• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    1532683 Reinforced electrolysis membrane E I DU PONT DE NEMOURS & CO 27 April 1976 [29 April 1975] 17064/76 Heading C7B [Also in Division B5] An ion-exchange membrane for brine electrolysis comprises a film of a fluorine-containing polymor having pendant side chains containing ionic groups derived from sulphonyl groups SO 2 X where X is Cl or F, each group being attached to a carbon atom which has at least one fluorine atom attached thereto, and a fabric comprising supporting fibres embedded in or laminated to the film, the fabric originally comprising fibres which have been removed by chemical destruction or leaching. The iqn exchange groups may have the formula -(SO 2 NH) n Q where Q has a valency n and is H, NH4 or an alkali or alkaline earth metal or -(SO 3 ) n Me where Me is a cation of valency n.
    公开号:SU904529A3
    申请号:SU762353364
    申请日:1976-04-27
    公开日:1982-02-07
    发明作者:Густав Грот Вальтер
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    (five)
    METHOD OF OBTAINING A CATHION PENETTED DIVIDER
    The invention relates to a method for producing a cation-permeable separator, which is a diaphragm used in electrolyzers for separating the anode and cathode spaces in the electrolysis of brine in the production of chlorine and caustic soda.
    A known method of producing diaphragms of this kind from a copolymer of tetrafluoroethylene and perfluoro (3, 6-diox-α-methyl-7-octene-phonyl fluoride and yes) by converting the sulfonyl groups into inorganic 1 J.
    Closest to the present invention is a method for producing a cation-permeable separator by reinforcing a film of a copolymer of tetrafluoroethylene-and perfluoro (3,6-dioxa-4-methyl-7 octyl-sulfonylptoid) with a fabric of f2 teflon fibers.
    A large number of reinforcing fibers in a cation-permeable separator is undesirable because, when operating in an electrolytic cell, the productivity decreases and / or the voltage increases compared to the use of separators with a smaller number of reinforcing (reinforcing) 5 fibers.
    The use of a small number of reinforcing fibers in a fabric, whether openly woven or knitted, causes the fibers to shift relative to each other in the process of apiopomania. Heterogeneity in the reinforcement due to the accumulation of fibers is undesirable.
    When reinforced with a relatively small number of reinforcing fibers, 18 the surface of the cation-permeable separator becomes less smooth and flat (as if grooved) than in the case of reinforcement with a large number of fibers.
    20Bubbles acting as insulators may accumulate on the corrugated surface of the separator during electrolysis.
    The purpose of the invention is to increase the efficiency of the separator.
    This aim dostigates heme that in Preparation kationopronitsaemsgo separator film nyTBhi reinforcing cloth cononni-iepa of tetrafluoroethylene and perfluoro (3 jS-flHOK-ca- -gmetil octene sul fonilftoridz 7) is carried out reinforcement cloth sotsermoschey reinforcing fiber-th itetraftoretilena m destroys 5e viscose fibers at a ratio of /; retrofitting and killing fibers, followed by removal of the fibers being destroyed and conversion of sulonyl groups into ion exchange.
    The film used preferably has a thickness of 0.01-0.75 mm.
    The nature of the fibers being destroyed and their removal aid must be chimi so as not to affect the properties of the polymer.
    Since the reinforcement was carried out at 240-320 ° C, the reinforcing fibers should be stable at these temperatures, as well as resistant to chemical attack (for example, to the action of chlorine and caustic soda). Owing to their chemical inertness, perfluorinated fibers made of tetrafluoroethylene meet these requirements.
    A separator is obtained on the basis of the said perfluorinated polymer containing sulfonyl fluoride groups, from which the film is formed, then it is reinforced with tissue, reinforcing fibers and destroyable fibers, the sulfonyl fluoride groups of the polymer are converted into ionic treatment with alkali or amine and the destroyed fibers are removed.
    The last two operations can be performed in reverse order.
    When treated with alkali or amine, the sulfonyl groups are converted to ionic groups Q, where Q is H, NHl, alkali metal or alkaline earth metal cation; n is the valence of the cation, or. where Me is a cation; n is the valence of this cation.
    Reinforcement is usually carried out by pressing a fabric into the polymer at 20 ° C to 220 ° C.
    The fiber # 1e destroyed can remain in the separator until it is used by the electrolytic cell and removed from it during the electrolysis of the brine.
    four
    .-illiuus jusKzty (pores) provide a hydraulic flow of Bocru-reinforcing fluid in the window and help increase the passage of tone through a separator.
    The greatest advantages of the separator are found in the electrolysis of brine; however, it can be widely used in the 3 electrolytic cells used for the electrolysis of alkali or alkaline earth metal halide solutions.
    Examples 1 and 2. In this and subsequent examples, a tetrafluoroethylene copolymer is used as an intermediate polymer.
    CFg CFOCF2GFOCF2CF2SC 2F
    SGS
    Equivalent weight of a polymer is weight in grams corresponding to one equivalent potential ion exchange capacity. A film with a thickness of 0.18 mm 1200 of equivalent weight (3. V.) of the intermediate polymer is treated from the surface with ethylenediamine to a depth of 0.023 f-W5. The bottom of the film is then reinforced in vacuum with the following fabrics:
    1. A fabric containing both the warp and the weft of the threads / cm 222 decitex of Teflon (gf = tetrafluoroethylene yarn) and 22 threads / cm 55 of the decitex of viscose. Thickness of fabric is 0,15 mm.
    2.8 T-12 fabric, containing approximately 15 7 strands / cm kkk decitex of Teflon (tetrafluoroethylene yarn), both in the base and in the
    in ducks, about 0.25 mm.
    After layering, both samples are treated with a hot solution of potassium hydroxide in aqueous dimethyl sulfoxide to convert the remaining groups 502 into groups.
    After that, the samples are removed from the hydrolysis bath, then impregnated for half an hour in dilution (about 10) with caustic soda. Then they are placed in a laboratory electrolytic chlor-alkali cell. The used / electrode ".1 is an anode with constant times 4amers and a perforated stainless steel plate used as a cathode. The distance between the laminates and the electrode and each electrode is approximately 3.2 mm. Thin (about 1.6 mm) plates of spongy material of nerprene are used as gaskets.
    During electrolysis, a saline solution containing 1bOg NaCl (1 liter of solution, 0; 25 ml of concentrated HC), 1 liter of solution and 0.022 g of monobasic sodium phosphate (), 1 liter of solution is fed continuously into the anode space. The concentration of the outgoing salt is 135 g / l of solution. First, 10 n is introduced into the cathode space in each example.
    Teflon / Viscose Fabric
    Formed by fabric T-12 (control)
    Analysis of sample 1 after removal from the cell indicates that viscose was removed during electrolysis.
    Examples ZiA. The fabrics described in examples 1 and 2 are used to reinforce an intermediate polymer film of 1100 eV. O, 1 and intermediate polymer 1500 eV thick 0.04 mm thick. The fabric is contained in a polymer with an eV. 1100. After the reinforcement, the sulfonyl groups of the polymer are transformed into SOjK groups (as described in examples 1 and 2) by treating with a hot solution of sodium hypochlorite, which destroys the viscose in example 3, after removing the two layered samples from the hydrolysis bath, they are boiled for half an hour in distilled water. Then placed in the laboratory chlor-alkali
    Sodium hydroxide solution to fill the space. As the cell warms up to its final operating temperature, the current density increases successively to its final value, equal to 0.31 A / cm. The cell is then operated continuously at 80 and 0.31 A / cm for several days, and then the cell capacity is measured by comparing the amount of current that passes through the cell.
    The results are shown in Table. one,
    .Table
    11.8
    5.10
    11.6
    5.63
    a cell similar to that described in example 1.
    During electrolysis, a 25% saline solution is continuously fed into the anode space. To the cathode space is added n. caustic soda solution for filling the space. After that, a sufficient amount of distilled water is fed into the cathode space during each electrolysis in order to maintain the normality of the catholyte in the range of about 5.5-5.6.
    Three days after the start of the process, at and 0.31 A / cm, cell throughput is measured by comparing the amount of caustic soda produced with the amount of current passing through the cell.
    The results are shown in Table. 2
    .Educated from About, About mm 1500 eV film, 0.1 mm 1100 eV film and cloth Teflon / viscose
    Educated
    OiO mm 1500 e.v.
    film, 0.1 mm
    1000 eV film
    and T-12 fabric
    (control) Approximation 5. A microporous separator is formed by layering the next set of materials in a vacuum evaporator for approximately 2 minutes: offset to printing paper (top), unfilled paper, two layers of soft filter paper. paper, 0.18 mm intermediate polymer 1200 eV, one layer of soft filter paper, Teflon / viscose fabric according to Example 1, | two layers of soft filter paper; Gy, unfilled paper, 0.25 mm of transfer paper (bottom) After layering, the intermediate polymer penetrates through all five layers, but stops before a layer of unfilled paper. The multilayer formation is hydrolyzed in a solution of potassium hydroxide in aqueous dimethyl sulfoxide and the paper and viscose are destroyed by treatment with a hot solution of sodium hypochlorite. The separator is then boiled for t hours in distilledTable 2
    5.6
    3.8
    5.5
    ““ .Z bathtub water. Left wet, it is installed in a laboratory chlor-alkali cell, similar to that described in Example 1-8, however, the cell is supplied with a vertical pipeline, such that the anolyte has a hydraulic pressure of 41.9 cm relative to the catholyte, and saturated brine is used as the load in the anolyte. 2 N is added to the cathode space to fill the space with NaOH. During the experiment, no additional material is fed into the cathode space. While the cell is heated to its final operating temperature, the current density increases successively to its final value of ≤ 0.155 A / cm. The cell then runs continuously for several days. After that, the current performance is measured by means of comparison of the obtained caustic soda with the amount of current passing through the cell. The results are shown in Table. 3Table 3 9a Examples 6 and 7. The liquid is not subjected to hydrolysis of the multilayer element of the example; 5 is heated again under the molding conditions (15 minutes at) to obtain a deeper penetration of the polymer into the paper. The sheet is then chemically treated as in the previous case. Resulting from section a b
    The faces of the littel are then boiled in distilled water and placed in a similar laboratory chlor-alkali cell. The start-up of the cell in the course and process in the cell is the same as described in Example 5. After several days of carrying out the process, the results are shown in Table. f.
    权利要求:
    Claims (2)
    [1]
    Claim
    1. A method of obtaining a cation-permeable separator by reinforcing with a fabric a film of a copolymer of tetrafluoroethylene and perfluoro (3,6-dioxa-4-methyl-7 “octene ~ sulfonyl fluoride), characterized in that 45 in order to increase the efficiency of the divider, reinforcement is carried out with a fabric containing reinforcing fibers of polytetrafluoroethylene and destructible fibers from viscose with a ratio of reinforcing and destructible fibers of 1: 1.8, followed by removal of destructible fibers and the transformation of sulfonyl groups into ion exchange ones.
    [2]
    2. The method according to π.1, characterized in that a film with a thickness of 0.01-0.75 mm is used.
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    同族专利:
    公开号 | 公开日
    FR2309651B1|1980-02-15|
    US4021327A|1977-05-03|
    CA1066665A|1979-11-20|
    BE841223A|1976-10-28|
    BR7602592A|1976-11-23|
    AU1333976A|1977-11-03|
    FR2309651A1|1976-11-26|
    JPS5720328B2|1982-04-28|
    GB1532683A|1978-11-22|
    IT1059013B|1982-05-31|
    DE2607242A1|1976-11-11|
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    NL7604627A|1976-11-02|
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    IL49484D0|1976-06-30|
    IL49484A|1978-09-29|
    JPS51131489A|1976-11-15|
    DE2607242C2|1985-11-14|
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    GB1468355A|1973-07-18|1977-03-23|Ici Ltd|Making porous diaphragms in electrolytic cells|
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    US4610764A|1984-02-07|1986-09-09|Asahi Glass Company Ltd.|Electrolytic cation exchange membrane|
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    US4666573A|1985-09-05|1987-05-19|Ppg Industries, Inc.|Synthetic diaphragm and process of use thereof|
    US5152882A|1990-09-28|1992-10-06|Rosemount Inc.|Integral hydrolysis layer junction|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/572,832|US4021327A|1975-04-29|1975-04-29|Reinforced cation permeable separator|
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