CN114908364B - Method for continuously preparing copper sulfate crystals by ionic membrane electrolysis method - Google Patents
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- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 63
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 63
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 239000013078 crystal Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 118
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 24
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract 2
- 238000003860 storage Methods 0.000 claims description 47
- 150000002500 ions Chemical class 0.000 claims description 24
- 239000012452 mother liquor Substances 0.000 claims description 23
- 239000013589 supplement Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 85
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000010413 mother solution Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000002198 insoluble material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- -1 hydrogen ions Chemical class 0.000 abstract description 2
- 239000003011 anion exchange membrane Substances 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- VONLASUMRVUZLY-UHFFFAOYSA-N [Ir].[Ti].[Ta] Chemical compound [Ir].[Ti].[Ta] VONLASUMRVUZLY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- 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
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- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a preparation method of copper sulfate crystals, in particular to a method for continuously preparing copper sulfate crystals by an ionic membrane electrolysis method. The method uses an ionic membrane to divide an electrolytic tank into an anode chamber and a cathode chamber, and sulfuric acid solution is introduced into the electrolytic tank, wherein a copper sheet is used as an anode, and insoluble materials are used as a cathode. At a temperature of 20-85 ℃ and a speed of 50A/m 2 ~8000A/m 2 The electrolysis is carried out according to the current density of the anode chamber, hydrogen ions in the cathode chamber are reduced into hydrogen gas for recovery, copper anodes are oxidized to generate copper ions for dissolution, copper sulfate solution is obtained in the anode chamber, and the tank voltage is 0.30V-2.00V. Filtering and impurity removing the copper sulfate solution, cooling to the temperature of minus 20-30 ℃ to separate out copper sulfate crystals, heating the filtered mother solution by a heat exchange device, and returning the mother solution to an anode chamber circulation tank to realize continuous electrolysis of the solution without waste liquid. The method solves the problems of complex process, higher cost, longer time consumption and the like of the existing high-purity copper sulfate preparation method, has simple process and can realize continuous production and large-scale industrial application.
Description
Technical Field
The invention relates to a preparation method of copper sulfate crystals, in particular to a method for continuously preparing copper sulfate crystals by an ionic membrane electrolysis method.
Background
In recent years, the rapid development of the lithium battery industry drives the high-speed growth of electrolytic copper foil, and electrolyte used for producing the lithium electric copper foil is copper sulfate aqueous solution, which can be prepared by directly dissolving copper sulfate crystals in water, or can be prepared by dissolving high-purity cathode copper or standard cathode copper in sulfuric acid medium after air is introduced for oxidation. The purity of the copper sulfate for electroplating of HG/T3592-2010, which is carried out according to the product quality standard in the market, is more than 98 percent by mass, and the requirement on the purity in the production process of the electrolytic copper foil cannot be met. Therefore, the latter method is generally adopted in the actual production of electrolytic copper foil, but this method has problems of slow copper dissolution rate, acid mist pollution, low efficiency, and the like.
At present, the copper sulfate in the market is mostly derived from the purification of crude copper sulfate, and the crude copper sulfate produced by taking copper ore as a raw material contains more impurities and needs to be further purified to prepare a copper sulfate product meeting the quality standard. The purification process adopts extraction method, ion exchange method and the like, and has the advantages of complex process, high cost and long time consumption. Therefore, the development of a low-cost large-scale high-purity copper sulfate crystal preparation method has very important significance, not only can reform the traditional electrolytic copper foil copper dissolving and liquid making process, but also can meet the requirements of other fields on high-purity copper sulfate.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a method for continuously preparing copper sulfate crystals by an ionic membrane electrolysis method. The invention has simple process and can be continuously and massively produced.
The invention relates to a method for continuously preparing copper sulfate crystals by an ionic membrane electrolysis method, which uses an ionic membrane to divide an electrolytic tank into an anode chamber and a cathode chamber, and sulfuric acid solution is introduced into the electrolytic tank, a copper sheet is used as an anode, and an insoluble electrode material is used as a cathode. After direct current is connected, hydrogen ions in the cathode chamber are reduced into hydrogen gas for recovery; the copper anode is oxidized to generate copper ions to be dissolved, the dissolved copper ions are blocked by the ionic membrane from entering the cathode chamber from the anode chamber, the copper ions are prevented from being separated out on the cathode again, and the copper sulfate solution is obtained in the anode chamber. The copper sulfate solution is filtered, mixed and cooled, copper sulfate crystals are separated out, and the filtered mother liquor is heated by a heat exchange device and then returned to the anode chamber circulation tank, so that the solution is continuously utilized, and no waste liquid is generated. The electrode reaction formula is as follows:
anode: （1）
and (3) cathode: （2）
the technical scheme of the invention comprises the following operation steps:
step (1), dilute sulfuric acid in a sulfuric acid storage tank is heated to a certain temperature through a heat exchanger, a cathode chamber and an anode chamber of an ion membrane electrolytic tank are respectively introduced through a cathode chamber circulation tank and an anode chamber circulation tank, then electrolyte circulation among the cathode chamber, the anode chamber and the cathode chamber circulation tank is respectively started, direct current is conducted, electrolysis is conducted under certain sulfuric acid concentration, temperature and current density, copper sulfate solution is obtained in the anode chamber, and hydrogen generated in the cathode chamber is recovered through a gas collecting device;
step (2), filtering and impurity removing after copper ions of the solution in the anode chamber circulation tank reach a certain concentration, and then introducing the solution into a copper-dissolving solution storage tank;
step (3), directly cooling and crystallizing the solution obtained in the step (2), and filtering to obtain a prepared copper sulfate crystal;
step (4), heating the mother liquor filtered in the step (3) by a heat exchanger and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
In the step (1), an ion membrane used in the ion membrane electrolyzer divides the electrolyzer into an anode chamber and a cathode chamber, and further, the adopted ion membrane is one of strong acid resistant arbitrary commercial ion membranes which do not allow copper ions to pass through;
in the step (1), copper is used as an anode, and further high-purity copper is used;
in the step (1), the insoluble material is a cathode, and further is any one or a mixture of coating cathode materials such as copper, titanium, stainless steel, platinum, noble metal and the like;
in the step (1), the concentration of sulfuric acid is 30 g/L-500 g/L, the conductivity of the solution is reduced due to the excessively low concentration, and the solubility of copper sulfate is reduced due to the excessively high concentration;
in the step (1), the electrolysis temperature is 20-85 ℃, the conductivity of the electrolyte is not good, the acid mist is easily evaporated at the excessively high temperature, the raw materials are wasted, the energy consumption is increased, and the ionic membrane is easily damaged;
in the step (1), the current density is 50A/m 2 ~8000A/m 2 Too low a current density slows down the dissolution rate of copper, too high a current density increases the cell voltage, increasing energy consumption;
in the step (1), the tank voltage is 0.30-2.00V;
in the step (2), the concentration of copper ions is as follows: the concentration of copper ions is not favorable for cooling crystallization precipitation, and the concentration of copper ions is too low, namely 12g/L to 180g/L, so that the tank voltage is increased, and the energy consumption is increased.
In the step (3), the cooling temperature is-20-30 ℃, preferably 20-30 ℃, the low temperature is favorable for more precipitation of copper sulfate, but the excessively low cooling temperature increases the energy required for heating when the mother solution returns to the electrolyte;
in the step (4), the temperature of the heating solution of the heat exchanger is 20-85 ℃.
The invention has the beneficial effects that:
(1) Impurity ions are not introduced in the preparation process, and the purity and quality of the product are not affected.
(2) The hydrogen which is an electrolysis byproduct is green energy, can be recycled, and realizes the high-efficiency utilization of resources; the filtered mother liquor can be returned to electrolysis, no waste liquid is generated, and the method is environment-friendly.
(3) The invention has simple process and low cost, is easy to assemble each unit electrolytic tank, and can realize continuous production and large-scale industrial application.
Drawings
FIG. 1 is an ionic membrane electrolysis apparatus of the present invention;
FIG. 2 is a schematic structural view of an ionic membrane electrolyzer;
FIG. 3 is an XRD pattern of the prepared copper sulfate pentahydrate crystals;
in the figure: 1-electrolytic tank, 2-cathode chamber, 3-anode chamber, 4-ion membrane, 5-sulfuric acid storage tank, 6-heat exchanger, 7-cathode chamber circulation tank, 8-anode chamber circulation tank, 9-circulation pump, 10-filter device, 11-copper solution storage tank and 12-crystallization device.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
A device for continuously preparing copper sulfate crystals by an ionic membrane electrolysis method comprises an electrolytic tank 1, an anion circulation tank 7, a cation circulation tank 8, a sulfuric acid storage tank 5, a filtering device 10, a copper solution storage tank 11, a crystallization device 12, a heat exchanger 6, a circulation pump 9 and a connecting pipeline.
An electrolytic tank 1, a connecting pipeline, an ion membrane 4 is used for dividing the electrolytic tank 1 into a cathode chamber and an anode chamber, and an insoluble material cathode and a copper anode are respectively arranged in the cathode chamber 2 and the anode chamber 3;
diluting high-purity concentrated sulfuric acid with deionized water to prepare a dilute sulfuric acid solution, and storing the dilute sulfuric acid solution in a sulfuric acid storage tank 5; the sulfuric acid solution in the sulfuric acid storage tank 5 is heated to a certain electrolysis temperature through the heat exchanger 6, and is respectively introduced into the cathode chamber 2 and the anode chamber 3 of the electrolytic tank 1 through the cathode circulation tank 7 and the anode chamber circulation tank 8 through pipelines; simultaneously, a circulating pump 9 connected between the cathode chamber 2 and the anode chamber 3 and between the cathode circulating tank 7 and the anode chamber circulating tank 8 is respectively started to circulate the solution; under certain current density, temperature and sulfuric acid concentration, direct current electrolysis is carried out on the electrolyte, copper anode in the anode chamber 3 is dissolved, and hydrogen generated in the cathode chamber 2 is recovered by a recovery device; after the concentration of copper ions in the solution in the anode chamber circulation tank 8 reaches the target concentration, the solution flows into a copper-dissolving solution storage tank 11 at a certain flow rate after filtered and filtered by a filtering device 10 to remove impurities; the solution in the copper-dissolving solution storage tank 11 is directly cooled and crystallized by the crystallization device 12, and is filtered by the filtering device 10, the prepared copper sulfate crystal is obtained from the solid phase, and the liquid phase is the mother solution with low concentration. The mother liquor is heated to a certain temperature by the heat exchanger 6 and then returns to the anode chamber circulation tank 8, and meanwhile, the sulfuric acid in the sulfuric acid storage tank 5 supplements the anode chamber circulation tank 8 with liquid at a certain flow rate, so that the volume and concentration of the solution in the anode chamber circulation tank 8 are kept stable.
Example 1 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: introducing 200g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, using Cu-CATH-2 cathode copper as a cathode, having a pole spacing of 25mm, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling current density to be 500A/m 2 Electrolyzing at 55 deg.c, and recovering hydrogen produced in the cathode chamber with the gas collector to obtain electrolyzer with voltage of 0.90V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 90g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to 20 ℃, precipitating copper sulfate crystals, and filtering, wherein the mass of the copper sulfate crystals prepared by each liter of solution is 180g;
step 4: heating the mother liquor filtered in the step 3 to 55 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
Example 2 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: 200g/L dilute sulfuric acid in a sulfuric acid storage tankIntroducing into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, iridium tantalum titanium-based coating material as a cathode, enabling the electrode spacing to be 25mm, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling the current density to be 500A/m 2 Electrolyzing at the reaction temperature of 85 ℃, and recovering hydrogen generated by a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic tank is 0.79V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 140g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to 30 ℃, precipitating copper sulfate crystals, and filtering, wherein the mass of the copper sulfate crystals prepared by each liter of solution is 320g;
step 4: heating the mother liquor filtered in the step 3 to 85 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
Example 3 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: introducing 500g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, using Cu-CATH-2 cathode copper as a cathode, having a pole spacing of 25mm, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling current density to be 500A/m 2 Electrolyzing at 55 deg.c, and recovering hydrogen produced in the cathode chamber with the gas collector to obtain electrolyzer with voltage of 0.78V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 40g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to 10 ℃, precipitating copper sulfate crystals, and filtering, wherein the mass of the copper sulfate crystals prepared by each liter of solution is 130g;
step 4: heating the mother liquor filtered in the step 3 to 55 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
Example 4 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: introducing 500g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, using Cu-CATH-2 cathode copper as a cathode, having a pole spacing of 25mm, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling current density to 8000A/m 2 Electrolyzing at 55 deg.c, and recovering hydrogen produced in the cathode chamber with the gas collector to obtain electrolyzer with voltage of 1.28V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 40g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to 10 ℃, precipitating copper sulfate crystals, and filtering, wherein the mass of the copper sulfate crystals prepared by each liter of solution is 130g;
step 4: heating the mother liquor filtered in the step 3 to 55 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
Example 5 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: introducing 500g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, using Cu-CATH-2 cathode copper as a cathode, having a pole spacing of 25mm, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling current density to be 500A/m 2 Electrolyzing at 20 deg.c, and recovering hydrogen produced in the cathode chamber with the gas collector to obtain electrolyzer of 0.95V voltage;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 12g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to-20 ℃, precipitating copper sulfate crystals, and filtering, wherein the quality of the copper sulfate crystals prepared by each liter of solution is 40g;
step 4: heating the mother liquor filtered in the step 3 to 20 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
Example 6 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: introducing 30g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, using Cu-CATH-2 cathode copper as a cathode, having a pole spacing of 25mm, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling current density to be 50A/m 2 Electrolyzing at 55 deg.c, and recovering hydrogen produced in the cathode chamber with a gas collector to obtain electrolyzer with voltage of 2.00V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 120g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to 20 ℃, precipitating copper sulfate crystals, and filtering, wherein the quality of the copper sulfate crystals prepared by each liter of solution is 195g;
step 4: heating the mother liquor filtered in the step 3 to 55 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
Example 7 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: introducing 30g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, using a commercial platinum electrode as a cathode, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling the current density to be 50A/m 2 Electrolyzing at 85 deg.c, recovering hydrogen produced in the cathode chamber via the gas collector,the cell voltage is 1.15V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 180g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to 30 ℃, precipitating copper sulfate crystals, and filtering, wherein the quality of the copper sulfate crystals prepared by each liter of solution is 350g;
step 4: heating the mother liquor filtered in the step 3 to 85 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
Example 8 this example provides a process for continuously preparing copper sulfate crystals by ionic membrane electrolysis comprising the steps of:
step 1: introducing 400g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic tank, using Cu-CATH-2 cathode copper as an anode, using a commercial platinum electrode as a cathode, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling the current density to be 50A/m 2 Electrolyzing at 85 ℃ with the reaction temperature, and recovering hydrogen generated by a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic tank is 0.30V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 100g/L, filtering and impurity removing the solution, and then introducing the solution into a copper solution storage tank;
step 3: cooling the solution in the copper-dissolving solution storage tank to 30 ℃, precipitating copper sulfate crystals, and filtering, wherein the quality of the copper sulfate crystals prepared by each liter of solution is 220g;
step 4: heating the mother liquor filtered in the step 3 to 85 ℃ through a heat exchange device, and returning the mother liquor to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable.
The copper sulfate crystals prepared in examples 1 to 8 were analyzed by inductively coupled plasma mass spectrometry (ICP-MS), and the inspection results of metallic impurity elements of typical ultra-pure copper sulfate crystals are shown in table 1. As can be seen from Table 1, the contents of As, pb, sb and Zn are not detected, and the contents of Bi, fe, sn and Ni are 16ppm,4ppm,2ppm and 2ppm respectively, which shows that the purity of the copper sulfate crystal continuously prepared by the ionic membrane electrolytic method is very high, which is superior to the current national copper sulfate standard HG/T3592-2010 for electroplating, and is suitable for the requirement of the high-purity copper sulfate solution of the lithium copper foil.
TABLE 1
| Element(s) | As | Bi | Fe | Pb | Sb | Sn | Ni | Zn |
| Content (%) | Not detected | 0.0016 | 0.0004 | Not detected | Not detected | 0.0002 | 0.0002 | Not detected |
FIG. 3 shows XRD patterns of the prepared copper sulfate pentahydrate and standard card PDF#72-2355 patterns, and by comparison, main peaks basically correspond to each other one by one, and no impurity peak exists, so that the prepared product is high-purity copper sulfate pentahydrate. The X-ray diffraction peak in the graph is quite sharp, which indicates that the crystallinity of the copper sulfate after cooling crystallization is quite high.
The foregoing is merely illustrative of the embodiments of this invention and it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, which are also intended to be within the scope of the invention.
Claims (2)
1. The method for continuously preparing the copper sulfate crystal by the ionic membrane electrolysis method is characterized by comprising the following steps of:
heating dilute sulfuric acid in a sulfuric acid storage tank to a certain temperature through a heat exchanger, respectively introducing a cathode chamber and an anode chamber of an ion membrane electrolytic tank through a cathode chamber circulation tank and an anode chamber circulation tank, respectively starting electrolyte circulation among the cathode chamber, the anode chamber, the cathode chamber circulation tank and the anode chamber circulation tank, switching on direct current, electrolyzing the dilute sulfuric acid under a certain sulfuric acid concentration, a certain temperature and a certain current density, obtaining a copper sulfate solution in the anode chamber, and recovering hydrogen generated in the cathode chamber through a gas collecting device, wherein the sulfuric acid concentration is 30-500 g/L;
step (2), filtering and impurity removing after copper ions of the solution in the anode chamber circulation tank reach a certain concentration, and then introducing the solution into a copper-dissolving solution storage tank;
step (3), directly cooling and crystallizing the solution obtained in the step (2), and filtering to obtain a prepared copper sulfate crystal;
step (4), heating the mother liquor filtered in the step (3) by a heat exchanger and returning the mother liquor to the anode chamber circulation tank; meanwhile, sulfuric acid in the sulfuric acid storage tank supplements liquid for the anode chamber circulation tank at a certain flow rate, so that the volume and concentration of the anode chamber circulation tank solution are kept stable, the anode material in the anode chamber is high-purity copper, and the cathode in the cathode chamber is insoluble;
in the step (1), the electrolysis temperature is 20-85 ℃ and the current density is 50A/m 2 ~8000A/m 2 ；
The cooling temperature in the step (3) is-20-30 ℃, and the tank voltage in the step (1) is 0.30-2.00V;
the ionic membrane adopted in the ionic membrane electrolytic tank is a strong acid resistant commercial ionic membrane which does not allow copper ions to pass through;
the concentration of copper ions in the step (2) is 12 g/L-180 g/L.
2. The method of claim 1, wherein the temperature of the heat exchanger heating solution in step (4) is 20 ℃ to 85 ℃.
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