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公开(公告)号：US4126536A
公开(公告)日：1978-11-21
申请号：US754655
申请日：1976-12-27
CPC分类号： C25B13/04
摘要： Synthetic-fiber diaphragms are further improved by incorporating in the diaphragm an effective proportion of a suitable inorganic material such as TiO.sub.2, BaSO.sub.4 or K.sub.2 Ti.sub.8 O.sub.17, which is more hydrophilic than the fluoropolymer forming the diaphragm. This is done either by mixing the inorganic material with the resin before it is made into fiber or by supplying sub-micron-sized particles of the inorganic material, during or even after diaphragm formation. A principal benefit is that this lowers the cell voltage which is required during an initial period (up to about 300 hours) of the operation of a chlor-alkali cell provided with such a diaphragm, making it possible to avoid such drawbacks as suffering an initial period of low production or the necessity of providing external cooling to the cell during such an initial period.
摘要翻译： 合成纤维隔膜通过在隔膜中结合有效比例的合适的无机材料例如TiO 2，BaSO 4或K 2 Ti 8 O 17，比形成隔膜的氟聚合物更亲水，进一步改进。 这可以通过在制成纤维之前将无机材料与树脂混合，或者在隔膜形成期间或甚至在隔膜形成之后通过供应亚微米级的无机材料颗粒来完成。 主要的好处是这降低了在设置有这种隔膜的氯碱电池的操作的初始阶段（高达约300小时）期间所需的电池电压，使得可以避免诸如遭受初始 在生产初期或在这样的初始阶段对电池提供外部冷却的必要性。
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公开(公告)号：US4183793A
公开(公告)日：1980-01-15
申请号：US935038
申请日：1978-08-18
摘要： Fibers about micron size in cross-section of certain fluorine-containing polymers can be treated after being deposited as a diaphragm, either during operation or separately before installation, so that they develop a 0.25-millimeter-thick ply on either side of a central body which is substantially different in chemical composition. This yields a diaphragm 1 to 5 millimeters thick which has a Mullen burst strength approximately three to five times greater than that of an untreated diaphragm (20-25 pounds per square inch versus 5 to 7 pounds per square inch) and a remarkably improved service life in the treated diaphragm (200 days and up) in comparison with such untreated diaphragm (30 days or less). Use of a polymer based upon a major proportion of chlorotrifluoroethylene appears to be required. This discovery is economically significant, in that it is an essential element in the technology of the replacement of asbestos diaphragms now used with a synthetic material. Health-hazard and pollution-control considerations have made it desirable to replace asbestos, and this invention provides the key to the solution of the problem.Moreover, a synthetic-polymer diaphragm has two significant advantages that an asbestos one lacks--it will withstand washing or cleaning with an acid solution, and it does not swell in service and resists erosion, so that a closer electrode spacing can be used and the cell voltage can thus be lower.
摘要翻译： 在某些含氟聚合物的横截面上的微米尺寸的纤维可以在操作期间或在安装之前分开沉积后作为隔膜进行处理，使得它们在中心体的两侧形成0.25毫米厚的层 这在化学组成上是显着不同的。 这产生了1至5毫米厚的隔膜，其具有比未经处理的隔膜（20-25磅/平方英寸，相对于5至7磅/平方英寸）大约3至5倍的马伦爆裂强度，并且显着改善的使用寿命 与经处理的隔膜（200天及以上）相比，未经处理的隔膜（30天以内）。 似乎需要使用基于主要比例的三氟氯乙烯的聚合物。 这个发现在经济上是重要的，因为它是现在与合成材料一起使用的石棉隔膜的替代技术的基本要素。 健康危害和污染控制的考虑已经取代了石棉，本发明提供了解决问题的关键。 此外，合成聚合物隔膜具有两个显着的优点，即石棉一个缺点，它将承受用酸溶液的洗涤或清洗，并且不会在使用中膨胀并抵抗侵蚀，使得可以使用更近的电极间距，并且 因此，电池电压可以更低。
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公开(公告)号：US4126535A
公开(公告)日：1978-11-21
申请号：US742818
申请日：1976-11-18
CPC分类号： C25B13/08
摘要： Fibers about micron size in cross-section of certain fluorine-containing polymers can be treated after being deposited as a diaphragm, either during operation or separately before installation, so that they develop a 0.25-millimeter-thick ply on either side of a central body which is substantially different in chemical composition. This yields a diaphragm 1 to 5 millimeters thick which has a Mullen burst strength approximately three to five times greater than that of an untreated diaphragm (20-25 pounds per square inch versus 5 to 7 pounds per square inch) and a remarkably improved service life in the treated diaphragm (200 days and up) in comparison with such untreated diaphragm (30 days or less). Use of a polymer based upon a major proportion of chlorotrifluoroethylene appears to be required. This discovery is economically significant, in that it is an essential element in the technology of the replacement of asbestos diaphragms now used with a synthetic material. Health-hazard and pollution-control considerations have made it desirable to replace asbestos, and this invention provides the key to the solution of the problem. Moreover, a synthetic-polymer diaphragm has two significant advantages that an asbestos one lacks--it will withstand washing or cleaning with an acid solution, and it does not swell in service and resists erosion, so that a closer electrode spacing can be used and the cell voltage can thus be lower.
摘要翻译： 在某些含氟聚合物的横截面上的微米尺寸的纤维可以在操作期间或在安装之前分开沉积后作为隔膜进行处理，使得它们在中心体的两侧形成0.25毫米厚的层 这在化学组成上是显着不同的。 这产生了1至5毫米厚的隔膜，其具有比未经处理的隔膜（20-25磅/平方英寸，相对于5至7磅/平方英寸）大约3至5倍的马伦爆裂强度，并且显着改善的使用寿命 与经处理的隔膜（200天及以上）相比，未经处理的隔膜（30天以内）。 似乎需要使用基于主要比例的三氟氯乙烯的聚合物。 这个发现在经济上是重要的，因为它是现在与合成材料一起使用的石棉隔膜的替代技术的基本要素。 健康危害和污染控制的考虑已经取代了石棉，本发明提供了解决问题的关键。 此外，合成聚合物隔膜具有两个显着的优点，即石棉一个缺点，它将承受用酸溶液的洗涤或清洗，并且不会在使用中膨胀并抵抗侵蚀，使得可以使用更近的电极间距，并且 因此，电池电压可以更低。
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4.发明授权Method for the recovery of mercury and other heavy metal ions from a liquid stream 失效从液体流中回收汞和其他重金属离子的方法
公开(公告)号：US4208258A
公开(公告)日：1980-06-17
申请号：US910560
申请日：1978-05-30
申请人： Edward N. Balko , Shyam D. Argade
发明人： Edward N. Balko , Shyam D. Argade
CPC分类号： C02F1/46114 , C01D3/14 , C02F1/4678 , C25B9/168
摘要： Small quantities of metal ions can be removed from an aqueous solution by subjecting the solution to an electric current in the presence of an anode and a fibrous metal cathode. The invention also provides an electrolytic apparatus having such electrodes. The process is particularly adaptable to the removal of mercury contamination from liquid brine streams.
摘要翻译： 通过在阳极和纤维状金属阴极的存在下使溶液经受电流，可以从水溶液中除去少量的金属离子。 本发明还提供一种具有这种电极的电解装置。 该过程特别适用于从液体卤水流中除去汞污染物。
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公开(公告)号：US4138296A
公开(公告)日：1979-02-06
申请号：US803133
申请日：1977-06-03
申请人： Edward N. Balko , Shyam D. Argade
发明人： Edward N. Balko , Shyam D. Argade
CPC分类号： C01B7/0743
摘要： In a process for making chlorine electrolytically in which a build-up of nitrogen trichloride occurs in the bottoms of cooling apparatus, a method and apparatus is provided wherein the nitrogen trichloride is dissolved in an organic solvent such as carbon tetrachloride, the chlorine removed, and the solution treated to destroy the otherwise hazardous nitrogen trichloride. The solvent is then separated and recycled to avoid environmentally undesirable waste products.
摘要翻译： 在冷却装置的底部产生氯化氢的电解方法中，提供了一种方法和装置，其中将三氯化氮溶解在有机溶剂如四氯化碳中，除去氯和 该溶液被处理以破坏否则有害的三氯化氮。 然后将溶剂分离并再循环，以避免环境不良的废物。
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公开(公告)号：US4230673A
公开(公告)日：1980-10-28
申请号：US9635
申请日：1979-02-05
申请人： Edward N. Balko , Shyam D. Argade
发明人： Edward N. Balko , Shyam D. Argade
CPC分类号： C01B7/0743
摘要： In a process for making chlorine electrolytically in which a build-up of nitrogen trichloride occurs in the bottoms of cooling apparatus, a method and apparatus is provided wherein the nitrogen trichloride is dissolved in an organic solvent such as carbon tetrachloride, the chlorine removed, and the solution treated to destroy the otherwise hazardous nitrogen trichloride. The solvent is then separated and recycled to avoid environmentally undesirable waste products.
摘要翻译： 在冷却装置的底部产生氯化氢的电解方法中，提供了一种方法和装置，其中将三氯化氮溶解在有机溶剂如四氯化碳中，除去氯和 该溶液被处理以破坏否则有害的三氯化氮。 然后将溶剂分离并再循环，以避免环境不良的废物。
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公开(公告)号：US4193861A
公开(公告)日：1980-03-18
申请号：US1445
申请日：1979-01-08
IPC分类号： C25B13/08
CPC分类号： C25B13/08
摘要： Initial cell voltages are reduced by decreasing the resistance of the diaphragm through a degassing procedure prior to or at installation thereof. This degassing procedure involves subjecting the diaphragm to subatmospheric pressure while contacting the diaphragm with electrolyte, said electrolyte being an aqueous saline solution having a surface active agent therein in an amount sufficient to reduce the surface tension below the critical surface tension for wetting the fibers, and increasing the pressure to atmospheric or cell working pressure to force electrolyte solution into the interstices of the diaphragm.
摘要翻译： 通过在其安装之前或在安装时通过脱气程序减小隔膜的电阻来降低初始电池电压。 该脱气方法包括使膜片在低于大气压力的同时使膜片与电解质接触，所述电解质是其中具有表面活性剂的盐水溶液，其量足以将表面张力降低到用于润湿纤维的临界表面张力以下，以及 将压力增加到大气压力或电池工作压力，以迫使电解质溶液进入隔膜的间隙。
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8.发明授权Carbon fiber reinforced fluorocarbon-graphite bipolar current collector-separator 失效碳纤维增强氟碳石墨双极集电器分离器
公开(公告)号：US4339322A
公开(公告)日：1982-07-13
申请号：US142583
申请日：1980-04-21
IPC分类号： C08K7/06 , C08K13/04 , C25B9/00 , C25B9/04 , C25B9/20 , C25B11/10 , H01M8/02 , C25B11/00 , C25B11/12
CPC分类号： C25B9/206 , C08K13/04 , C08K7/06 , C25B9/00 , C25B9/04 , H01M8/0213 , H01M8/0226
摘要： A bipolar current collector-separator for electrochemical cells consists of a molded aggregate of electro-conductive graphite and a thermoplastic fluoropolymer particles reinforced with carbon fibers to increase the strength and maintain high electrical conductivity. The graphite and the thermoplastic fluoropolymer are combined in weight ratio ranging from 2.5:1 to 16:1. The carbon fibers may constitute from 10 to 80 weight percent of the conductive graphite. The bulk resistivity of such a molded bipolar current collector is less than 4.times.10.sup.-3 ohm inches (.sigma. in.) It has excellent corrosion resistance to a variety of feed stocks such as brine, aqueous HCl, water, etc. and to various electrolysis products, such as caustic, chlorine, hydrogen, etc.This invention relates to a molded, conductive, fiber reinforced, current collecting-separator structure for electrochemical cells and, more particularly, to one utilizing thermoplastic fluoropolymer resin binders for bonding electroconductive particles into a solid, current collecting-separator structure reinforced by carbon or graphite fibers or fiber structures.
摘要翻译： 用于电化学电池的双极集电器分离器由导电石墨的模制聚集体和用碳纤维增强的热塑性氟聚合物颗粒组成，以增加强度并保持高导电性。 石墨和热塑性氟聚合物以2.5:1至16:1的重量比组合。 碳纤维可以占导电石墨的10至80重量％。 这种模制的双极集电器的体电阻率小于4×10-3欧姆英寸（西格玛）它对各种原料如盐水，HCl水溶液，水等具有优异的耐腐蚀性，以及各种电解产品 ，诸如苛性碱，氯，氢等。本发明涉及一种用于电化学电池的模制的，导电的，纤维增强的电流收集分离器结构，更具体地，涉及一种利用热塑性含氟聚合物树脂粘合剂将导电颗粒粘结成固体 ，由碳或石墨纤维或纤维结构增强的电流收集分离器结构。
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9.发明授权Electrolysis of alkali metal halides in a three-compartment cell with a pressurized buffer compartment 失效在具有加压缓冲隔室的三室电池中电解碱金属卤化物
公开(公告)号：US4214958A
公开(公告)日：1980-07-29
申请号：US38812
申请日：1979-05-14
摘要： The invention describes a pressurized, three compartment membrane cell for the electrolyzing aqueous alkali metal halides at low cell voltages and with high cathodic current efficiencies. Unitary electrode-electrolyte structures, in the form electrochemically active electrodes physically bonded to ion transporting permselective membranes divide the cell into anode, cathode and buffer compartments. The buffer compartment feed is pressurized to maintain at a positive pressure differential with respect to the anode and cathode compartment feeds. The flexible unitary electrode-membrane electrolytes are forced outwardly against electronically conductive anode and cathode current collectors to provide uniform, constant and controllable contact between the bonded electrodes and thereby minimizing ohmic losses. A three compartment cell operated in this fashion not only minimizes the voltage required to electrolyze the halide solution, but also increases the cathodic current efficiency at high caustic concentrations by providing multiple hydroxide rejection stages in a single cell process. The improvement in cathodic current efficiency is realized by forming a lower caustic concentration in the buffer compartment than in the cathode compartment thereby reducing backmigration of OH.sup.- ions into the anode compartment.
摘要翻译： 本发明描述了一种用于在低电池电压和高阴极电流效率下电解碱金属卤化碱水溶液的加压三室膜电池。 单电极 - 电解质结构，以电化学活性电极的形式物理键合到离子传输选择性选择膜将细胞分成阳极，阴极和缓冲隔室。 缓冲室进料被加压以相对于阳极和阴极室进料保持在正压差。 柔性单体电极 - 膜电解质被强制向外抵靠电子导电阳极和阴极集电器，以在接合的电极之间提供均匀的，恒定的和可控制的接触，从而最小化欧姆损耗。 以这种方式操作的三室单元不仅使电解卤化物溶液所需的电压最小化，而且通过在单个电池工艺中提供多个氢氧化物排除阶段来提高高苛性碱浓度下的阴极电流效率。 阴极电流效率的提高通过在缓冲室中形成比在阴极室中更低的苛性碱浓度来实现，从而减少OH-离子进入阳极室的反向迁移。
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公开(公告)号：US06003307A
公开(公告)日：1999-12-21
申请号：US19085
申请日：1998-02-06
CPC分类号： F02D41/0055 , F01N11/00 , F01N11/007 , F01N13/009 , F02D41/1444 , F01N2550/02 , F02D2041/1432 , F02D2041/288 , F02D41/1408 , Y02T10/47
摘要： An on-board catalytic monitoring system uses an intrusive technique to cause the vehicle's engine to cycle between first and second operating conditions. The first and second operating conditions are chosen such that different concentrations of emissions with different chemistries are present at the first and second operating conditions. A calorimetric sensor with a selective catalyst senses exothermic oxidation reactions produced by the emissions in the exhaust gas passing over the sensor. By matching the catalyst activity with the emission concentrations occurring at the operating conditions, the difference between the heat release sensor signals detected between the first and second operating conditions is indicative of the actual concentration of specific emissions in the exhaust gas stream. The difference or delta signal, obtained without reference to a zero point, provides an excellent correlation to the efficiency of the vehicle's catalytic converter for converting the sensed emission, i.e., hydrocarbons.
摘要翻译： 车载催化监测系统使用侵入式技术来使车辆的发动机在第一和第二操作条件之间循环。 选择第一和第二操作条件使得在第一和第二操作条件下存在不同浓度的不同化学物质的排放。 具有选择性催化剂的量热传感器感测由通过传感器的废气中的排放产生的放热氧化反应。 通过将催化剂活性与在操作条件下发生的排放浓度相匹配，在第一和第二操作条件之间检测到的放热传感器信号之间的差异表示废气流中特定排放物的实际浓度。 在不参考零点的情况下获得的差值或δ信号与车辆用于转换感测发射的催化转化器即碳氢化合物的效率有很好的相关性。
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