• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Electrodes for use in electrochemical processes, particularly as cathodes for hydrogen evolution in cells for the electrolysis of alkali metal halides, said electrodes comprising an electrocatalytic ceramic coating obtained by thermal deposition. Elements of the groups IB, IIB, IIIA, IVA, VA, V B; VI A; VI B and VIII are added to the solutions or dispersions of precursor compounds of electrocatalytic ceramic materials, said solutions or dispersions being thermally decomposed to obtain the coating. The surface of the doped coating thus obtained is substantially immune to poisoning by metal impurities, when the electrode according to the present invention is used as cathode in poisoned alkali solutions.
    公开号:SU1637667A3
    申请号:SU4028594
    申请日:1986-12-03
    公开日:1991-03-23
    发明作者:Нидола Антонио；Скиро Ренато
    申请人:Де Нора Пермелек, С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to electrodes provided with an electrocatalytic ceramic coating applied by thermal deposition, intended for use in electrochemical processes, in particular as cathodes for hydrogen depolarization in electrolyzers for the electrolysis of alkali metal halides.
    The purpose of the invention is to increase the service life of the cathode by increasing its resistance to the deactivating effect of iron and heavy metal ions.
    Example 1 o Different mesh samples (25 m), made of nickel wire with a diameter of 0.1 mm, are subjected to degreasing with steam and subsequent etching in 15% nitric acid for 60 s. Nickel meshes used as substrates are coated by electroplating, g / l: Nickel sulphate
    (NiS04-7HzO) 210 Nickel chloride
    (NiCl2 6H20) 60
    Borna acid30
    Ruthenium oxide 40
    about with
    j
    se o
    4j
    The operating conditions are as follows: temperature 50 ° C, cathode current density 100 A / qm, particle diameter Ru02, µm: average 2, minimum 0.5, maximum 5, mechanical mixing, electrodeposition time 2h, coating thickness about 30 µm, coating composition : 10% dispersed Ru02, 90% Ni, dendritic surface morphology.

    s
    After washing in deionized water and drying the coating from an aqueous solution, the dyes are applied to the samples obtained, and the coating composition is as follows: ruthenium chloride 10 g (as metal), titanium chloride 1 g (as metal), 30% peroxide aqueous solution hydrogen 50 ml, an aqueous solution of 20% hydrochloric acid 150 ml, water up to 1000 ml.
    Cadmium chloride is added to the paint in an amount of 1-1000 ppm (as metal).
    After drying at 60 ° C for about 10 minutes, the samples are heated in an oven at 480 ° C for 10 minutes in the presence of air and then cooled to room temperature. The study showed that under the scanning electron microscope a surface oxidation coating was formed, which consists of a solid solution of ruthenium oxide and titanium oxide (according to x-ray diffraction data).
    The thickness of the surface oxide coating is about 2 µm, and the amount determined by weight is 4 g / m2.
    The obtained samples were tested as cathodes in a 33% alkali solution (NaOH) at 90 ° C and a cathode current density of 3 kA / m2, and they were also tested under similar operating conditions and in similar solutions containing 50 h o / ml of mercury.
    Table 1 shows the potentials of the elec- trodes measured at different times for cathode samples free from additives, with a coating containing 1.10 and 1000 ppm cadmium applied to the cathode samples.
    A quantitative analysis of the coating confirms that cadmium is present in the coating in an amount of 0.01; 0.1 and 10 at „%, which corresponds to a concentration in the paint of 1, 10 and 1000 ppm, respectively. i PRI mme R 2. Various samples
    grids (25 mei) made of nickel wire with a diameter of 0.1 mm are degreased with steam and then pickled in 15% nitric acid for 60 s „
    Nickel meshes used as substrates are coated by electroplating from a galvanic bath having the following composition, g / l:
    ten

    15
    20
    25
    thirty
    35
    40
    45
    50
    55
    Nickel sulfate
    (NiS04-7H20) 210
    Nickel chloride
    (NiCl2 6H20) 60
    Borna acid30
    Ruthenium oxide 40
    The operating conditions are as follows: temperature, cathode current density 100 A / m2, particle diameter RuOj, µm: average 2, minimum 0.5, maximum 5, mechanical mixing, electrodeposition time 2 h, coating thickness about 30 µm, coating composition - 10% - dispersed silicon oxide, 90% Ni, morphology of the surface of the dendritic coating
    After washing in deionized water and drying, water paint is applied to the various samples obtained, the paint having the following composition: ruthenium chloride 26 g (as metal), zirconium chloride 8 g (as metal), aqueous solution of 20% hydrochloric acid 305 ml, isopropyl alcohol 150 ml, water to a volume of 1000 ml,
    10 ppm cadmium chloride is added to the paint.
    The obtained samples were tested as cathodes in 33% alkaline solutions (NaOH) at 90 ° C and a current density of 3 kA / m2 and, for comparison, were tested in similar conditions and in similar formulations poisoned with Fe (50 ppm) and Hg (10 ppm) instead of with undoped cathodes about
    The true potentials of the electrodes in the value of the working time are shown in Table 2.
    Example Samples of nickel rolled sheets (10x20 mm, thickness 0.5 mm) are sandblasted and pickled in a 15% solution of nitric acid for about 60 seconds. Then the samples are activated using an electrocatalytic coating of ceramic oxides, obtained by thermal decomposition in a furnace using a paint of the following composition: ruthenium chloride 26 g (on metal), zirconium chloride 8 g (on metal), an aqueous solution of 20% hydrochloric acid 305 ml, isopropyl alcohol 150 ml, water up to a volume of 1000 ml „
    II
    500 ppm CdClfc (as metal) is also added to the paint. After drying at 60 ° C for 10 minutes, the samples
    five
    bathe in an oven at 500 ° C for Yu min and then cool.
    The coating, drying, and decomposition operations are repeated until an oxide coating is obtained containing ruthenite in an amount of 10 g / m2 (according to X-ray fluorescence) of a cadmium concentration in the coating of 1.5%.
    I test the activated samples as cathodes at 90 ° С, at a current density of 3 kA / m2 in 33% NaO solutions, not poisoned or poisoned by mercury (10 and 50 ppm) and iron (50 and 100 ppm) „
    The results are presented in table 3
    PRI me R 4. Various mesh samples (25 mesh.) Of nickel wire with a diameter of 0.1 mm are prepared as in Example 1.
    A certain amount of FeClg or Pb (NO), 5nCl1, As203, SbOCl, BiOCl concentration 1-10-1000 ppm as metal is added to the paint.
    After drying at 60 ° C for 10 minutes, the samples are treated in an oven at 480 ° C in the presence of air for 10 minutes and then cooled to room temperature. The examination under a scanning electron microscope shows the formation of an oxide surface coating, which, as X-rays showed, consists of RuO and TiO2.
    The thickness of the oxide coating is 2 µm, and the amount determined by weight is 4 g / m2.
    The quantitative analysis of alloying elements of coatings after thermal decomposition is as follows: thallium, lead, bismuth 0.005; 0.05 and 5 at.%, H, corresponds to 1, 10 and 1000 h, ppm, respectively, in this paint; Oloko arsenium, antimony is 0.01, 0.1 and 9 at.%, which corresponds to 1, 10 and 1000 h / ml, respectively, in this paint.
    The samples obtained are cathodes in a 33% NaOH solution at 90 ° C and a current density of 3 kA / m2, and under the same conditions and under single conditions containing 50 ppm of mercury.
    Table 4 shows the true potentials of the electrodes, measured at different working times for each case.
    Example 5. Various mesh patterns (25 mesh n.) Of nickel wire








    ki diameter O, 1 mm prepared analogously to example 2.
    The amount determined for each case, for CdCl2 or FeCl, Pb (MO,) g, SnClz, As203, SbOCl, BiOCl concentration of 10 ppm as the metal is added to the solution. After drying 60 ° C for 10 minutes, the samples are treated in an oven at 480 ° C in the presence of air for. Yu min, and then cooled to room temperature
    The obtained samples are tested as cathodes in 33% NaOH solution with
    90 ° C and a current density of 3 kA / m2, and under the same conditions and in similar solutions containing 10, 20, 30, 40 and 50 ppm of mercury, then compared with equivalent undoped cathodes
    Table 5 shows the true potentials of the electrodes measured at different times for each case.
    PRI me R 6, Several mesh samples (25 mesh) made of nickel wire with a diameter of 0 mm were prepared in a manner similar to Example 2,
    The number and type of alloying elements added to the paint, which is used for thermal activation, are listed in Table 6.
    Samples were then tested as cathodes under the operating conditions described in Example 5.
    Cathode potentials are listed in Table 6 as a function of electrolysis time.
    The use of the proposed cathode makes it possible to increase its service life by introducing additives. The introduction of additives in the amount of less than 0, 005 at.% Does not give a positive effect, and the introduction of additives in the amount of more than 10 at.% Leads to mechanical instability of the coating.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A cathode for chlorine electrolysis containing a nickel base coated with an electrocatalytic coating of a mixture of ruthenium oxides, titanium, zirconium, and a doping metal oxide, distinguished so that, in order to increase the service life of the cathode by increasing its durability against deactivating effect iron and heavy metal ions, it contains
    oxides of the alloying metal selected from the group of cadmium, thallium, lead, tin, mouse, antimony, bismuth, vanadium, molybdenum or tungsten, in an amount of 0.005-10 at.%. Priority featured
    04/12/85 - use of cadmium, thallium, lead, tin, mouse, antimony and bismuth.
    02.21.86- use of vanadium, molybdenum and tungsten.
    Table 1
    Table4
    Table3
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    同族专利:
    公开号 | 公开日
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    EP0218706B1|1990-08-01|
    NO864898D0|1986-12-05|
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    引用文献:
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    IT1208128B|1984-11-07|1989-06-06|Alberto Pellegri|ELECTRODE FOR USE IN ELECTROCHEMICAL CELLS, PROCEDURE FOR ITS PREPARATION AND USE IN THE ELECTROLYSIS OF DISODIUM CHLORIDE.|
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    法律状态:
    2005-01-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: PD4A |
    2007-09-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20050412 |
    优先权:
    申请号 | 申请日 | 专利标题
    IT2030985A|IT1200451B|1985-04-12|1985-04-12|ELECTRODES FOR USE IN ELECTROCHEMICAL PROCESSES AND PROCEDURE FOR THEIR PREPARATION|
    IT1950486A|IT1189971B|1986-02-21|1986-02-21|Electrode esp. for alkali chloride soln. electrolysis|
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