WO2014048050A1 - 一种膜法金属氯化物电积精炼生产方法及该法中所采用的阳离子选择性隔膜的制备方法 - Google Patents

一种膜法金属氯化物电积精炼生产方法及该法中所采用的阳离子选择性隔膜的制备方法 Download PDF

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WO2014048050A1
WO2014048050A1 PCT/CN2013/000292 CN2013000292W WO2014048050A1 WO 2014048050 A1 WO2014048050 A1 WO 2014048050A1 CN 2013000292 W CN2013000292 W CN 2013000292W WO 2014048050 A1 WO2014048050 A1 WO 2014048050A1
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solution
parts
anode
cathode
base film
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PCT/CN2013/000292
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English (en)
French (fr)
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王三反
周键
王挺
赵红晶
张学敏
李乐卓
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兰州交通大学
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Priority to EP13834356.1A priority Critical patent/EP2743379A4/en
Publication of WO2014048050A1 publication Critical patent/WO2014048050A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention provides a novel membrane metal chloride electrowinning production method, which is a new technology technology for combining electrochemical and membrane separation, and belongs to the field of metal smelting. Background technique
  • Ion membrane electrolysis technology is a combination of membrane separation and electrolysis with comprehensive functional properties.
  • the cation exchange membrane or the anion exchange membrane is used to divide the electrolytic cell into a plurality of compartments (eg, a cathode chamber, an anode chamber, a middle compartment), and each compartment can be used under the action of the electric field force and the selective transmission characteristics of the ion exchange membrane.
  • the electrolyte solution anion and cation selectively pass or block to achieve the purpose of material concentration, desalination, purification, purification and electrochemical synthesis.
  • the high-efficiency, high-quality, non-polluting properties of ionic membrane electrolysis technology have attracted people's attention. They have been widely used in the production of chlor-alkali, the desalination of seawater and brackish water, the preparation of industrial water and ultrapure water, but in metal smelting. There are very few industry applications.
  • nano-scale inorganic oxides are zirconium dioxide, silicon dioxide, titanium dioxide, Nanomaterials such as aluminum oxide.
  • nano-sized silica to the organic polymer improves the selective permeability of the ion exchange membrane, but reduces the conductivity of the ion exchange membrane, and has high membrane resistance and high energy consumption.
  • the preparation process of nano-sized zirconium dioxide and nano-sized titanium dioxide is complicated, the production cost is high, and it is not suitable for large-scale commercial applications.
  • the object of the invention is to overcome the shortcomings of serious chlorine gas environmental pollution, high treatment cost and quality of metal products in the conventional metal chloride electrowinning process, and to provide a novel membrane for avoiding chlorine gas generation from the production source and completely solving the chlorine gas pollution environment.
  • a method for producing a metal chloride electrowinning refining method and a method for preparing a cation selective membrane used in the method are provided.
  • a novel membrane metal chloride electrowinning production method which uses a cation selective membrane and an anion selective membrane to sequentially divide the electrolytic cell into an anode chamber, a middle compartment, a cathode chamber, an anode and a cathode,
  • the anolyte and the catholyte are respectively placed in the anode chamber and the cathode chamber, the anolyte is a dilute sulfuric acid solution, the catholyte is an acidic metal chloride solution, the middle compartment is filled with a dilute hydrochloric acid solution, and when the direct current electrolysis is performed, the metal cation is The cathode is reduced and precipitated in a simple form.
  • the anode undergoes a water oxidation reaction to obtain oxygen
  • the intermediate compartment can obtain a 5% to 10% hydrochloric acid solution.
  • the anode is a lead-based alloy or a titanium-based semiconductor coated electrode.
  • the anode current density is from 100 A/m 2 to 500 A/m 2
  • the cathode is a nickel plate, a copper plate, a cobalt plate, or a zinc plate corresponding to the metal cation in the catholyte.
  • the concentration of the dilute hydrochloric acid solution in the middle compartment is 0.5% to 1%.
  • a preparation method of a cation selective membrane comprising the following two steps,
  • Step 1 Preparation of a sulfonic acid group-containing base film by manganese dioxide/polyvinylidene fluoride blending
  • a mixture of glycidyl ester or glycidyl methacrylate uniformly mixed, and then added an initiator, and the solution is uniformly mixed under ultrasonication, allowed to stand for 1 to 2 days, and then defoamed and matured to form a casting solution, wherein
  • the substances involved in the step are: by weight: 5-10 parts of polyvinylidene fluoride, 1.2 ⁇ 2 parts of styrene, 0.05 ⁇ 0.5 parts of manganese dioxide, 0.6 ⁇ 1.3 parts of high pressure polyethylene, glycidyl acrylate or 2 to 3 parts of glycidyl methacrylate, 82 to 90 parts of an organic solvent containing a reactive group, and 0.5 to 2 parts of an initiator; b. casting the above-mentioned casting solution on a glass plate at a normal temperature to form a film Placed in an incubator, heated at 120 ° C ⁇ 150 ° C for 8 hours, cooled at room temperature to form a base film;
  • Step 2 Plasma irradiation base film grafting phenolic group
  • the one side of the base film obtained in the first step is insulated, placed in a plasma reactor, and subjected to surface activation treatment to increase the surface energy and hydrophilicity of the base film, specifically using a normal pressure pulse corona discharge irradiation time. 20s ⁇ 100s, wherein the voltage is 8kV ⁇ 12kV, and the working gas is any one or more of pure argon gas, pure nitrogen gas and pure helium gas;
  • the above-mentioned polymerized grafted base film is once again placed in a plasma reactor for radical graft copolymerization reaction, and the irradiation time of the atmospheric pressure pulse corona discharge is 20s to 100s, wherein the voltage is 8kV ⁇ 12kV, work
  • the gas is any one or two or more kinds of pure argon gas, pure nitrogen gas, and pure helium gas, and then immersed in deionized water for 24 hours to remove unreacted monomers.
  • the organic solvent containing the active group in the step a of the step 1 is a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylformamide in a weight ratio of 8 to 9:1-2.
  • a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylacetamide in a weight ratio of 8 to 9:1 to 2, or an allyl group having a weight ratio of 8 to 9: 1-2 A mixed solution of sodium sulfonate and dimethylformamide.
  • the organic solvent containing a reactive group is a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylformamide in a weight ratio of 8:1.
  • the initiator in the step a of the first step is a mixture of dodecyl peroxide and di-tert-butyl peroxide in a weight ratio of 8:2.
  • each substance is divided into parts by weight: 8 parts of polyvinylidene fluoride, 2 parts of styrene, 0.1 parts of manganese dioxide, 0.9 parts of high-pressure polyethylene, 2.5 parts of glycidyl acrylate or glycidyl methacrylate, 85 parts of an organic solvent containing a reactive group, and 1.5 parts of an initiator.
  • the phenol group-containing monomer in the step b of the second step is one or a mixture of 2-allyl phenol and 4-vinyl phenol, and the mass percentage of the solution A is 5% to 20%.
  • 2-allylphenol is used, and the mass percentage of the solution A is preferably 15%.
  • the crosslinking agent in the step b of the second step is divinylbenzene or diisocyanate, and the mass percentage of the solution A is 0.5% to 1%, preferably 0.8%.
  • the nanometer manganese dioxide has a particle diameter of 10 nm to 50 nm.
  • the cation selective membrane comprises the cation selective membrane of claim 7, wherein one side of the phenolic group is a middle compartment, and is contacted with a dilute hydrochloric acid solution, and the other side without a phenolic group is The anode chamber is in contact with a dilute sulfuric acid solution.
  • the metal cation of the metal chloride solution in the cathode chamber is attracted by the cathode, directional migration to the cathode, and an electrode reduction reaction occurs on the cathode to precipitate in the form of a metal element;
  • the evolved cathode chamber passes through the anion selective membrane and enters the intermediate compartment, and is fixed in the middle compartment by the barrier of the cation selective membrane;
  • the anode chamber contains a dilute sulfuric acid solution, and the oxidation potential of the H 2 0 on the anode is lower than S0 4 2 —
  • the oxidation potential at the anode so that the water is oxidized, and the electrode oxidation reaction occurs to generate H+ and 0 2 ;
  • H + is pulled by the DC electric field force, and moves out of the anode chamber through the cation selective membrane into the intermediate compartment.
  • the cation selective membrane and its preparation method are the key contents of the present invention because the cation selective membrane of the present invention is selected, and the side having a phenol group is exposed to a dilute hydrochloric acid solution, and the membrane has a high cr barrier function. , cr blocking rate can reach 99.9%, cation selective membrane side graft polymerization of phenolic group-containing monomer, can increase hydrophilicity, while ionizing hydrogen ions, weakly acidic, with a negative layer on the membrane surface The electric charge can form a negative electric field, which can effectively block the migration of chloride ions in the metal chloride solution in the cathode chamber to the anode, and an oxidation reaction occurs to generate chlorine gas.
  • the invention adopts the method of adding nano-scale inorganic materials and plasma irradiation graft polymerization technology to prepare a cation selective membrane with high anion blocking rate, large exchange capacity and good mechanical strength.
  • the ion exchange capacity can be increased. This is due to the electrostatic attraction, which increases the relative ion concentration on the surface of the base film, which is manifested by an increase in the fixed charge density on the surface of the base film. The number of ion migrations also increases, and at the same time, the conductivity and mechanical properties of the base film are increased, and the hydrophilicity of the base film is increased.
  • corona discharge by using plasma to activate and graft polymerize the organic monomer on the surface of the base film is as follows: Corona discharge is not strong, and the penetration thickness is shallow, which will not cause mechanical damage to the base film, and will not affect the base. Membrane body performance, only need to act on the surface of the base film, simple and easy to process, fast processing. High-energy particles generated during corona discharge, the energy of high-energy particles is huge, generally about several to several tens of electron volts, such as electron energy of 0 ⁇ 20eV, metastable particles of 0 ⁇ 20eV, ultraviolet light/ The visible light is 3 ⁇ 40eV.
  • the active, excited state molecules are unstable, decomposed into self-sulfonating groups or ions, and can be polymerized with organic monomers to form a designable coating on the surface of the film.
  • the surface of the base film material can be activated, which is more favorable for contact with the phenol-based organic monomer, so that the highly hydrophilic phenolic group which is difficult to graft is smoothly graft-polymerized to the hydrophobic polyposition.
  • the 2-allyl phenol and 4-vinyl phenol are grafted to the side of the polyvinylidene fluoride and the styrene base film by polymerization to increase the hydrophilicity of the base film.
  • the side of the base film can ionize hydrogen ions, has weak acidity, and has a negative charge on the surface of the base film to form a negative electric field.
  • the base film itself contains a fixed group-sulfonic acid cation exchange membrane based on cation.
  • the electric double layer theory of the selective separator repels the isotropic ions, which greatly increases the anion blocking rate, especially the negatively charged ions. Table 1 Performance parameters of different cation selective membranes
  • Membrane A - a cation selective membrane of the present invention, a membrane B-manganese dioxide/polyvinylidene fluoride blend to prepare a sulfonic acid group-containing base film, a membrane C-perfluorosulfonic acid membrane.
  • the performance parameters of membrane A are superior to membrane B and membrane C.
  • the anion non-permeability rate, chloride ion blocking rate can reach 99.9%, which is mainly due to a negative charge on the surface of the membrane A, forming a negative electric field to prevent chloride ion transmission; membrane ion ion exchange capacity and
  • the water content is better than that of membrane B and membrane C.
  • nano-sized manganese dioxide which increases the hydrophilic group in membrane A, thereby increasing the water content of membrane A and increasing the density of sulfonic acid groups in membrane A. Increase the number of exchangeable counterions and increase the ion exchange capacity.
  • Ion exchange capacity refers to the concentration of active groups in the ion exchange membrane and its chemical performance index with respect to reverse ion exchange capacity, with active groups per gram of dry film The number of milliequivalents expressed is (mmol/g).
  • a H+ - ion exchange capacity (mmol/g dry film), a-collection solution H + content (mol), V-NaOH dosage (L), W-water content (%), G wet - wet weight (g), G dry - dry weight (g).
  • the film to be tested is sandwiched between two compartments of different concentrations of the same type of electrolyte solution (such as KC1 solution), using a saturated calomel electrode as a reference electrode, and a salt bridge is used between the electrolyte solution and the calomel electrode.
  • electrolyte solution such as KC1 solution
  • a saturated calomel electrode as a reference electrode
  • a salt bridge is used between the electrolyte solution and the calomel electrode.
  • the invention transforms the electrolytic cell in the conventional electrolytic process into a membrane electrolysis process and an integrated electrolytic cell structure.
  • the electrolysis cell is divided into three compartments by two selective membranes to form an anode chamber, a cathode chamber and a middle compartment, in which different electrolytes or receiving liquids are injected.
  • the cathode chamber is still injected with the existing chloride-containing electrolyte, and the quality of the normal chlorinated refining electrode metal can be ensured without changing its composition, concentration and circulation mode.
  • the anode chamber is injected with a chlorine-free H 2 S0 4 dilute electrolyte.
  • the HC1 dilute receiving liquid is injected into the septum to collect chloride ions migrated from the cathode chamber and hydrogen ions migrated in the anode chamber. It can maintain the normal electrolysis process and prevent the generation of chlorine gas, thus completely solving the problem of chlorine gas generated by the conventional metal chloride electrowinning process and avoiding environmental pollution. It can also convert chlorine ions into high-concentration hydrochloric acid for recycling and utilization, and has high economic value.
  • the quality of the obtained metal products is a new method in line with the development direction of green metallurgy and environmental protection.
  • Figure 1 is a schematic diagram of a novel membrane metal chloride electrowinning production method
  • FIG. 2 is a schematic diagram of an electrochemical reaction of a novel membrane metal chloride electrowinning production method
  • 1-cation selective membrane 2-anion selective membrane
  • 3-anode chamber 4-intermediate compartment, 5-cathode chamber, 6-anode, 7-cathode, 8-anolyte, 9-catholyte, 10-electrolyzer.
  • a novel membrane metal chloride electrowinning production method which uses a cation selective membrane and an anion selective membrane to sequentially divide an electrolytic cell into an anode chamber, a middle compartment, a cathode chamber, an anode and a cathode, an anolyte and a catholyte respectively Correspondingly placed in the anode chamber and the cathode chamber, the anolyte is a dilute sulfuric acid solution, the catholyte is an acidic metal chloride solution, and the middle compartment is filled with a dilute hydrochloric acid solution.
  • the metal cation is reduced at the cathode and in a simple form.
  • the anode undergoes water oxidation reaction to obtain oxygen, and the intermediate compartment can obtain 5% ⁇ 10% hydrochloric acid solution.
  • the anode is a lead-based alloy or a titanium-based semiconductor coated electrode.
  • the anode current density is from 100 A/m 2 to 500 A/m 2
  • the cathode is a nickel plate, a copper plate, a cobalt plate, or a zinc plate corresponding to the metal cation in the catholyte.
  • the concentration of the dilute hydrochloric acid solution in the middle compartment is 0.5% to 1%.
  • the electrolyte temperature during electrolysis is controlled at 0: ⁇ 70 ⁇ .
  • the electrolysis method can be carried out by using a single electrolytic cell electrowinning or a multi-electrolytic cell in series.
  • the electrolysis method is the electrolysis of a single electrolytic cell, the anode 6 is made of an inert electrode titanium coated mesh, the cathode 7 is made of a pure metal nickel plate, the cation selective membrane 1 is Nafionl 17, and the anion selective membrane 2 is selected by JAM-II homogeneous anion exchange.
  • Membrane; anolyte 8 uses 0.5% dilute sulfuric acid aqueous solution; catholyte 9 uses 40g/L NiCl 2 solution, middle compartment 4 contains 0.5% dilute hydrochloric acid aqueous solution; DC electrolysis, anode current density is 100A/m 2 , metal Nickel ions were reduced at the cathode 7 and precipitated as a simple substance, and the purity thereof was found to be 99.8%; and the intermediate compartment 4 was obtained at a concentration of 7 °/. In the aqueous hydrochloric acid solution, the concentration of chloride ions in the anolyte 8 is almost zero.
  • the electrolysis method is a series electrowinning of multiple electrolyzers, a lead silver alloy plate is used for the anode 6, a pure metal nickel plate is used for the cathode 7, a Nafion 234 is selected for the cation selective membrane 1, and a JAM-II homogeneous anion exchange membrane is selected for the anion selective membrane 2;
  • the anolyte 8 is selected from 0.8% dilute sulfuric acid aqueous solution;
  • the catholyte 9 is selected from 50g/L CoCl 2 solution, the middle compartment 4 is filled with 0.5% dilute hydrochloric acid aqueous solution; the direct current electrolysis is applied, the anode current density is 200A/m 2 , and the metal cobalt ion is used.
  • the electrolysis method is the electrolysis of a single electrolyzer, the anode 6 is made of an inert electrode titanium coated mesh, the cathode 7 is made of a pure metal nickel plate; the cation selective membrane 1 is selected from the cation selective membrane of the invention, and the anion selective membrane 2 is selected to be a JAM-II type.
  • the side of the cation selective membrane 1 with a phenolic group is a middle compartment, in contact with a dilute hydrochloric acid solution, and the other side without a phenolic group is an anode chamber, in contact with a dilute sulfuric acid solution
  • the anolyte 8 uses 0.5% dilute sulfuric acid aqueous solution
  • the catholyte 9 uses 40g/L NiCl 2 solution
  • the middle compartment 4 contains 0.6% dilute hydrochloric acid aqueous solution
  • the direct current electrolysis the anode current density is 100A/m 2
  • metallic nickel metallic nickel
  • the intermediate compartment 4 can obtain a concentration of 7% hydrochloric acid aqueous solution, and the anodic liquid 8 has a chloride ion concentration of zero.
  • the cation selective membrane 1 is selected from the cation selective membrane of the present invention, and can completely prevent the CI in the middle compartment 4 from being attracted by the DC electric field. The gravitational force migrates to the anode and is fixed in the middle compartment 4, thereby completely solving the problem of chlorine generation in the conventional metal chloride electrowinning process and avoiding environmental pollution.
  • the H+ in the anolyte 8 is pulled by the DC electric field force, and moves out of the anode chamber 3 through the cation selective membrane into the intermediate compartment 4, thereby forming HC1 with C1 in the intermediate compartment 4, and the HC1 can be recycled and reused.
  • the cation exchange membrane of the invention has high ion exchange capacity, good hydrophilicity, good selective membrane permeability, especially for chloride ions, high blocking rate and long service life.
  • the electrolyte is prepared by solid cobalt chloride, which is used as the electrowinning raw material solution after purification and turbidity.
  • concentration of CoCl 2 electrolyte is 50g/L
  • the electrolysis method of pH-3.0o is the electrowinning of multiple electrolyzers
  • the lead 6 is made of lead-silver alloy.
  • the plate, the cathode 7 is made of a pure metal nickel plate;
  • the cation selective membrane 1 is selected from the cation selective membrane of the invention, and the anion selective membrane 2 is selected from the JAM-II type homogeneous anion exchange membrane, and the cation selective membrane 1 is provided with a phenolic group.
  • One side is a middle compartment, in contact with a dilute hydrochloric acid solution, the other side without a phenolic group is an anode chamber, and is in contact with a dilute sulfuric acid solution;
  • the anolyte 8 is selected from a 0.8% dilute sulfuric acid aqueous solution:
  • the catholyte 9 is selected to be 50 g/ L CoCl 2 solution, the middle compartment 4 contains 0.5% dilute hydrochloric acid aqueous solution;
  • the direct current electrolysis the anode current density is 500 A/m 2 , the metal cobalt ion is reduced at the cathode 7 and precipitated as a simple substance, and the purity is 99.9.
  • the middle compartment 4 can obtain a 10% hydrochloric acid aqueous solution, and the anolyte 8 is detected to have a chloride ion concentration of zero.
  • the cation selective membrane 1 is selected from the cation selective membrane of the present invention, and can completely prevent the C1 in the middle compartment 4 from migrating to the anode under the traction of the direct current electric field, and is fixed in the intermediate compartment 4, thereby completely solving the conventional metal chloride.
  • the problem of chlorine generated during the electrowinning process avoids environmental pollution.
  • the H+ in the anolyte 8 is pulled by the DC electric field force, and moves out of the anode chamber 3 through the cation selective membrane into the intermediate compartment 4, thereby forming HC1 with the CI in the intermediate compartment 4, and the HC1 can be recycled and reused.
  • the cation exchange membrane of the invention has high ion exchange capacity, good hydrophilicity, good selective membrane permeability, especially for chloride ions, high blocking rate and long service life.
  • a preparation method of a cation selective membrane comprising the following two steps,
  • Step 1 Preparation of a sulfonic acid group-containing base film by manganese dioxide/polyvinylidene fluoride blending
  • the materials involved in this step are: by weight: 8 parts of polyvinylidene fluoride, 2 parts of styrene, 0.1 parts of manganese dioxide, 0.9 parts of high-pressure polyethylene, glycidyl acrylate or glycidyl methacrylate , containing 85 parts of active group organic solvent and 1.5 parts of initiator.
  • the organic solvent containing a reactive group is a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylformamide in a weight ratio of 8:1.
  • the initiator is a mixture of dodecyl peroxide and di-tert-butyl peroxide in a weight ratio of 8:2;
  • the above casting solution is cast on a glass plate to form a film, placed in an incubator, heated at 120 ° C ⁇ 150 ° C for 8 hours, cooled at room temperature to form a base film ;
  • Step two the plasma bake base film grafts phenolic groups
  • the base film obtained in the first step is placed in a plasma reactor, and surface activation treatment is performed to increase the surface energy and hydrophilicity of the base film, and the irradiation time of the atmospheric pressure pulse corona discharge is specifically 20s to 100s, wherein the voltage
  • the working gas is 8kV ⁇ 12kV, and the working gas is any one or more of pure argon gas, pure nitrogen gas and pure helium gas;
  • the crosslinking agent is divinylbenzene, and the mass percentage of the solution A is 0.8%;
  • the above-mentioned polymerized grafted base film is once again placed in a plasma reactor for radical graft copolymerization reaction, and the irradiation time of atmospheric pressure pulse corona discharge is 20s ⁇ 100s, wherein the voltage is 8kV ⁇ 12kV, work
  • the gas is any one or two or more kinds of pure argon gas, pure nitrogen gas, and pure helium gas, and then immersed in deionized water for 24 hours to remove unreacted monomers.
  • a preparation method of a cation selective membrane comprising the following two steps,
  • Step 1 Preparation of a sulfonic acid group-containing base film by manganese dioxide/polyvinylidene fluoride blending
  • the materials involved in this step are in parts by weight: 5 parts of polyvinylidene fluoride, 1.2 parts of styrene, 0.05 parts of manganese dioxide, 0.6 parts of high-pressure polyethylene, glycidyl acrylate or glycidyl methacrylate. , 82 parts of organic solvent containing active group, 0.5 part of initiator,
  • the organic solvent containing a reactive group is a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylacetamide in a weight ratio of 9:1.
  • the initiator is a mixture of dodecyl peroxide and di-tert-butyl peroxide in a weight ratio of 8:2; b. casting the above casting solution on a glass plate at room temperature, and placing it In the incubator, at 12 (TC ⁇ 150 ° C, after heating and curing for 8 hours, room temperature cooling to make the base film;
  • Step 2 Plasma irradiation base film grafting phenolic group
  • the base film obtained in the first step is placed in a plasma reactor, and surface activation treatment is performed to increase the surface energy and hydrophilicity of the base film, and the irradiation time of the atmospheric pressure pulse corona discharge is specifically 20s to 100s, wherein the voltage
  • the working gas is 8kV ⁇ 12kV, and the working gas is any one or more of pure argon gas, pure nitrogen gas and pure helium gas;
  • the crosslinking agent is a diisocyanate, and the mass percentage of the solution A is 0.5%;
  • the above-mentioned polymerized grafted base film is once again placed in a plasma reactor for radical graft copolymerization reaction, and the irradiation time of atmospheric pressure pulse corona discharge is 20s ⁇ 100s, wherein the voltage is 8kV ⁇ 12kV, work
  • the gas is any one or two or more kinds of pure argon gas, pure nitrogen gas, and pure helium gas, and then immersed in deionized water for 24 hours to remove unreacted monomers.
  • a preparation method of a cation selective membrane comprising the following two steps,
  • Step 1 Preparation of a sulfonic acid group-containing base film by manganese dioxide/polyvinylidene fluoride blending
  • the materials involved in this step are: by weight: 10 parts of polyvinylidene fluoride, 2 parts of styrene, 0.5 parts of manganese dioxide, 1.3 parts of high-pressure polyethylene, glycidyl acrylate or 2 parts of glycidyl methacrylate. , 90 parts of active solvent organic solvent, 2 parts of initiator,
  • the organic solvent containing a reactive group is a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylacetamide in a weight ratio of 4:1.
  • the initiator is a mixture of dodecyl peroxide and di-tert-butyl peroxide in a weight ratio of 8:2;
  • Step 2 Plasma irradiation base film grafting phenolic group
  • the base film obtained in the first step is placed in a plasma reactor, and surface activation treatment is performed to increase the surface energy and hydrophilicity of the base film, and the irradiation time of the atmospheric pressure pulse corona discharge is specifically 20s to 100s, wherein the voltage
  • the working gas is 8kV ⁇ 12kV, and the working gas is any one or more of pure argon gas, pure nitrogen gas and pure helium gas;
  • the crosslinking agent is a diisocyanate, and the mass percentage of the solution A is 1%;
  • the above-mentioned polymerized grafted base film is once again placed in a plasma reactor for radical graft copolymerization reaction, and the irradiation time of atmospheric pressure pulse corona discharge is 20s to 100s, wherein the voltage is 8kV ⁇ 12kV, work
  • the gas is any one or two or more kinds of pure argon gas, pure nitrogen gas, and pure helium gas, and then immersed in deionized water for 24 hours to remove unreacted monomers.
  • a preparation method of a cation selective membrane comprising the following two steps,
  • Step 1 Preparation of a sulfonic acid group-containing base film by manganese dioxide/polyvinylidene fluoride blending
  • the materials involved in this step are in parts by weight: 6 parts of polyvinylidene fluoride, 1.5 parts of styrene, 0.08 parts of manganese dioxide, 1 part of high pressure polyethylene, glycidyl acrylate or 2.5 parts of glycidyl methacrylate. , 84 parts of organic solvent containing active groups, 0.9 parts of initiator,
  • the organic solvent containing a reactive group is a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylacetamide in a weight ratio of 9:1.
  • the initiator is a mixture of dodecyl peroxide and di-tert-butyl peroxide in a weight ratio of 8:2;
  • the above casting solution is cast on a glass plate to form a film, placed in an incubator, heated at 120 ° C ⁇ 150 ° C for 8 hours, cooled at room temperature to form a base film ;
  • Step 2 Plasma irradiation base film grafting phenolic group
  • the base film obtained in the first step is placed in a plasma reactor, and surface activation treatment is performed to increase the surface energy of the base film and Hydrophilic, specifically using atmospheric pressure pulse corona discharge irradiation time 20s ⁇ 100s, wherein the voltage is 8kV ⁇ 12kV, the working gas is pure argon gas, pure nitrogen gas, pure helium gas or any one or more mixed gases ;
  • the crosslinking agent is a diisocyanate, and the mass percentage of the solution A is 0.7%;
  • the above-mentioned polymerized grafted base film is once again placed in a plasma reactor for self-ruthenium-based graft copolymerization reaction, and the irradiation time of the atmospheric pressure pulse corona discharge is 20 s to 100 s, wherein the voltage is 8 kV to 12 kV.
  • the working gas is any one or two or more kinds of pure argon gas, pure nitrogen gas, and pure helium gas, and then immersed in deionized water for 24 hours to remove unreacted monomers.
  • a preparation method of a cation selective membrane comprising the following two steps,
  • Step 1 Preparation of a sulfonic acid group-containing base film by manganese dioxide/polyvinylidene fluoride blending
  • the materials involved in this step are in parts by weight: polyvinylidene fluoride 9 parts, styrene 1.8 parts, manganese dioxide 0.2 parts, high pressure polyethylene 1.2 parts, glycidyl acrylate or glycidyl methacrylate 2.5 parts , containing 88 parts of active group organic solvent and 1.5 parts of initiator,
  • the organic solvent containing a reactive group is a mixed solution of 2-acrylamido-2-methylpropanesulfonic acid and dimethylformamide in a weight ratio of 9:1.
  • the initiator is a mixture of dodecyl peroxide and di-tert-butyl peroxide in a weight ratio of 8:2;
  • the above casting solution is cast on a glass plate to form a film, placed in an incubator, heated at 120 ° C ⁇ 150 ° C for 8 hours, cooled at room temperature to form a base film ;
  • Step 2 Plasma irradiation base film grafting phenolic group
  • the base film obtained in the first step is placed in a plasma reactor, and surface activation treatment is performed to increase the surface energy and hydrophilicity of the base film, and the irradiation time of the atmospheric pressure pulse corona discharge is specifically 20s to 100s, wherein the voltage
  • the working gas is 8kV ⁇ 12kV, and the working gas is any one or more of pure argon gas, pure nitrogen gas and pure helium gas;
  • b. Mixing the phenol group-containing monomer and the crosslinking agent in dimethylformamide or dimethylacetamide to form a solution A having a uniform concentration, and immersing the activated base film in the solution A for 30mi. Polymerization grafting is carried out at n ⁇ 200 min, wherein the monomer containing a phenol group is 4-vinylphenol, and the mass percentage of the solution A is 18%.
  • the crosslinking agent is a diisocyanate, and the mass percentage of the solution A is 0.9%;
  • the above-mentioned polymerized grafted base film is once again placed in a plasma reactor for radical graft copolymerization reaction, and the irradiation time of atmospheric pressure pulse corona discharge is 20s ⁇ 100s, wherein the voltage is 8kV ⁇ 12kV, work
  • the gas is any one or two or more kinds of pure argon gas, pure nitrogen gas, and pure helium gas, and then immersed in deionized water for 24 hours to remove unreacted monomers.
  • a preparation method of a cation selective membrane comprising the following two steps,
  • Step 1 Preparation of a sulfonic acid group-containing base film by manganese dioxide/polyvinylidene fluoride blending
  • the materials involved in this step are: by weight: 10 parts of polyvinylidene fluoride, 1.9 parts of styrene, 0.3 parts of manganese dioxide, 1 part of high-pressure polyethylene, glycidyl acrylate or glycidyl methacrylate , 90 parts of active solvent organic solvent and 1.8 parts of initiator
  • the initiator is a mixture of dodecyl peroxide and di-tert-butyl peroxide in a weight ratio of 8:2;
  • the above casting solution is cast on a glass plate to form a film, placed in an incubator, heated at 120 ° C ⁇ 150 ° C for 8 hours, cooled at room temperature to form a base film ;
  • Step 2 Plasma irradiation base film grafting phenolic group
  • the base film obtained in the first step is placed in a plasma reactor, and surface activation treatment is performed to increase the surface energy and hydrophilicity of the base film, and the irradiation time of the atmospheric pressure pulse corona discharge is specifically 20s to 100s, wherein the voltage
  • the working gas is 8kV ⁇ 12kV, and the working gas is any one or more of pure argon gas, pure nitrogen gas and pure helium gas;
  • the crosslinking agent is divinylbenzene, and the mass percentage of the solution A is 0.6%;
  • the above-mentioned polymerized grafted base film is once again placed in a plasma reactor for radical graft copolymerization reaction, and the irradiation time of atmospheric pressure pulse corona discharge is 20s to 100s, wherein the voltage is 8kV ⁇ 12kV, work
  • the gas is any one or two or more kinds of pure argon gas, pure nitrogen gas, and pure helium gas, and then immersed in deionized water for 24 hours to remove unreacted monomers.

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Abstract

提供了一种膜法金属氯化物电积精炼生产方法，利用阳离子选择性隔膜和阴离子选择性隔膜将电解槽依次分隔为阳极室、中隔室、阴极室，阳极与阴极、阳极液与阴极液分别对应置于阳极室和阴极室中，阳极液为稀硫酸溶液，阴极液为酸性金属氯化物溶液，中隔室盛有稀盐酸溶液，通入直流电电解时，金属阳离子在阴极还原并以单质形态析出，同时，阳极发生水氧化反应，得到氧气，中隔室可得到5%〜10%盐酸溶液。上述方法彻底解决常规金属氯化物电积工艺中氯气产生的问题，并且可得到高浓度盐酸副产品，回收再利用，经济价值高，所得金属产品质量好，是符合绿色冶金环保发展方向的一项方法。

Description

一种膜法金属氯化物电积精炼生产方法及该法中所采用的 阳离子选择性隔膜的制备方法 技术领域
本发明提供一种新型膜法金属氯化物电积精炼生产方法， 是一种将电化学与膜分离有机 结合的新工艺技术， 属于金属冶炼领域。 背景技术
金属精炼常规的工业规模方法是电积工艺， 就是采用高浓高纯的金属电解液， 以电化学 阴极还原的方式， 使电解液中的金属离子在阴极上还原为金属， 从而得到高纯度的金属， 铜、 镍、 钴等的精炼均采用此工艺。 在电积生产工艺中最常见的金属电解液是氯化电解液， 电解 液以金属氯化物配制， 并以盐酸调节 pH， 由于电解液中含有高浓度的氯离子， 会在电积过程 中被阳极氧化为氯气， 氯气的产生不仅会改变电解液的性质， 影响电钴质量， 同时氯气溢出 造成生产车间内部环境严重污染， 甚至操作人员必须戴防毒面具工作。 大量产生的氯气还必 须进行收集后采用碱吸收， 以消除氯气对外环境的影响 ， 碱吸收又造成了生产成本的进一 步提高。 目前国内金属氯化电积均采用上述工艺， 也均存在上述弊病。 为防止氯化电解过程 氯气污染， 国外普遍采用封闭式无隔膜电解槽技术， 以解决氯气污染工作环境问题， 但是存 在拆卸阴极的操作不便、 反复拆卸造成密封面不严或易损坏的问题。
离子膜电解技术是将膜分离与电解相结合的具有综合功能特性技术。 利用阳离子交换膜 或阴离子交换膜将电解槽分隔为若干个隔室 （如： 阴极室、 阳极室、 中隔室）， 在电场力和 离子交换膜选择透过特性作用下， 可将各个隔室电解质溶液阴阳离子选择性地通过或阻挡， 以达到物质浓缩、 脱盐、 净化、 提纯以及电化合成的目的。 离子膜电解技术的高效、 优质、 无污染特性引起了人们的高度关注， 已广泛应用于氯碱的生产,海水和苦咸水的淡化， 工业 用水和超纯水的制备等方面， 但在金属冶炼行业应用极少。
目前， 商品化阳离子交换膜普遍存在的问题是阴离子阻挡率不是很高， 一般为 90%以上， 尺寸稳定性较差， 机械强度较低。 将纳米级无机氧化物填充到有机聚合物 （如聚偏氟乙烯、 苯乙烯等单体） 中是国内外研究的热点， 常见的纳米级无机氧化物有二氧化锆、 二氧化硅、 二氧化钛、 三氧化二铝等纳米材料。 纳米级二氧化硅加入到有机聚合物中， 虽然可以提高离 子交换膜的选择透过性， 但是会降低离子交换膜导电性， 膜电阻较高， 能耗高。 纳米级二氧 化锆与纳米级二氧化钛制备过程较复杂， 制作成本较高， 不适用大规模商业应用。
发明内容 本发明目的在于克服常规金属氯化物电积精炼工艺中所产生氯气环境污染严重、 处理成 本高、 影响金属产品质量等缺点， 提供一种从生产源头避免氯气产生、 彻底解决氯气污染环 境的新型膜法金属氯化物电积精炼生产方法以及该方法中所釆用的阳离子选择性隔膜的制 备方法。
具体的技术方案如下： 一种新型膜法金属氯化物电积精炼生产方法， 利用阳离子选择性 隔膜和阴离子选择性隔膜将电解槽依次分隔为阳极室、 中隔室、 阴极室， 阳极与阴极、 阳极 液与阴极液分别对应置于阳极室和阴极室中， 阳极液为稀硫酸溶液， 阴极液为酸性金属氯化 物溶液， 中隔室盛有稀盐酸溶液， 通入直流电电解时， 金属阳离子在阴极还原并以单质形态 析出， 同时， 阳极发生水氧化反应， 得到氧气， 中隔室可得到 5%〜10%盐酸溶液。
所述的阳极为铅系合金或钛基半导体塗层电极。
所述的阳极电流密度为 100A/m2〜500 A/m2
所述的酸性金属氯化物溶液可以是 NiCl2、 CuCl2、 CoCl2、 ZnCl2溶液， pH=2~5。
所述的阴极为与阴极液中金属阳离子所对应的镍板、 铜板、 钴板、 锌板。
所述的中隔室中的稀盐酸溶液浓度为 0.5%~1%。
一种阳离子选择性隔膜的制备方法， 包括如下两大步骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸缩水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均匀混合后加入引发剂， 将上述溶液在超声下均匀混合， 静置 1~2天， 待脱泡熟化后制成铸膜液， 其中， 该歩骤中所涉及的各物质按重量份计： 聚偏氟乙 烯 5~10份、 苯乙烯 1.2〜2份、 二氧化锰 0.05〜0.5份、 高压聚乙烯 0.6~1.3份、 丙烯酸缩水甘 油酯或甲基丙烯酸縮水甘油酯 2~3份、 含有活性基团有机溶剂 82〜90份、 引发剂 0.5~2份； b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 120°C〜150°C 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体辐照基膜接枝酚基基团
a.将步骤一所得基膜一侧进行绝缘处理后， 置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和亲水性， 具体采用常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体；
b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30min~200min进行聚合接枝； c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自由基接枝共聚反应， 采用 常压脉冲电晕放电辐照时间 20s〜100s， 其中， 电压为 8kV〜12kV， 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24 小时， 除去未反应的 单体即可。
所述步骤一的步骤 a中的含有活性基团有机溶剂为重量比为 8〜9： 1-2的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基甲酰胺的混合溶液， 或重量比为 8~9： 1~2的 2-丙烯酰胺基 -2-甲基丙 磺酸和二甲基乙酰胺的混合溶液， 或重量比为 8〜9： 1-2的烯丙基磺酸钠和二甲基甲酰胺的 混合溶液。 优选的， 含有活性基团有机溶剂为重量比为 8 : 1 的 2-丙烯酰胺基 -2-甲基丙磺酸 和二甲基甲酰胺的混合溶液。
所述步骤一的步骤 a中的引发剂为重量比为 8: 2的过氧化十二酰与二叔丁基过氧化物 的混合物。
作为上述方案的进一步优化方案， 所述歩骤一的歩骤 a中， 各物质按重量份计： 聚偏氟 乙烯 8份、 苯乙烯 2份、 二氧化锰 0.1份、 高压聚乙烯 0.9份、 丙烯酸缩水甘油酯或甲基丙 烯酸缩水甘油酯 2.5份、 含有活性基团有机溶剂 85份、 引发剂 1.5份。
所述步骤二的步骤 b中的含有酚基的单体为 2-烯丙基酚、 4-乙烯基苯酚的一种或两种混 合物， 所占溶液 A的质量百分数为 5%~20%， 优选 2-烯丙基酚， 所占溶液 A的质量百分数 以 15%为佳。
所述步骤二的步骤 b中的交联剂为二乙烯基苯或二异氰酸酯，所占溶液 A的质量百分数 为 0.5%〜1%， 以 0.8%为佳。
所述纳米级二氧化锰粒径为 10nm~50nm。
所述的阳离子选择性隔膜选用权利要求 7所述的阳离子选择性隔膜， 其带酚基基团的一 侧为中隔室， 与稀盐酸溶液接触， 不带酚基基团的另一侧为阳极室， 与稀硫酸溶液接触。
具体地说， 在直流电场力的牵引下， 阴极室中的金属氯化物溶液的金属阳离子受到阴极 吸引， 向阴极做定向迁移， 并在阴极上发生电极还原反应， 以金属单质形态析出； 而 cr迁出 阴极室穿过阴离子选择性隔膜进入中隔室， 并受到阳离子选择隔膜的阻挡被固定于中隔室； 阳极室盛有稀硫酸溶液， ώ于 H20在阳极上的氧化电位低于 S04 2—在阳极上的氧化电位， 因 而水被氧化， 发生电极氧化反应， 生成 H+和 02 ; H+受到直流电场力牵引， 迁出阳极室穿过 阳离子选择性隔膜进入中隔室， 由于阴离子选择性隔膜的阻挡作用也被固定于中隔室， 从而 形成 HC1, 电化学反应式如 （1 )、 （2)、 （3 )。 阴极室还原反应： Mn++ne ~~ >M I (1) 阳极室氧化反应： H20-2e ^ > 2H++io2 † (2)
中隔室反应： H++C1——— > HC1 (3)
阳离子选择性隔膜及其制备方法是本发明的关键性内容， 这是因为选用本发明的阳离子 选择性隔膜， 且带酚基基团的一侧接触稀盐酸溶液， 该膜具有高的 cr阻挡功能， cr阻挡率 可达到 99.9%， 阳离子选择性隔膜一侧面接枝聚合含酚基基团的单体， 可增加亲水性， 同时 可电离出氢离子， 具有弱酸性， 膜表面带一层负电荷， 可形成负电场， 能够有效地阻挡阴极 室中的金属氯化物溶液中的氯离子迁移到阳极， 发生氧化反应， 生成氯气。
本发明采用添加纳米级无机物与等离子体辐照接枝聚合技术制备一种阴离子阻挡率高、 交换容量大、 机械强度好的阳离子选择性隔膜。
选用纳米级二氧化锰加入到基膜材料中， 可使其离子交换容量增加， 这是由于静电引力 作用， 使基膜表面相对离子浓度增加， 表现为基膜表面固定电荷密度增加， 相应的， 离子迁 移数也会增加， 同时还可提高基膜的导电性与机械性能， 增加基膜亲水性。
利用等离子体对基膜表面活化及接枝聚合有机单体， 采用电晕放电方式的好处有： 电晕 放电穿透力不强， 穿透厚度浅， 不会造成基膜机械损伤， 不影响基膜本体性能， 只需作用于 基膜表面， 简单易行， 处理速度快。 电晕放电过程中会产生的高能粒子， 高能粒子的能量巨 大， 一般约为几个到几十个电子伏特， 如电子的能量为 0〜20eV、 亚稳态粒子为 0~20eV、 紫 外光 /可见光为 3~40eV。而聚合物中常见化学键的键能为： C-H为 4.3eV、 C-N为 2.9eV、 C-F 为 4.4eV、 C = 0为 8.0eV、 C一 C为 3. 4eV、 C = C为 6.1eV。 由此可知， 电晕放电产生的绝 大部分粒子能量都高于聚合物的化学键能。 这些高能粒子在高压电场作用下被加速直接撞击 基膜表面， 使基膜高分子有机物的 C-H、 C = C、 C = 0等化合键断裂或打开， 同时接受高能 粒子部分能量， 成为激发态分子而具有活性， 激发态分子不稳定， 分解成为自 ώ基或离子， 可与有机单体发生聚合反应， 沉积在膜表面形成具有可设计性的涂层。 采用等离子体辐射基 膜， 可使基膜材料表面活化， 更利于与酚基的有机单体接触， 使较难接枝的强亲水性酚基基 团顺利接枝聚合到疏水性的聚偏氟乙烯和苯乙烯基膜上， 即通过聚合反应将 2-烯丙基酚、 4- 乙烯基苯酚接枝到聚偏氟乙烯和苯乙烯基膜一侧， 可增加基膜的亲水性， 同时该基膜这一侧 可电离出氢离子， 具有弱酸性， 基膜表面带一层负电荷， 可形成负电场， 加上基膜本身含有 固定基团-磺酸基阳离子交换膜，基于阳离子选择性隔膜的双电层理论与同性离子相斥，会极 大提高阴离子阻挡率， 尤其可阻止带负电荷的离子透过。 表 1 不同阳离子选择性隔膜性能参数
Figure imgf000007_0001
膜 A-本发明的阳离子选择性隔膜，膜 B-二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜， 膜 C-全氟磺酸膜。
由表 1可知， 膜 A各项性能参数均优于膜 B和膜 C。尤其是阴离子不透过率， 氯离子阻 挡率可达到 99.9%， 这主要归因于膜 A表面一侧带一层负电荷， 形成负电场， 阻止氯离子透 过； 膜 A的离子交换容量与含水率好于膜 B和膜 C的， 这是由于添加纳米级二氧化锰， 使 膜 A内亲水基团增加， 从而使膜 A的含水率提高， 同时提高膜 A中磺酸基团密度， 使可交 换反离子数量增加， 提高离子交换容量。
离子交换容量与含水率的测定方法： 离子交换容量是指离子交换膜内活性基团浓度的大 小和它与反离子交换能力高低的一项化学性能指标， 以每克干膜所含活性基团的毫克当量数 表示（mmol/g)。 将阳离子选择性隔膜浸泡 lmol/L HCl溶液中， 将其转化为 H型； 用去离子 水充分冲洗膜， 排出膜内的 HC1， 直至中性； 滤纸将膜表面水分吸干， 称出膜湿重 Gwet， 再 将其浸泡在 2mol/L NaCl溶液， 浸泡 6小时； 然后用去离子水充分洗涤膜， 并收集浸液和洗 涤水， 最后用 0.1mol/L NaOH滴定收集液中的 H+， 记录 NaOH用量 V； 用滤纸擦干膜， 在 65°C的恒温箱中干燥至恒重 Gdry。
离子交换容量的计算公式： AH+= a/ G^， a=0.1 *V。
含水率的计算公式： W= (Gwer Gdry) / Gdry* 100。
AH+-离子交换容量 （mmol/g干膜）， a-收集液中 H+含量 （mol )， V— NaOH用量 （L)， W-含水率 （％), Gwet-湿重 （g)， Gdry -干重 （g)。
膜电位的测定方法：
将待测膜夹于盛有不同浓度的同一种类电解质溶液（如 KC1溶液）的两个隔室之间， 使 用饱和甘汞电极作为参考电极， 在电解质溶液与甘汞电极之间用盐桥连接， 构成一种复杂的 原电池， 用 DT-830数字万用表测定该原电池电位 E «， Eo为不同浓度的同一种类电解质溶液 的理论电位差。 膜电位计算公式： E ^=E sr E0.
本发明将常规电解工艺中的电解槽改造为膜电解工艺及一体化电解槽结构。采用两张选 择性隔膜将电解槽分隔为三个隔室， 形成阳极室， 阴极室和中隔室， 在不同的隔室内注入不 同的电解液或接收液。 阴极室仍注入现有的含氯化物电解液， 不改变其成分、 配比浓度及循 环方式， 可保证正常的氯化精炼电积金属的质量。 而阳极室注入不含氯的 H2S04稀电解液。 中隔室内注入 HC1稀接收液， 以收集阴极室迁移的氯离子和阳极室中迁移的氢离子。 即可维 持正常的电解过程又可防止氯气的产生， 从而彻底解决常规金属氯化物电积过程氯气产生的 问题， 避免环境污染； 并可将氯离子转化为高浓度盐酸回收再利用， 经济价值高； 所得金属 产品质量好， 是符合绿色冶金环保发展方向的一项新方法。 附图说明
图 1 是一种新型膜法金属氯化物电积精炼生产方法示意图；
图 2 是一种新型膜法金属氯化物电积精炼生产方法电化学反应示意图；
其中， 1-阳离子选择性隔膜， 2-阴离子选择性隔膜， 3-阳极室， 4-中隔室， 5-阴极室 , 6- 阳极， 7-阴极， 8-阳极液， 9-阴极液， 10-电解槽。 具体实施方式
一种新型膜法金属氯化物电积精炼生产方法， 利用阳离子选择性隔膜和阴离子选择性隔 膜将电解槽依次分隔为阳极室、 中隔室、 阴极室， 阳极与阴极、 阳极液与阴极液分别对应置 于阳极室和阴极室中， 阳极液为稀硫酸溶液， 阴极液为酸性金属氯化物溶液， 中隔室盛有稀 盐酸溶液， 通入直流电电解时， 金属阳离子在阴极还原并以单质形态析出， 同时， 阳极发生 水氧化反应， 得到氧气， 中隔室可得到 5%~10%盐酸溶液。
所述的阳极为铅系合金或钛基半导体塗层电极。
所述的阳极电流密度为 100A/m2~500 A/m2
所述的酸性金属氯化物溶液可以是 NiCl2、 CuCl2、 CoCl2、 ZnCl2溶液， pH=2~5。
所述的阴极为与阴极液中金属阳离子所对应的镍板、 铜板、 钴板、 锌板。 所述的中隔室中的稀盐酸溶液浓度为 0.5%〜1%。
电解时电解液温度控制在 0 ：〜 70Ό。
电解方式可采用单电解槽电积或多电解槽串联电积。
实施例 1
以含镍废渣作为电积原料液， 经酸溶浸出、 离子交换富集得到高浓度 Ν ¾溶液， NiCl2 溶液浓度为 40g/L， pH=4.5。 电解方式为单电解槽电积， 阳极 6选用惰性电极钛塗钌网， 阴 极 7选用纯金属镍板；阳离子选择性隔膜 1选用 Nafionl 17，阴离子选择性隔膜 2选用 JAM- II 型均相阴离子交换膜； 阳极液 8选用 0.5%稀硫酸水溶液； 阴极液 9选用 40g/L NiCl2溶液， 中隔室 4盛有 0.5%稀盐酸水溶液； 通入直流电电解， 阳极电流密度为 100A/m2， 金属镍离子 在阴极 7还原并以单质形态析出，经检测其纯度为 99.8%; 同时中隔室 4可得到浓度 7°/。盐酸 水溶液， 阳极液 8中氯离子浓度几乎接近零。
实施例 2
以固体氯化钴配制电解液， 经净化除浊后作为电积原料液， CoCl2电解液浓度为 50g/L， pH=3.0。 电解方式为多电解槽串联电积， 阳极 6选用铅银合金板， 阴极 7选用纯金属镍板； 阳离子选择性隔膜 1选用 Nafion234，阴离子选择性隔膜 2选用 JAM- II型均相阴离子交换膜； 阳极液 8选用 0.8%稀硫酸水溶液； 阴极液 9选用 50g/L CoCl2溶液， 中隔室 4盛有 0.5%稀盐 酸水溶液； 通入直流电电解， 阳极电流密度为 200A/m2， 金属钴离子在阴极 7还原并以单质 形态析出， 经检测其纯度为 99.8%; 同时中隔室 4可得到浓度 8%盐酸水溶液， 阳极液 8中氯 离子浓度几乎接近零。
实施例 3
以含镍废渣作为电积原料液， 经酸溶浸出、 离子交换富集得到高浓度 NiCl2溶液， NiCl2 溶液浓度为 40g/L, pH=4.5。 电解方式为单电解槽电积， 阳极 6选用惰性电极钛塗钌网， 阴 极 7选用纯金属镍板； 阳离子选择性隔膜 1选用本发明阳离子选择性膜， 阴离子选择性隔膜 2选用 JAM- II型均相阴离子交换膜，将阳离子选择性隔膜 1带酚基基团的一侧为中隔室， 与 稀盐酸溶液接触， 不带酚基基团的另一侧为阳极室， 与稀硫酸溶液接触； 阳极液 8选用 0.5% 稀硫酸水溶液； 阴极液 9选用 40g/L NiCl2溶液， 中隔室 4盛有 0.6%稀盐酸水溶液； 通入直 流电电解， 阳极电流密度为 100A/m2， 金属镍离子在阴极 7还原并以单质形态析出， 经检测 其纯度为 99.9%; 同时中隔室 4可得到浓度 7%盐酸水溶液， 阳极液 8中氯离子浓度为零。 阳 离子选择性隔膜 1选用本发明阳离子选择性膜，能够完全阻止中隔室 4中的 CI—在直流电场牵 引力作用下向阳极迁移， 而被固定于中隔室 4， 从而彻底解决常规金属氯化物电积过程氯气 产生的问题， 避免环境污染。而阳极液 8中 H+受到直流电场力牵引， 迁出阳极室 3穿过阳离 子选择性隔膜进入中隔室 4， 从而与中隔室 4中的 C1—形成 HC1， 该 HC1可回收再利用。 本发 明阳离子交换膜的离子交换容量高， 亲水性好， 选择性膜选择透过性好， 尤其对氯离子来说， 具有很高的阻挡率， 使用寿命长。
实施例 4
以固体氯化钴配制电解液， 经净化除浊后作为电积原料液， CoCl2电解液浓度为 50g/L， pH-3.0o 电解方式为多电解槽串联电积， 阳极 6选用铅银合金板， 阴极 7选用纯金属镍板； 阳离子选择性隔膜 1选用本发明阳离子选择性膜， 阴离子选择性隔膜 2选用 JAM- II型均相 阴离子交换膜， 将阳离子选择性隔膜 1带酚基基团的一侧为中隔室， 与稀盐酸溶液接触， 不 带酚基基团的另一侧为阳极室， 与稀硫酸溶液接触； 阳极液 8选用 0.8%稀硫酸水溶液： 阴极 液 9选用 50g/L CoCl2溶液， 中隔室 4盛有 0.5%稀盐酸水溶液； 通入直流电电解， 阳极电流 密度为 500A/m2， 金属钴离子在阴极 7还原并以单质形态析出， 经检测其纯度为 99.9%; 同 时中隔室 4可得到浓度 10%盐酸水溶液， 阳极液 8经检测氯离子浓度为零。 阳离子选择性隔 膜 1选用本发明阳离子选择性膜，能够完全阻止中隔室 4中的 C1—在直流电场牵引力作用下向 阳极迁移， 而被固定于中隔室 4， 从而彻底解决常规金属氯化物电积过程氯气产生的问题， 避免环境污染。而阳极液 8中 H+受到直流电场力牵引， 迁出阳极室 3穿过阳离子选择性隔膜 进入中隔室 4， 从而与中隔室 4中的 CI—形成 HC1， 该 HC1可回收再利用。 本发明阳离子交换 膜的离子交换容量高， 亲水性好， 选择性膜选择透过性好， 尤其对氯离子来说， 具有很高的 阻挡率， 使用寿命长。
实施例 5
一种阳离子选择性隔膜的制备方法， 包括如下两大步骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸缩水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均匀混合后加入引发剂， 将上述溶液在超声下均匀混合， 静置 1~2天， 待脱泡熟化后制成铸膜液， 其中，
该步骤中所涉及的各物质按重量份计：聚偏氟乙烯 8份，苯乙烯 2份，二氧化锰 0.1份， 高 压聚乙烯 0.9份,丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯 2.5份,含有活性基团有机溶剂 85 份， 引发剂 1.5份， 所述含有活性基团有机溶剂是重量比为 8 : 1的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基甲 酰胺的混合溶液，
所述引发剂为重量比为 8 : 2的过氧化十二酰与二叔丁基过氧化物的混合物；
b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 120°C~150°C 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体福照基膜接枝酚基基团
a.将步骤一所得基膜置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和 亲水性， 具体采用常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV〜12kV， 工作气 体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体；
b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30min~200min进行聚合接枝，其中， 含有酚基的单体为 2-烯丙基酚、 4-乙烯基苯酚的按重量比为 3:2 的混合物， 所占溶液 A 的质量百分数为 15%，
交联剂为二乙烯基苯， 所占溶液 A的质量百分数为 0.8%;
c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自由基接枝共聚反应， 采用 常压脉冲电晕放电辐照时间 20s~100s, 其中， 电压为 8kV~12kV， 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24小时， 除去未反应的 单体即可。
实施例 6
一种阳离子选择性隔膜的制备方法， 包括如下两大步骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸缩水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均匀混合后加入引发剂， 将上述溶液在超声下均勾混合， 静置 1~2天， 待脱泡熟化后制成铸膜液， 其中，
该步骤中所涉及的各物质按重量份计： 聚偏氟乙烯 5份、 苯乙烯 1.2份、 二氧化锰 0.05 份、 高压聚乙烯 0.6份、 丙烯酸縮水甘油酯或甲基丙烯酸缩水甘油酯 3份、 含有活性基团有 机溶剂 82份、 引发剂 0.5份，
所述含有活性基团有机溶剂是重量比为 9: 1的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基乙 酰胺的混合溶液， 所述引发剂为重量比为 8 : 2的过氧化十二酰与二叔丁基过氧化物的混合物； b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 12(TC~150°C 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体辐照基膜接枝酚基基团
a.将步骤一所得基膜置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和 亲水性， 具体采用常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气 体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体；
b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30min~200min进行聚合接枝，其中， 含有酚基的单体为 2-烯丙基酚， 所占溶液 A的质量百分数为 5%，
交联剂为二异氰酸酯， 所占溶液 A的质量百分数为 0.5%;
c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自由基接枝共聚反应， 采用 常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24小时， 除去未反应的 单体即可。 实施例 7
一种阳离子选择性隔膜的制备方法， 包括如下两大步骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸縮水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均匀混合后加入引发剂， 将上述溶液在超声下均匀混合， 静置 1~2天， 待脱泡熟化后制成铸膜液， 其中，
该步骤中所涉及的各物质按重量份计：聚偏氟乙烯 10份、苯乙烯 2份、二氧化锰 0.5份、 高压聚乙烯 1.3份、 丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯 2份、 含有活性基团有机溶 剂 90份、 引发剂 2份，
所述含有活性基团有机溶剂是重量比为 4: 1的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基乙 酰胺的混合溶液，
所述引发剂为重量比为 8 : 2的过氧化十二酰与二叔丁基过氧化物的混合物；
b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 12(TC~15(TC 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体辐照基膜接枝酚基基团
a.将步骤一所得基膜置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和 亲水性， 具体采用常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气 体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体；
b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30min~200min进行聚合接枝，其中， 含有酚基的单体为 4-乙烯基苯酚， 所占溶液 A的质量百分数为 20%,
交联剂为二异氰酸酯， 所占溶液 A的质量百分数为 1%;
c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自由基接枝共聚反应， 采用 常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV〜12kV， 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24 小时， 除去未反应的 单体即可。
实施例 8
一种阳离子选择性隔膜的制备方法， 包括如下两大步骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸缩水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均匀混合后加入引发剂， 将上述溶液在超声下均匀混合， 静置 1~2天， 待脱泡熟化后制成铸膜液， 其中，
该步骤中所涉及的各物质按重量份计： 聚偏氟乙烯 6份、 苯乙烯 1.5份、 二氧化锰 0.08 份、 高压聚乙烯 1份、 丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯 2.5份、 含有活性基团有 机溶剂 84份、 引发剂 0.9份，
所述含有活性基团有机溶剂是重量比为 9: 1的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基乙 酰胺的混合溶液，
所述引发剂为重量比为 8: 2的过氧化十二酰与二叔丁基过氧化物的混合物；
b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 120°C~150°C 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体辐照基膜接枝酚基基团
a.将步骤一所得基膜置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和 亲水性， 具体采用常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气 体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体；
b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30min~200min进行聚合接枝，其中， 含有酚基的单体为 2-烯丙基酚， 所占溶液 A的质量百分数为 12%，
交联剂为二异氰酸酯， 所占溶液 A的质量百分数为 0.7%;
c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自 ώ基接枝共聚反应， 采用 常压脉冲电暈放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24小时， 除去未反应的 单体即可。 实施例 9
一种阳离子选择性隔膜的制备方法， 包括如下两大步骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸缩水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均勾混合后加入引发剂， 将上述溶液在超声下均匀混合， 静置 1~2天， 待脱泡熟化后制成铸膜液， 其中，
该步骤中所涉及的各物质按重量份计： 聚偏氟乙烯 9份、 苯乙烯 1.8份、 二氧化锰 0.2 份、 高压聚乙烯 1.2份、 丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯 2.5份、 含有活性基团 有机溶剂 88份、 引发剂 1.5份，
所述含有活性基团有机溶剂是重量比为 9: 1的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基甲 酰胺的混合溶液，
所述引发剂为重量比为 8 : 2的过氧化十二酰与二叔丁基过氧化物的混合物；
b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 120°C〜150°C 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体辐照基膜接枝酚基基团
a.将步骤一所得基膜置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和 亲水性， 具体采用常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV〜12kV， 工作气 体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体； b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30min~200min进行聚合接枝，其中， 含有酚基的单体为 4-乙烯基苯酚， 所占溶液 A的质量百分数为 18%，
交联剂为二异氰酸酯， 所占溶液 A的质量百分数为 0.9%;
c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自由基接枝共聚反应， 采用 常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24 小时， 除去未反应的 单体即可。 实施例 10
一种阳离子选择性隔膜的制备方法， 包括如下两大步骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸缩水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均匀混合后加入引发剂， 将上述溶液在超声下均匀混合， 静置 1~2天， 待脱泡熟化后制成铸膜液， 其中，
该步骤中所涉及的各物质按重量份计： 聚偏氟乙烯 10份、 苯乙烯 1.9份、 二氧化锰 0.3 份、 高压聚乙烯 1份、 丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯 2.5份、 含有活性基团有 机溶剂 90份、 引发剂 1.8份，
所述含有活性基团有机溶剂重量比为 4: 1的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基乙酰 胺的混合溶液，
所述引发剂为重量比为 8: 2的过氧化十二酰与二叔丁基过氧化物的混合物；
b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 120°C~150°C 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体辐照基膜接枝酚基基团
a.将步骤一所得基膜置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和 亲水性， 具体采用常压脉冲电晕放电辐照时间 20s〜100s, 其中， 电压为 8kV〜12kV， 工作气 体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体；
b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30mir！〜 200min进行聚合接枝，其中， 含有酚基的单体为 4-乙烯基苯酚， 所占溶液 A的质量百分数为 12%，
交联剂为二乙烯基苯， 所占溶液 A的质量百分数为 0.6%;
c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自由基接枝共聚反应， 采用 常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV〜12kV, 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24 小时， 除去未反应的 单体即可。
以上所述仅为本发明的优选实施例而已， 并不用于限制本发明， 尽管参照前述实施例对 本发明进行了详细的说明， 对于本领域的技术人员来说， 其依然可以对前述各实施例所记载 的技术方案进行修改， 或者对其中部分技术特征进行等同替换。 凡在本发明的精神和原则之 内， 所作的任何修改、 等同替换、 改进等， 均应包含在本发明的保护范围之内。

Claims

权利要求书
1. 一种新型膜法金属氯化物电积精炼生产方法，利用阳离子选择性隔膜和阴离子选择性 隔膜将电解槽依次分隔为阳极室、 中隔室、 阴极室， 阳极与阴极、 阳极液与阴极液分别对应 置于阳极室和阴极室中， 阳极液为稀硫酸溶液， 阴极液为酸性金属氯化物溶液， 中隔室盛有 稀盐酸溶液， 通入直流电电解时， 金属阳离子在阴极还原并以单质形态析出， 同时， 阳极发 生水氧化反应， 得到氧气， 中隔室可得到 5%〜10%盐酸溶液。
2. 根据权利要求 1所述的一种新型膜法金属氯化物电积精炼生产方法， 其特征在于： 所 述的阳极为铅系合金或钛基半导体塗层电极。
3. 根据权利要求 1所述的一种新型膜法金属氯化物电积精炼生产方法， 其特征在于： 所 述的阳极电流密度为 100A/m2〜500 A/m2
4. 根据权利要求 1所述的一种新型膜法金属氯化物电积精炼生产方法， 其特征在于： 所 述的酸性金属氯化物溶液可以是 NiCl2、 CuCl2、 CoCl2、 ZnCl2溶液， pH=2〜5。
5. 根据权利要求 1所述的一种新型膜法金属氯化物电积精炼生产方法， 其特征在于： 所 述的阴极为与阴极液中金属阳离子所对应的镍板、 铜板、 钴板、 锌板。
6. 根据权利要求 1所述的一种新型膜法金属氯化物电积精炼生产方法， 其特征在于： 所 述的中隔室中的稀盐酸溶液浓度为 0.5%~1%。
7. 一种阳离子选择性隔膜的制备方法， 其特征在于： 包括如下两大歩骤，
步骤一、 二氧化锰 /聚偏氟乙烯共混制备含磺酸基团基膜
a.将聚偏氟乙烯和苯乙烯加入装有含有活性基团有机溶剂的超声振荡器中， 边振荡边加 入纳米级二氧化锰， 当二氧化锰充分溶解后， 再加入高压聚乙烯和丙烯酸缩水甘油酯或甲基 丙烯酸缩水甘油酯的混合物， 均匀混合后加入引发剂， 将上述溶液在超声下均匀混合， 静置 1〜2天， 待脱泡熟化后制成铸膜液， 其中，
该步骤中所涉及的各物质按重量份计： 聚偏氟乙烯 5~10份、苯乙烯 1.2~2份、 二氧化锰 0.05〜0.5份、 高压聚乙烯 0.6~1.3份、 丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯 2~3份、含 有活性基团有机溶剂 82〜90份、 引发剂 0.5~2份；
b.在常温下， 将上述铸膜液在玻璃板上流延成膜， 将其置于恒温箱中， 在 120°C〜150°C 条件下， 加热固化 8小时之后， 室温冷却制成基膜；
步骤二、 等离子体辐照基膜接枝酚基基团
a.将步骤一所得基膜一侧进行绝缘处理后， 置于等离子体反应器中， 进行表面活化处理， 增加基膜的表面能和亲水性， 具体采用常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV, 工作气体为纯氩气、 纯氮气、 纯氦气中任意一种或两种以上混合气体； b.将含有酚基的单体和交联剂混合于二甲基甲酰胺或二甲基乙酰胺中配制形成浓度均匀 的溶液 A， 再将活化处理过的基膜浸泡于上述溶液 A中 30mir！〜 200min进行聚合接枝；
c.将上述聚合接枝的基膜再一次置于等离子体反应器中进行自由基接枝共聚反应， 采用 常压脉冲电晕放电辐照时间 20s~100s， 其中， 电压为 8kV~12kV， 工作气体为纯氩气、 纯氮 气、 纯氦气中任意一种或两种以上混合气体， 之后用去离子水浸泡 24 小时， 除去未反应的 单体即可。
8、 根据权利要求 7所述的阳离子选择性隔膜的制备方法， 其特征在于： 所述步骤一的 步骤 a中，
所述含有活性基团有机溶剂为重量比为 8~9: 1-2的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲 基甲酰胺的混合溶液， 或重量比为 8〜9: 1~2的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基乙酰胺 的混合溶液， 或重量比为 8〜9: 1〜2 的烯丙基磺酸钠和二甲基甲酰胺的混合溶液， 优选重量 比为 8: 1的 2-丙烯酰胺基 -2-甲基丙磺酸和二甲基甲酰胺的混合溶液；
所述引发剂为重量比为 8: 2的过氧化十二酰与二叔丁基过氧化物的混合物； 各物质按重量份计： 聚偏氟乙烯 8份、 苯乙烯 2份、 二氧化锰 0.1份、 高压聚乙烯 0.9 份、 丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯 2.5份、 含有活性基团有机溶剂 85份、 引发 剂 1.5份。
9、 根据权利要求 7所述的阳离子选择性隔膜的制备方法， 其特征在于： 所述步骤二的 步骤 b中，
所述含有酚基的单体为 2-烯丙基酚、 4-乙烯基苯酚的一种或两种混合物， 所占溶液 A的 质量百分数为 5%~20%， 优选 2-烯丙基酚， 占溶液 A的质量百分数最佳为 15%。
所述交联剂为二乙烯基苯或二异氰酸酯， 所占溶液 A的质量百分数为 0.5%〜1%， 最佳 为 0.8%。
10、 根据权利要求 1所述的一种新型膜法金属氯化物电积精炼生产方法， 其特征在于： 所述的阳离子选择性隔膜选用权利要求 7至 9任一项所述的阳离子选择性隔膜， 其带酚基基 团的一侧为中隔室， 与稀盐酸溶液接触， 不带酚基基团的另一侧为阳极室， 与稀硫酸溶液接 触。
PCT/CN2013/000292 2012-09-26 2013-03-15 一种膜法金属氯化物电积精炼生产方法及该法中所采用的阳离子选择性隔膜的制备方法 WO2014048050A1 (zh)

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