CN1548585A - Composite diaphragm for electrolyzing Co and its prepn - Google Patents
Composite diaphragm for electrolyzing Co and its prepn Download PDFInfo
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- CN1548585A CN1548585A CNA031287824A CN03128782A CN1548585A CN 1548585 A CN1548585 A CN 1548585A CN A031287824 A CNA031287824 A CN A031287824A CN 03128782 A CN03128782 A CN 03128782A CN 1548585 A CN1548585 A CN 1548585A
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Abstract
The composite diaphragm for electrolyzing Co features that the industrial filtering cloth as selected base material has good performance of combining with film material, homogeneous pores and even thickness; the filming liquid consists of the first polymer component, the second polymer component, solvent, non-solvent and additive; the porous film is formed on one or two sides of industrial filtering cloth via transforming process; and the electrode diaphragm bag is then produced via post-treatment. The present invention is used in electrolytic deposition of Co, and has stable physical and chemical performance, acid resistance, Cl2 resistance, long service life over 0.5 year, and no Cl2 leakage, and pore size, liquid penetrating rate and filtering precision capable of meeting the requirement of depositing Co.
Description
(1), technical field:
The present invention relates to membrane technique and be used for the electrolytic metallurgy field, is a kind of cobalt electrolysis composite diaphragm and preparation method thereof specifically.
(2), background technology:
In the electrolytic metallurgy production practice, need the electrode diaphragm bag that anode and cathode is separated.Liquid level of electrolyte in the diaphragm bag need be higher than the liquid level of electrolyte in the electrolyzer and keep certain liquid level poor, requires aperture, porosity, the saturating liquid speed of barrier film each point to be consistent simultaneously, so that metal can be deposited on the negative plate uniformly.This just requires the electrode diaphragm bag to have suitable aperture, porosity and definite saturating liquid speed.Because electrolytic solution is acidic solution and keeps certain temperature that diaphragm bag need have acidproof, heat resistance.Adopting CoCl
2In the production process of solution electrodeposited cobalt, also have Cl
2Discharge.Thereby also need cathode diaphragm bag to have anti-preferably Cl
2Performance.
At present, domestic enterprise mainly adopts the terylene filter cloth to make the electrode diaphragm bag, keeps liquid level difference and gets rid of Cl with the mode that vacuumizes
2But because of the performances such as aperture, porosity and saturating liquid speed of terylene filter cloth are difficult to satisfy production requirement.And the anti-Cl of terylene material
2Performance is also relatively poor, and work-ing life is short, needs frequently to change.Because of its density is low, keeps the liquid level difference that requires and get rid of Cl
2, just need the powerful facility that vacuumizes, make energy consumption higher, and row Cl
2Effect is also undesirable, often makes Cl
2Leak in the production environment, cause severe contamination and infringement production operation personnel health.
(3), summary of the invention:
The purpose of this invention is to provide and a kind of industrial filter cloth and membrane technique are combined, as base material, adopt phase inversion process cobalt electrolysis composite diaphragm that composite micro porous film is efficient to prepare, energy-conservation, durable on industrial filter cloth, physical and chemical performance is stable and preparation method thereof with industrial filter cloth.
The object of the present invention is achieved like this:
A kind of cobalt electrolysis composite diaphragm, it is characterized in that selecting, porous nickel good, the uniform industrial filter cloth of thickness as base material with the mould material composite performance, make film-casting liquid by following constituent materials and proportioning, adopt phase inversion process to form microporous membrane, be processed into the electrode diaphragm bag through aftertreatment again at the one or both sides of industrial filter cloth base material; Each constituent materials and the proportioning of preparation microporous membrane are:
A, first component polymer: physical and chemical performance stable polymer in cobalt electrolytic solution, as polyvinylidene difluoride (PVDF), polysulfones, polyethersulfone, polyarylsulphone, polypropylene fine and multipolymer, polyvinyl chloride and multipolymer thereof.First component polymer accounts for the 5%-20% of film-casting liquid weight.
B, second component polymer: physical and chemical performance stable polymer in cobalt electrolytic solution, comprise cellulose acetate and derivative thereof, polysulfones and derivative thereof, polyethersulfone, polyarylsulphone, the fine and multipolymer of polypropylene, polyvinyl chloride and multipolymer thereof or derivative, Polyvinylpyrolidone (PVP), polyoxyethylene glycol.Second polymkeric substance accounts for the 0.0%-10% of film-casting liquid weight.
C, solvent: can dissolve first component polymer, as pimelinketone, butanone, tetrahydrofuran (THF), methylene dichloride, trichloromethane, dimethyl formamide, N,N-DIMETHYLACETAMIDE, diethylformamide, dimethyl sulfoxide (DMSO), methyl-2-pyrrolidone, diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), Di Iso Decyl Phthalate, ethylene glycol monoemethyl ether.Solvent accounts for the 45%-90% of film-casting liquid weight.
D, non-solvent: can be miscible with solvent, as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, acetone, butanone, ethylene glycol monoemethyl ether, dimethyl sulfoxide (DMSO), ethylene glycol ether acetate, water.Non-solvent accounts for the 5%-35% of film-casting liquid weight.
E, additive: can play pore-forming, solubilising or regulating effect, as methylcellulose gum, ethyl cellulose, Natvosol, Polyvinylpyrolidone (PVP), polyoxyethylene glycol, ethylene glycol ether acetate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), Di Iso Decyl Phthalate, zinc chloride, lithium chloride, sodium-chlor, calcium chloride, cobalt chloride, nitrocalcite, SODIUMNITRATE, water.Additive accounts for the 0.0%-10% of film-casting liquid weight.
The preparation method of above-mentioned cobalt electrolysis composite diaphragm may further comprise the steps:
A, preparation film-casting liquid: with solvent, first component polymer, non-solvent, mix by proportioning, heated and stirred is to dissolving after-filtration, standing and defoaming fully;
B, film forming: in envrionment temperature is 15 ℃-35 ℃, and ambient moisture is 30%-60%, and the film-casting liquid temperature is under 30 ℃ of-75 ℃ of conditions, adopts dip-coating to add roll-in or blade coating mode film forming on the industrial filter cloth base material;
C, evaporation: in envrionment temperature is 15 ℃-35 ℃, and ambient moisture is under the 30%-60% condition, evaporates 0.1 minute-60 minutes.
D, inversion of phases: will be immersed by the film of above-mentioned steps (2) and (3) gained in non-solvent-solvent bath, wherein solvent accounts for the 0%-30% of non-solvent weight.
E, thermal treatment: will under 60 ℃ of-250 ℃ of temperature, handle 1 minute-60 minutes through the film of step (4).
By performance test and the probationary certificate to electrode diaphragm of the present invention: its physical and chemical performance in cobalt electrolytic deposition production process is stable, acidproof, anti-Cl
2Long service life reaches and surpasses half a year; No chlorine leakage; Aperture, saturating liquid speed and filtering accuracy satisfy the electrodeposited cobalt production requirement.
Table 1
| Numbering | Membrane pore size (um) | Permeability rate (ml/cm 2.min) | Filtering accuracy (um) | Work-ing life (moon) | |
| Maximum | On average | ||||
| ????1 | ????5.1 | ????3.3 | ????17.48×10 -2 | ????≤2 | ????≥6 |
| ????2 | ????7.4 | ????4.1 | ????18.48×10 -2 | ????≤2 | ????≥6 |
| ????3 | ????6.2 | ????3.2 | ????13.46×10 -2 | ????≤2 | ????≥6 |
| ????4 | ????5.5 | ????3.1 | ????12.63×10 -2 | ????≤2 | ????≥6 |
| ????5 | ????5.2 | ????4.5 | ????14.57×10 -2 | ????≤2 | ????≥6 |
| ????6 | ????5.4 | ????3.3 | ????17.86×10 -2 | ????≤2 | ????≥6 |
[embodiment 1]
Press polysulfones 12wt.%, dimethyl formamide 58wt.%, dimethyl sulfoxide (DMSO) 29wt.%, the proportioning of polyvinylpyrrolidone 1wt.%, after each component mixing, heated and stirred is incubated standing and defoaming to dissolving fully; Under 25 ℃ of envrionment temperatures, humidity 30%, 50 ℃ of conditions of film-casting liquid temperature, adopt dip-coating to add mode multiple film on industrial filter cloth of roll-in, evaporated 10 minutes, immerse inversion of phases in the water, dried 10 minutes down at 150-180 ℃.
[embodiment 2]
Press polysulfones 12wt.%, dimethyl formamide 58wt.%, dimethyl sulfoxide (DMSO) 29wt.%, the proportioning of polyvinylpyrrolidone 1wt.%, after each component mixing, heated and stirred is to dissolving fully, and the insulation standing and defoaming is under 35 ℃ of envrionment temperatures, humidity 60%, 75 ℃ of conditions of film-casting liquid temperature, adopt mode multiple film on industrial filter cloth of blade coating, evaporated 0.1 minute, and immersed inversion of phases in the water, dried 60 minutes down at 50-100 ℃.
[embodiment 3]
Press polysulfones 12wt.%, dimethyl formamide 58wt.%, dimethyl sulfoxide (DMSO) 29wt.%, the proportioning of polyvinylpyrrolidone 1wt.%, after each component mixing, heated and stirred is to dissolving fully, and the insulation standing and defoaming is under 15 ℃ of envrionment temperatures, humidity 30%, 30 ℃ of conditions of film-casting liquid temperature, adopt dip-coating to add mode multiple film on industrial filter cloth of roll-in, evaporated 60 minutes, and immersed inversion of phases in the water, dried 1 minute down at 200 ℃-250 ℃.
[embodiment 4]
Press polysulfones 5wt.%, polyethersulfone 10wt.%, dimethyl formamide 90wt.%, the proportioning of polyvinylpyrrolidone 1wt.%, after each component mixing, heated and stirred is to dissolving fully, and the insulation standing and defoaming is under 25 ℃ of envrionment temperatures, humidity 50%, 50 ℃ of conditions of film-casting liquid temperature, adopt mode multiple film on industrial filter cloth of blade coating, evaporated 6 minutes, and immersed water: inversion of phases during the inversion of phases of dimethyl formamide=70: 30 is bathed, 150 ℃-180 ℃ oven dry 10 minutes down.
[embodiment 5]
Press polysulfones 20wt.%, dimethyl formamide 45wt.%, dimethyl sulfoxide (DMSO) 34wt.%, the proportioning of polyvinylpyrrolidone 1wt.%, after each component mixing, heated and stirred is to dissolving fully, and the insulation standing and defoaming is under 25 ℃ of envrionment temperatures, humidity 50%, 75 ℃ of conditions of film-casting liquid temperature, adopt mode multiple film on industrial filter cloth of blade coating, evaporated 1 minute, and immersed inversion of phases in the water, dried 10 minutes down at 150 ℃-180 ℃.
[embodiment] 6
Press polysulfones 12wt.%, dimethyl formamide 82wt.%, the proportioning of water 5wt.%, Polyvinylpyrolidone (PVP) 1wt.%, after each component mixing, heated and stirred is to dissolving fully, the insulation standing and defoaming, under 30 ℃ of envrionment temperatures, humidity 40%, 75 ℃ of conditions of film-casting liquid temperature, adopt dip-coating to add mode multiple film on industrial filter cloth of roll-in, evaporated 10 minutes, immerse inversion of phases in the water, dried 10 minutes down at 150 ℃-180 ℃.
Claims (6)
1, a kind of cobalt electrolysis composite diaphragm, it is characterized in that selecting, porous nickel good, the uniform industrial filter cloth of thickness as base material with the mould material composite performance, make film-casting liquid by following constituent materials and proportioning, adopt phase inversion process to form microporous membrane, be processed into the electrode diaphragm bag through aftertreatment again at the one or both sides of industrial filter cloth base material; Each constituent materials and the proportioning of preparation microporous membrane are:
A, first component polymer: physical and chemical performance stable polymer in cobalt electrolytic solution, as polyvinylidene difluoride (PVDF), polysulfones, polyethersulfone, polyarylsulphone, polypropylene fine and multipolymer, polyvinyl chloride and multipolymer thereof.First component polymer accounts for the 5%-20% of film-casting liquid weight.
B, second component polymer: physical and chemical performance stable polymer in cobalt electrolytic solution, comprise cellulose acetate and derivative thereof, polysulfones and derivative thereof, polyethersulfone, polyarylsulphone, the fine and multipolymer of polypropylene, polyvinyl chloride and multipolymer thereof or derivative, Polyvinylpyrolidone (PVP), polyoxyethylene glycol.Second polymkeric substance accounts for the 0.0%-10% of film-casting liquid weight.
C, solvent: can dissolve first component polymer, account for the 45%-90% of film-casting liquid weight.
D, non-solvent: can be miscible with solvent, account for the 5%-35% of film-casting liquid weight.
E, additive: can play pore-forming, solubilising or regulating effect, account for the 0.0%-10% of film-casting liquid weight.
2, a kind of electrode composite diaphragm according to claim 1 is characterized in that described solvent can be a pimelinketone, butanone, tetrahydrofuran (THF), methylene dichloride, trichloromethane, dimethyl formamide, N,N-DIMETHYLACETAMIDE, diethylformamide, dimethyl sulfoxide (DMSO), methyl-2-pyrrolidone, diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), Di Iso Decyl Phthalate, ethylene glycol monoemethyl ether.
3, a kind of electrode composite diaphragm according to claim 1 is characterized in that described non-solvent can be a methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, acetone, butanone, ethylene glycol monoemethyl ether, dimethyl sulfoxide (DMSO), ethylene glycol ether acetate, water.
4, a kind of electrode composite diaphragm according to claim 1 is characterized in that described additive can be a methylcellulose gum, ethyl cellulose, Natvosol, Polyvinylpyrolidone (PVP), polyoxyethylene glycol, ethylene glycol ether acetate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), Di Iso Decyl Phthalate, zinc chloride, lithium chloride, sodium-chlor, calcium chloride, cobalt chloride, nitrocalcite, SODIUMNITRATE, water.
5, a kind of method for preparing cobalt electrolysis composite diaphragm as claimed in claim 1 is characterized in that it may further comprise the steps:
A, preparation film-casting liquid: solvent, first component polymer, non-solvent, additive are mixed by proportioning, and heated and stirred is to dissolving after-filtration, standing and defoaming fully;
B, film forming: in envrionment temperature is 15 ℃-35 ℃, and ambient moisture is 30%-60%, and the film-casting liquid temperature is under 30 ℃ of-75 ℃ of conditions, adopts dip-coating to add roll-in or blade coating mode film forming on the industrial filter cloth base material;
C, evaporation: in envrionment temperature is 15 ℃-35 ℃, and ambient moisture is under the 30%-60% condition, evaporates 0.1 minute-60 minutes.
D, inversion of phases: will be immersed by the film of above-mentioned steps (2) and (3) gained in non-solvent-solvent bath, wherein solvent accounts for the 0%-30% of non-solvent weight.
E, thermal treatment: will under 50 ℃ of-250 ℃ of temperature, handle 1 minute-60 minutes through the film of step (4).
6, a kind of method for preparing cobalt electrolysis composite diaphragm as claimed in claim 1 according to claim 5 is characterized in that also can comprising second component polymer in the material of preparation casting Mo liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031287824A CN100516124C (en) | 2003-05-10 | 2003-05-10 | Composite diaphragm for electrolyzing Co and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031287824A CN100516124C (en) | 2003-05-10 | 2003-05-10 | Composite diaphragm for electrolyzing Co and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1548585A true CN1548585A (en) | 2004-11-24 |
| CN100516124C CN100516124C (en) | 2009-07-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031287824A Expired - Fee Related CN100516124C (en) | 2003-05-10 | 2003-05-10 | Composite diaphragm for electrolyzing Co and its preparation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102258915A (en) * | 2011-05-13 | 2011-11-30 | 张掖市西龙产业用纺织品有限公司 | Single side composite filter membrane, and preparation method thereof |
| US8205754B2 (en) | 2006-07-25 | 2012-06-26 | Toray Industries, Inc. | Fluororesin polymer separation membrane and process for producing the same |
| CN102839389A (en) * | 2012-09-26 | 2012-12-26 | 兰州交通大学 | Novel production method of electro-depositing and refining metal chloride by membrane process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034991C (en) * | 1991-09-27 | 1997-05-28 | 中国科学院大连化学物理研究所 | Preparation of sulfonated polyary-ether-sulfone nanometer filter film |
| CN1214853C (en) * | 2001-09-04 | 2005-08-17 | 华东理工大学 | Millipore filter film for fermentation industry and its preparing process |
| CN1124175C (en) * | 2002-01-25 | 2003-10-15 | 中国科学院化学研究所 | Preparation method of dry type polyacrylointrile ultrafiltration membrane |
-
2003
- 2003-05-10 CN CNB031287824A patent/CN100516124C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8205754B2 (en) | 2006-07-25 | 2012-06-26 | Toray Industries, Inc. | Fluororesin polymer separation membrane and process for producing the same |
| CN101500695B (en) * | 2006-07-25 | 2012-09-26 | 东丽株式会社 | Fluororesin polymer separation membrane and process for producing the same |
| CN102258915A (en) * | 2011-05-13 | 2011-11-30 | 张掖市西龙产业用纺织品有限公司 | Single side composite filter membrane, and preparation method thereof |
| CN102839389A (en) * | 2012-09-26 | 2012-12-26 | 兰州交通大学 | Novel production method of electro-depositing and refining metal chloride by membrane process |
| WO2014048050A1 (en) * | 2012-09-26 | 2014-04-03 | 兰州交通大学 | Production method of electro-depositing and refining metal chloride by membrane process and preparation method for cation selective diaphragm used therein |
| CN102839389B (en) * | 2012-09-26 | 2015-06-03 | 兰州交通大学 | Novel production method of electro-depositing and refining metal chloride by membrane process |
| EP3002349A1 (en) * | 2012-09-26 | 2016-04-06 | Lanzhou Jiaotong University | Membrane process of electro-depositing and refining metal chloride and preparation of cation selective membrane |
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|---|---|
| CN100516124C (en) | 2009-07-22 |
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