-07-05
申请号：US228796
申请日：1981-01-26
申请人： Bernd D. Struck , Robert Junginger , Dagmar Boltersdorf
发明人： Bernd D. Struck , Robert Junginger , Dagmar Boltersdorf
IPC分类号： C25B1/02 , C25B1/22
CPC分类号： C25B1/22 , C25B1/02
摘要： A reduction of the voltage across the electrolysis cell in which hydrogen is produced in the sulfuric acid hybrid closed cycle process by use of an electrolysis cell having an intermediate chamber between the anode and cathode chamber through which a separate electrolyte is caused to flow, is obtainable under operation with the electrolytes in both the cathode and the anode chambers having a concentration of sulfuric acid by weight of about 50% or more. It is found that the undesired formation of hydrogen sulfide and of sulfur remains at a tolerable small level if the catholyte is continuously renewed. A low specific resistance cation membrane is preferably used between the cathode and intermediate chambers, as well as between the anode and intermediate chambers.
摘要翻译：可以通过使用在阳极室和阴极室之间具有中间室的电解池在硫酸混合封闭循环过程中产生氢的电解池中的电压降低，通过该中间室使单独的电解液流过。在阴极和阳极室中的电解质的操作中，其浓度为约50重量％以上的硫酸浓度。发现如果阴极电解液连续更新，硫化氢和硫的不期望的形成将保持在可容许的小水平。优选在阴极和中间室之间以及阳极和中间室之间使用低电阻率阳离子膜。

3. 发明授权

US4873121A Cathode/membrane assembly and method of making same 失效
标题翻译：阴极/膜组件及其制造方法
公开(公告)号：US4873121A
公开(公告)日：1989-10-10
申请号：US118416
申请日：1987-11-06
申请人： Bernd D. Struck , Herbert Neumeister , Aristides Naoumidis
发明人： Bernd D. Struck , Herbert Neumeister , Aristides Naoumidis
IPC分类号： C25B11/04 , C25B9/10
CPC分类号： C25B9/10
摘要： A cathode/membrane assembly for an electrolysis cell capable of producing hydrogen in a cathode compartment, utilizes as the cathode material on a proton-permeable solid-electrolite ion-exchange membrane, a layer of porous graphite in the form of carbonaceous fibers coated with tungsten carbide. The graphite felt can be impregnated with an aqueous solution of para-ammoniumtungstate or with an alcoholic solution of tungsten hexachloride and the tungsten compounds are then converted to the tungsten oxides. The tungsten oxide coated graphite felt is then subjected to carburization at a temperature of 620.degree. to 950.degree. C. in a carburizing atmosphere, preferably a flowing CO/CO.sub.2 mixture.
摘要翻译：用于在阴极室中产生氢的电解池的阴极/膜组件在质子可渗透的固体 - 电石离子交换膜上用作阴极材料，涂覆有钨的碳质纤维形式的多孔石墨层碳化物。石墨毡可以用钨酸钨铵水溶液或六氯化钨的醇溶液浸渍，然后将钨化合物转化成钨氧化物。然后将氧化钨涂覆的石墨毡在渗碳气氛中，优选流动的CO / CO 2混合物中，在620℃至950℃的温度下进行渗碳。

4. 发明授权

US4702784A Process for production of a tungsten carbide-activated electrode 失效
标题翻译：生产碳化钨活化电极的方法
公开(公告)号：US4702784A
公开(公告)日：1987-10-27
申请号：US741637
申请日：1985-06-05
申请人： Aristides Naoumidis , Herbert Neumeister , Arno Schirbach , Bernd D. Struck , Dieter Triefenbach
发明人： Aristides Naoumidis , Herbert Neumeister , Arno Schirbach , Bernd D. Struck , Dieter Triefenbach
IPC分类号： C25B11/04 , C25B11/12 , C25B1/22
CPC分类号： C25B11/0447 , C25B11/12
摘要： A process is disclosed for the production of a tungsten carbide-activated electrode, particularly an electrode which is utilizable as a cathode, and which consists of an electrically-conductive substrate with an active surface layer of tungsten carbide. The tungsten carbide is adhesively bonded through chemical reaction to the surface of a substrate which is constituted of graphite or a graphite-like material. The graphite-like material is a graphite binder mixture, whose binder material components, other than the graphitic filler granules, are only carbonized, and may not be completely graphited.
摘要翻译：公开了用于生产碳化钨活化电极，特别是可用作阴极的电极，并且由具有碳化钨活性表面层的导电基底组成的方法。通过化学反应将碳化钨粘结到由石墨或石墨状材料构成的基板的表面上。石墨状材料是石墨粘合剂混合物，其除了石墨填料颗粒之外的粘合剂材料成分仅被碳化，并且可能不完全石墨化。

5. 发明授权

US4164457A Method of recovering hydrogen and oxygen from water 失效
标题翻译：从水中回收氢和氧的方法
公开(公告)号：US4164457A
公开(公告)日：1979-08-14
申请号：US917842
申请日：1978-06-22
申请人： Heiko Barnert , Mieczyslaw Perec , Bernd D. Struck
发明人： Heiko Barnert , Mieczyslaw Perec , Bernd D. Struck
IPC分类号： C25B1/04 , C01B3/02 , C01B13/02 , C25B1/02 , C25B1/22 , C01B13/00
CPC分类号： C25B1/02 , C25B1/22 , Y02E60/366
摘要： A method of recovering hydrogen and oxygen from water. Water and sulfur dide are supplied to, and hydrogen and sulfuric acid are removed from, a galvanic or electrolytic cell. Hydrogen ions are electrochemically liberated by anodic oxidation of the supplied sulfur dioxide accompanied by decomposition of the water and formation of sulfuric acid in the anolyte, and hydrogen gas is electrolytically generated at the cathode from the hydrogen ions. To evaporate water, electrolytic solution is removed from the anode chamber of the galvanic cell. The anode chamber is separated from the cathode chamber by means of a membrane. After the ensuing evaporation, the thus formed anhydride of the sulfuric acid is decomposed by being heated, and is accompanied by the formation of oxygen and sulfur dioxide gas. The sulfur dioxide is oxidized at a carbon and/or graphite anode in the presence of very small quantities, e.g. a minimum of 0.005% by weight, of hydriodic acid in the anolyte. The hydriodic acid which is found in that portion of the electrolyte which is removed from the anode chamber is evaporated together with the water. The evaporated water, together with the evaporated hydriodic acid, are again supplied to the anode chamber.
摘要翻译：从水中回收氢和氧的方法。供应水和二氧化硫，从电镀或电解池中除去氢和硫酸。通过所供应的二氧化硫的阳极氧化伴随着水的分解和在阳极电解液中形成硫酸而电化学释放氢离子，并且氢气在阴极从氢离子电解产生。为了蒸发水，从电池的阳极室去除电解液。阳极室通过膜与阴极室分离。在随后的蒸发之后，由此形成的硫酸酐被加热分解，伴随着形成氧气和二氧化硫气体。二氧化硫在非常少量的存在下在碳和/或石墨阳极氧化，例如，至少0.005重量％的阳离子中的氢碘酸。在从阳极室除去的电解质部分中发现的氢碘酸与水一起蒸发。蒸发的水与蒸发的氢碘酸一起再次供应到阳极室。

6. 发明授权

US4443316A Electrolysis cell with intermediate chamber for electrolyte flow 失效
标题翻译：具有电解液流中间室的电解槽
公开(公告)号：US4443316A
公开(公告)日：1984-04-17
申请号：US318457
申请日：1981-11-05
申请人： Bernd D. Struck
发明人： Bernd D. Struck
IPC分类号： C25B9/08 , C25B13/00 , C25B9/00 , C25B13/02 , C25B13/08
CPC分类号： C25B9/08 , C25B13/00
摘要： The economy of production of hydrogen and sulfuric acid in a three chamberlectrolysis cell in which an electrolyte flows through the intermediate chamber (11) which is bounded by ion exchanger membranes (9,10) can be improved by the provision of a porus supporting framework or skeleton (12) of graphite or of ion exchanger material against which the separators with the electrodes (7, 8) on them, can be pressed. The overall internal resistance of the cell can thus be reduced and its mechanical behavior improved. Substantial through passage porosity is desired in the supporting structure, which may be of graphite, but porous aggregates of ion exchanger material with fixedly applied or welded on separators in the form of stacked layers or rolled mats, are preferred for the relative simplicity of their provision in practice.
摘要翻译：电解质流过通过离子交换膜（9,10）界定的中间室（11）的三室电解池中的氢和硫酸的生产经济可以通过提供孔结构框架或石墨或离子交换器材料的骨架（12），其上具有电极（7,8）的分离器可以被按压。因此，可以减小电池的整体内阻，并改善其机械性能。对于可能是石墨的支撑结构，需要通过通道孔隙的重要性，但是优选的是它们提供的相对简单的方式，其中离子交换材料的多孔聚集体固定地施加或焊接在叠层或轧制垫的形式的隔板上在实践中。

7. 发明授权

US4191619A Process for conversion of materials in electrolytic solution 失效
标题翻译：电解液中材料转化工艺
公开(公告)号：US4191619A
公开(公告)日：1980-03-04
申请号：US945693
申请日：1978-09-25
申请人： Bernd D. Struck
发明人： Bernd D. Struck
IPC分类号： C25B1/04 , C01B7/09 , C01B17/74 , C25B1/00 , C25B1/02 , C25B1/22 , C25B9/00 , C25B9/08 , C25B15/00
CPC分类号： C25B15/00 , C25B1/00 , C25B1/22 , Y02E60/366 , Y02P20/132
摘要： An electrolyte in an intermediate space between permeable partitions respectively separating the intermediate space from the anode space and the cathode space of an electrolytic cell is caused to be circulated through the intermediate space so as to remove materials migrating from one electrode space before they have an opportunity to migrate into the other electrode space. It is also of advantage for the electrolyte to contain material for reacting chemically with materials so migrating from an electrode space, in which case the slow velocity may be reduced or, for reduction of the electrical resistance, the spacing between the permeable walls may be reduced.This type of electrolytic cell is applied especially to the sulfuric acid hybrid process.
摘要翻译：使分离中间空间与电解池的阳极空间和阴极空间的可渗透隔板之间的中间空间中的电解质循环通过中间空间，以便在具有机会之前移除从一个电极空间迁移的材料迁移到另一个电极空间。电解质含有与化学反应的材料的材料也是有利的，所述材料从电极空间迁移，在这种情况下可能会减慢速度，或为了减少电阻，可以减少可渗透壁之间的间隔。这种电解池特别适用于硫酸混合工艺。

8. 发明授权

US4512858A Method of producing an electrode usable as a flow-through anode 失效
标题翻译：制造可用作流通阳极的电极的方法
公开(公告)号：US4512858A
公开(公告)日：1985-04-23
申请号：US579654
申请日：1984-02-13
申请人： Bernd D. Struck , Francisco J. Dias , Hartmut Luhleich , Ursula Paffen nee Siebert
发明人： Bernd D. Struck , Francisco J. Dias , Hartmut Luhleich , Ursula Paffen nee Siebert
IPC分类号： B01D53/50 , C04B35/52 , C04B35/532 , C04B35/83 , C25B1/22 , C25B11/12 , G01N27/30
CPC分类号： B01D53/50 , C04B35/521 , C04B35/532 , C04B35/83 , C25B1/22 , C25B11/12
摘要： An anode for electrolytic oxidation of sulfur dioxide is made by coating anlectrode of a graphite-like carbon material with a layer of cokable organic material such as sugar, phenolic resin, and asphalt pitch, heating the coated electrode body in an inert atmosphere to a temperature of between 400.degree. to 800.degree. C. and thereafter heating the coated electrode to a temperature in the range of 1400.degree. to 2000.degree. C., so that the material is first coked on the graphite to produce a porous flow-through electrode body which, thereafter, is heated to a higher temperature, followed by cooling.
摘要翻译：用二氧化硫的电解氧化的阳极是通过用石墨状碳材料的电极涂覆一层可食用的有机材料如糖，酚醛树脂和沥青沥青，将涂覆的电极体在惰性气氛中加热至温度在400℃至800℃之间，然后将涂覆的电极加热至1400℃至2000℃的温度，使得该材料首先在石墨上焦化以产生多孔流通电极体然后将其加热到更高的温度，然后冷却。

9. 发明授权

US4304643A Process for the electrolysis of sulfur dioxide solutions 失效
标题翻译：二氧化硫溶液电解工艺
公开(公告)号：US4304643A
公开(公告)日：1981-12-08
申请号：US66861
申请日：1979-08-15
申请人： Jiri Divisek , Heinrich Schmitz , Bernd D. Struck
发明人： Jiri Divisek , Heinrich Schmitz , Bernd D. Struck
IPC分类号： C25B1/02 , C25B1/22 , C25B1/00
CPC分类号： C25B1/22 , C25B1/02
摘要： Particles of electrically conducting activated carbon of about 500 to 1,000 m.sup.2 /g specific surface added to an electrolyte provided by a solution of sulfur dioxide in water are found to provide a substantial reduction of the electrical energy requirement in the electrolysis of such an electrolyte for the production of hydrogen and sulfuric acid. A further reduction of energy consumption is obtained by additionally introducing iodine in the electrolyte in an amount not exceeding 1% by weight of the entire solution. Use of an anode in which the surface of a graphite base body is coated with a thin layer of activated carbon bonded to the graphite body by means of a binder, such as rubber, also reduces the electrical energy requirement for the electrolysis. To coat the surface of the electrode, carbon particles are first dispersed in a rubber solution and the suspension is then applied to the surface of the graphite body as a thin layer.
摘要翻译：发现添加到由二氧化硫溶于水的电解质中提供的电解质的约500至1,000m 2 / g比表面积的导电活性炭颗粒可显着减少用于电解的电解质中的电能需求生产氢和硫酸。通过在电解液中另外引入碘量不超过整个溶液的1重量％，可以进一步降低能量消耗。使用阳极，其中石墨基体的表面涂覆有通过诸如橡胶的粘合剂结合到石墨体的活性炭的薄层，还降低了电解所需的电能。为了涂覆电极的表面，首先将碳颗粒分散在橡胶溶液中，然后将悬浮液作为薄层施加到石墨体的表面。

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