CN101775617B - Exchange membrane containing fluorine ions and application thereof in basic industry - Google Patents
Exchange membrane containing fluorine ions and application thereof in basic industry Download PDFInfo
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- CN101775617B CN101775617B CN 200910231444 CN200910231444A CN101775617B CN 101775617 B CN101775617 B CN 101775617B CN 200910231444 CN200910231444 CN 200910231444 CN 200910231444 A CN200910231444 A CN 200910231444A CN 101775617 B CN101775617 B CN 101775617B
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- fluoropolymer
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- containing fluorine
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Abstract
The invention relates to an exchange membrane containing fluorine ions and an application thereof in the basic industry. The exchange membrane containing the fluorine ions is a multi-layer membrane containing at least two layers of fluoropolymer single membranes, wherein a perfluoropolymer containing metal ions is dispersed in at least one layer of fluoropolymer single membranes. The exchange membrane containing the fluorine ions is used in the basic industry and is suitable for preparing caustic soda within a concentration range of 20 to 45 percent in parts by mass. The invention not only has high current efficiency but also has favorable process stability after long-time operation.
Description
Technical field
The present invention relates to a kind of exchange membrane containing fluorine and the application in basic industry thereof, belong to the ionic membrane technical field.
Background technology
Ionic membrane legal system alkali by universally acknowledged for being present most advanced and the most rational economically production of caustic soda method, be the developing direction of current electrolysis system caustic soda technology.The current efficiency that improves electrolyzer in the ionic membrane alkali producing process is one of ionic membrane manufacturer and system alkali industry common goal in research.
The factor that influences ion-exchange membrane electrolyzer current efficiency has a lot, for example: the exchange capacity of ion-exchange membrane self, structure, thickness; The service temperature of electrolyzer, current density; The concentration of sodium-chlor and caustic soda concentration etc. in foreign matter content in the salt solution, the anolyte.
Wherein caustic soda concentration is very crucial to the influence of electrolytic cell currents efficient in the ionic membrane alkali producing process.When the structure of ionic membrane fixedly the time, caustic soda concentration rises from beginning than low value, and the concentration of non diffusible ion rises in the film, and current efficiency rises thereupon; But after caustic soda concentration surpassed certain value, the water content in the film was extremely not enough, causes current efficiency obviously to descend.
In order to obtain higher current efficiency, to use the ionic membrane of different exchange capacities to different system alkali concns.For example, the IEC value of the Flemion430 film of Asahi Glass company is 1.20mmol/g, when this film is used to produce the caustic soda of 22-28%, can obtain higher current efficiency; But when being used to prepare the high density caustic soda, its current efficiency obviously descends.The IEC value of Dui Ying Flemion230 film is 1.44mmol/g with it, when being used to produce 35% caustic soda, can obtain higher current efficiency; And when being used to prepare the lower concentration caustic soda, its current efficiency descends on the contrary.Introduced a kind of ion membrane electrolytic process of producing concentrated caustic among the patent CN 1036606A, this invention is started with from the material of ionic membrane and structure and is improved, and the concentration of the caustic soda of producing can reach 42-43wt%, and its current efficiency can remain on 93-97%; But this invention also is only applicable to production high density caustic soda, and current efficiency reduces in the production process of lower concentration caustic soda.
Patent US 4025405 and US 4135996 have reported that all concentration is higher than the preparation method of 40% NaOH caustic soda, but the current efficiency of electrolyzer all is lower than 90% in the alkali producing process.Patent US 4212713 and US 4202743 have reported the concentrated caustic that adopts high equivalent weight carboxylic acid group ionic membrane preparation 40%, can decompose gradually but the hydroxy-acid group of alkali producing process intermediate ion film is unstable.
Patent CN 1062382A discloses a kind of fluorine-containing cationic exchange membrane, this ionic membrane is applied in the electrolysis, be suitable for preparing the alkali metal hydroxide in the 20-54wt% concentration range, but this ionic membrane preparation technology more complicated, and can find that from embodiment the groove that this ionic membrane produces is pressed higher in electrolytic process.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of improved exchange membrane containing fluorine, this ion-exchange membrane is applied in the basic industry, and simply the prepared mass fraction is the caustic soda of the wide concentration range of 20-45%, and shows advantages of excellent stability in electrolytic process.
Technical scheme of the present invention is as follows:
A kind of exchange membrane containing fluorine, it is the multilayer film that contains at least 2 layers of fluoropolymer monofilm, wherein be dispersed with the (per) fluoropolymer of metal ion at least 1 layer of fluoropolymer monofilm, the fluoropolymer mass ratio (1～20) of the (per) fluoropolymer of this metal ion and place layer: (99～80).
Preferably, the fluoropolymer mass ratio (1～10) of the (per) fluoropolymer of metal ion and place layer: (99～90).
Described fluoropolymer is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer copolymerization that contain functional group, or the mixture of above-mentioned multipolymer; Preferably, Fluorine containing olefine is selected from: tetrafluoroethylene, and trifluorochloroethylene, trifluoro-ethylene, R 1216, and/or in the vinylidene one or more, preferred, Fluorine containing olefine is selected from tetrafluoroethylene.
The described fluorine-containing alkene monomer that contains functional group is selected from one or more as shown in the formula (I), (II) and/or (III):
Wherein, a, b, c are the integer of 0～l, but can not be zero simultaneously, and d is 0～5 integer, and n is 0 or l,
R
F1, R
F2And R
F3Can from perfluoroalkyl or freon base, choose respectively; Preferred C
1～C
10Perfluoroalkyl or freon base;
X is selected from F, Cl, Br, or I;
Y
1, Y
2, Y
3Be selected from SO
2M or COOR, wherein:
M is selected from F or Cl; R is selected from methyl, ethyl or propyl group.
The (per) fluoropolymer of described metal ion is selected from one or more in the polymer architecture shown in the following formula:
Wherein, M and M ' are selected from Ce, Mn, La, Zn, W, Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ta, Re, Ir, Pt, H, Na or K respectively; N, m represent the valence state of metal ion in the formula; The integer of a, b, c, d=1～10, and a '=b '=c '=d '=1; Y/ (x+y)=0.01～0.3%, x/ (x+y)=99.7～99.99%; T=2,3 or 4.
Preferably, M and M ' are selected from: W, Mo, La, Ce or Mn.
The dispersion of the (per) fluoropolymer of described metal ion in the fluoropolymer monofilm be by with the fluoropolymer of the (per) fluoropolymer of metal ion and place layer by (1～20): be dissolved in the water-alcohol solution after the mass ratio of (99～80) mixes, evenly film forming realizes then.
Preferably, the fluoropolymer mass ratio of the (per) fluoropolymer of metal ion and place layer is (1～10): (99～90).
Described water-alcohol solution, wherein water gets final product by conventional selection the in this area with the ratio of alcohol, pure particular methanol, ethanol, propyl alcohol, ethylene glycol or Virahol, preferably water is 1: 1 with the weight ratio of alcohol.
Preferably, the fluoropolymer of the (per) fluoropolymer of metal ion and place layer is 5-60wt% as solid mass content mutually in the water-alcohol solution; Preferred, the mass content that is suitable for making the solid phase of film is 15-40wt%.
The mixing water alcoholic solution of the fluoropolymer of the (per) fluoropolymer of above-mentioned metal ion and place layer forms exchange membrane containing fluorine with other fluoropolymer monofilm or multilayer film hot pressing after can directly adopting the casting technique film forming; Perhaps the mixing water alcoholic solution with the fluoropolymer of the (per) fluoropolymer of metal ion and place layer directly is coated in other polymkeric substance monofilm or multi-layer film surface, and coating is after drying as one deck monofilm and other polymkeric substance monofilms or the multilayer film formation exchange membrane containing fluorine of combining closely; Wherein coating processes can be selected methods such as brushing, roller coat, transfer printing or spin coating for use.Technological operation all gets final product by prior art.
Preferably, other polymkeric substance monofilm is a sulfonate film; Multilayer film is sulfonic acid/carboxylic acid composite membrane, sulfonic acid/sulfoacid carboxylic acid multipolymer composite membrane or sulfonic acid/sulfoacid carboxylic acid blend composite membrane.The preparation of these films is prior art.
The thickness of the fluoropolymer rete of the described (per) fluoropolymer that is dispersed with metal ion is the 4-20 micron.
Exchange membrane containing fluorine among the present invention can also adopt prior art to carry out the surface hydrophilic coating and handle, for example at the coated on both sides zirconium white hydrophilic coating of above-mentioned film, and specifically can be with reference to US 4367126, US 4666574, US 4652356 etc.
Exchange membrane containing fluorine among the present invention can adopt prior art to strengthen, for example: grid cloth enhancing, fiber reinforcement etc., specifically can be with reference to patent US 4477321, US 4021327, CN 101350419A etc.
Exchange membrane containing fluorine among the present invention need be through just possessing ion exchanging function after transition, preferably, can adopt prior art with above-mentioned film in the mixed aqueous solution that contains 15wt% dimethyl sulfoxide (DMSO) and 20wt%KOH, in 85 ℃ of following dippings 80 minutes, reach purpose transition.
The application of exchange membrane containing fluorine of the present invention:
Exchange membrane containing fluorine of the present invention is applied in the basic industry, as barrier film between the anolyte compartment and cathode compartment of electrolyzer.In the anolyte compartment, put into the aqueous solution of alkali metal chloride, make alkali metal hydroxide at cathode compartment after the electrolysis.
When exchange membrane containing fluorine is used, the described close cathode side of fluoropolymer rete that is dispersed with the (per) fluoropolymer of metal ion, when having only 1 tunic to be dispersed with the (per) fluoropolymer of metal ion in the exchange membrane containing fluorine, then this layer is near the cathode side the first layer; When having 2 tunics to be dispersed with the (per) fluoropolymer of metal ion in the exchange membrane containing fluorine, then be followed successively by the first layer and the second layer near cathode side.
Preferably, exchange membrane containing fluorine is near the (per) fluoropolymer that is not dispersed with metal ion in the first layer fluoropolymer monofilm of anode side.
The scheme that exchange membrane containing fluorine among the present invention is used for basic industry is, as the ion exchange membrane in the chlor-alkali electrolytic cells, is used to prepare the alkali metal hydroxide that concentration is 20-45wt%, guarantees higher current efficiency simultaneously.
The concrete application of exchange membrane containing fluorine of the present invention in basic industry be as shown in Figure 1: enter anolyte compartment 1 continuously through the dense common salt aqueous solution of purified, sodium ion sees through exchange membrane containing fluorine 2 and moves to cathode compartment 3 under electric field action, the hydroxide ion that enters brine electrolysis on the sodium ion of catholyte and the negative electrode and produce generates sodium hydroxide, simultaneously releasing hydrogen gas on negative electrode.Chlorion in the common salt aqueous solution is subjected to the restriction of film, can not enter cathode compartment basically and be oxidized into chlorine on anode.
The invention has the advantages that:
1, exchange membrane containing fluorine of the present invention can be used for preparing the alkali metal hydroxide of broad concentration range, and all can keep high current efficiency;
2, exchange membrane containing fluorine of the present invention can keep good technology stability in the life-time service process;
3, exchange membrane containing fluorine of the present invention has good tolerability to the inorganic impurity in the alkali metal chloride (for example: calcium, magnesium, silicon-dioxide).
Description of drawings
Fig. 1 is that exchange membrane containing fluorine is applied in the structural representation in the chlor-alkali ion-exchange membrane electrolyzer, and wherein 1 is that anolyte compartment, 2 is that exchange membrane containing fluorine, 3 is cathode compartment;
Fig. 2 is the structural representation of the exchange membrane containing fluorine of embodiment 1 and 3, and wherein 4 is that A layer or C layer, 5 are B layer or D layer;
Fig. 3 is the structural representation of the exchange membrane containing fluorine of embodiment 6, and wherein 6 is that H layer, 7 is that I layer, 8 is that J layer, 9 is for strengthening screen cloth.
Embodiment
Below by embodiment the present invention is described in detail.Embodiment only is used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention, and the person skilled in art can content make some nonessential improvement and adjustment to the present invention according to the present invention.
At first, adopt composite co-extruding prepared sulfonic acid/carboxylic acid composite membrane, wherein the sulfonate resin structure is:
Carboxylic acid resin's structure is:
The composite membrane A thickness that makes is 100 microns.Afterwards, water and ethanol are made into mixed solution according to 1: 1 weight ratio, with structure are then:
(per) fluoropolymer (wherein: y/ (x+y)=0.2%, x/ (x+y)=99.8%) and the structure of metal ion be:
Sulfonate resin mix according to 3: 97 mass ratio after, the preparation mass fraction is 20% water-alcohol solution, adopts casting technique film forming B then, film thickness is 12 microns.At last, above-mentioned A film and B tunic are carried out lamination hot pressing, form three layers of exchange membrane containing fluorine.After this film transition, coating handled, be installed in and carry out electrical property in the experiment type electrolyzer and measure, the unitary film B that wherein is dispersed with the (per) fluoropolymer of metal ion is the first layer near negative electrode.
Electrolyzer is at 90 ℃, 4KA/m
2Operate under the current density, change caustic soda concentration from 20% to 45%, obtain corresponding current efficiency and groove and press.Data are shown in Table 1:
Table 1
| Average N aOH concentration (%) | Mean current efficient (%) | Average groove is pressed (V) | The operate continuously fate |
| 22 | 96.4 | 2.97 | 8 |
| 28 | 96.8 | 2.99 | 8 |
| 34 | 97.1 | 2.93 | 8 |
| 39 | 96.9 | 2.96 | 14 |
| 44 | 97.3 | 3.0 | 14 |
As described in embodiment 1, different is when adopting electrolyzer to measure the electrical property of fluoride ion film, in the sodium chloride aqueous solution of supplying with, add inorganics Ca, Mg impurity 15ppb, caustic soda concentration is 39%, under the identical condition of embodiment 1, carry out 30 days electrolytic experiment, the mean current stabilised efficiency is 96.7%, and average groove is pressed and is stabilized in 2.99V.
At first, adopt composite co-extruding prepared sulfonic acid/sulfoacid carboxylic acid blend composite membrane, wherein the sulfonate resin structure is:
Carboxylic acid resin's structure is:
The composite membrane C thickness that makes is 100 microns.Afterwards, water and ethanol are made into mixed solution according to 1: 1 weight ratio, with structure are then:
(per) fluoropolymer (wherein: y/ (x+y)=0.08%, x/ (x+y)=99.92%) and the structure of metal ion be:
Sulfonate resin mix according to 1: 99 mass ratio after, the preparation mass fraction is 18% water-alcohol solution, adopts casting technique film forming D then, film thickness is 10 microns.At last, above-mentioned C film and D film are carried out lamination hot pressing, form three layers of exchange membrane containing fluorine.After this film transition, coating handled, be installed in and carry out electrical property in the experiment type electrolyzer and measure, the unitary film D that wherein is dispersed with the (per) fluoropolymer of metal ion is the first layer near negative electrode.
Electrolyzer is at 90 ℃, 4KA/m
2Operate under the current density, caustic soda concentration is 45%, operate continuously 15 days, and recording mean current efficient is 96.8%, groove is pressed is 2.96V.
At first, with structure be:
The sulfonate resin wiring solution-forming after film forming E, thickness is 70 microns; With structure be afterwards:
The sulfoacid carboxylic acid multipolymer make film F by expressing technique, thickness is 20 microns.Water and ethanol are made into mixed solution according to 1: 1 weight ratio, with structure are then:
(per) fluoropolymer (wherein: y/ (x+y)=0.1%, x/ (x+y)=99.9%) and the structure of metal ion be:
Sulfonate resin mix according to 10: 90 mass ratio after, the preparation mass fraction is 7% water-alcohol solution, adopts casting technique film forming G then, film thickness is 8 microns.At last, above-mentioned E film, F film and G film are carried out lamination hot pressing, form three layers of exchange membrane containing fluorine.After this film transition, coating handled, be installed in and carry out electrical property in the experiment type electrolyzer and measure, the unitary film G that wherein is dispersed with the (per) fluoropolymer of metal ion is the first layer near negative electrode.
Electrolyzer is at 90 ℃, 4KA/m
2Operate under the current density, caustic soda concentration is 28%, operate continuously 22 days, and recording mean current efficient is 97.1%, groove is pressed is 2.96V.
As described in embodiment 4, different employing electrolyzer when measuring the electrical property of fluoride ion film, in the sodium chloride aqueous solution of supplying with, add inorganics SiO
2Impurity 14ppm carries out 20 days electrolytic experiment under the identical condition of embodiment 1, the mean current stabilised efficiency is 96.8%, and average groove is pressed and is stabilized in 2.98V.
Embodiment 6
At first, with structure be:
The sulfonate resin wiring solution-forming after film forming H, thickness is 80 microns; Water and ethanol are made into mixed solution according to 1: 1 weight ratio, with structure are then:
(per) fluoropolymer (wherein: y/ (x+y)=0.1%, x/ (x+y)=99.9%) and the structure of metal ion be:
Sulfonate resin mix according to 3: 97 mass ratio after, the preparation mass fraction is 10% water-alcohol solution, adopts casting technique film forming I then, film thickness is 14 microns.(per) fluoropolymer and structure with the metal ion of said structure is again:
Sulfonate resin mix according to 4: 96 mass ratio after, the preparation mass fraction is 22% water-alcohol solution, adopts casting technique film forming J then, film thickness is 6 microns.At last, above-mentioned H film, I film, enhancing grid cloth and J film are carried out lamination hot pressing, form three layers of exchange membrane containing fluorine of enhanced.After this film transition, coating handled, be installed in and carry out electrical property in the experiment type electrolyzer and measure, unitary film J, the I that wherein is dispersed with the (per) fluoropolymer of metal ion is respectively the first layer, the second layer near negative electrode.
Electrolyzer is at 90 ℃, 4KA/m
2Operate under the current density, caustic soda concentration is 40%, operate continuously 12 days, and recording mean current efficient is 97.4%, groove is pressed is 2.93V.
Claims (10)
1. exchange membrane containing fluorine, it is characterized in that it being the multilayer film that contains at least 2 layers of fluoropolymer monofilm, wherein be dispersed with the (per) fluoropolymer of metal ion at least 1 layer of fluoropolymer monofilm, the fluoropolymer mass ratio (1～20) of the (per) fluoropolymer of this metal ion and place layer: (99～80);
The described fluoropolymer that is used to prepare the fluoropolymer monofilm is to be formed by Fluorine containing olefine, one or more fluorine-containing alkene monomer copolymerization that contain functional group, or the mixture of above-mentioned multipolymer.
2. exchange membrane containing fluorine as claimed in claim 1 is characterized in that the (per) fluoropolymer of described metal ion is selected from one or more in the polymer architecture shown in the following formula:
Wherein, M and M ' are selected from Ce, Mn, La, Zn, W, Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ta, Re, Ir, Pt, Na or K respectively; N, m represent the valence state of metal ion in the formula; The integer of a, b, c, d=1～10, and a '=b '=c '=d '=1; Y/ (x+y)=0.01～0.3%, x/ (x+y)=99.7～99.99%; T=2,3 or 4.
3. exchange membrane containing fluorine as claimed in claim 2 is characterized in that described M and M ' are selected from W, Mo, La, Ce or Mn.
4. exchange membrane containing fluorine as claimed in claim 1 is characterized in that described Fluorine containing olefine is selected from tetrafluoroethylene, trifluorochloroethylene, trifluoro-ethylene, one or more in R 1216 or the vinylidene.
5. exchange membrane containing fluorine as claimed in claim 1 is characterized in that the described fluorine-containing alkene monomer that contains functional group is selected from one or more as shown in the formula (I), (II) and/or (III):
Wherein, a, b, c are 0～1 integer, but can not be zero simultaneously, and d is 0～5 integer, and n is 0 or 1,
R
F1, R
F2And R
F3From perfluoroalkyl or freon base, choose respectively;
X is selected from F, Cl, Br or I;
Y
1, Y
2, Y
3Be selected from SO
2M or COOR, wherein: M is selected from F or Cl; R is selected from methyl, ethyl or propyl group.
6. exchange membrane containing fluorine as claimed in claim 1 is characterized in that the (per) fluoropolymer of described metal ion and the fluoropolymer mass ratio of place layer are (1～10): (99～90).
7. the application of each described exchange membrane containing fluorine of claim 1～6, be used for basic industry as barrier film between the anolyte compartment and cathode compartment of electrolyzer.
8. the application of exchange membrane containing fluorine as claimed in claim 7, when it is characterized in that exchange membrane containing fluorine is used, the described close cathode side of fluoropolymer rete that is dispersed with the (per) fluoropolymer of metal ion, when having only 1 tunic to be dispersed with the (per) fluoropolymer of metal ion in the exchange membrane containing fluorine, then this layer is near the cathode side the first layer; When having 2 tunics to be dispersed with the (per) fluoropolymer of metal ion in the exchange membrane containing fluorine, then be followed successively by the first layer and the second layer near cathode side.
9. the application of exchange membrane containing fluorine as claimed in claim 8 is characterized in that exchange membrane containing fluorine is near the (per) fluoropolymer that is not dispersed with metal ion in the first layer fluoropolymer monofilm of anode side.
10. the application of exchange membrane containing fluorine as claimed in claim 7 is characterized in that as the ion exchange membrane in the chlor-alkali electrolytic cells, is used to prepare the alkali metal hydroxide that concentration is 20-45wt%.
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