CN114908364A - Method for continuously preparing copper sulfate crystal by ion-exchange membrane electrolysis method - Google Patents
Method for continuously preparing copper sulfate crystal by ion-exchange membrane electrolysis method Download PDFInfo
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- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 62
- 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 62
- 239000013078 crystal Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 25
- 239000003014 ion exchange membrane Substances 0.000 title description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 120
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 40
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 150000002500 ions Chemical class 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
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 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
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000002198 insoluble material Substances 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 47
- 239000012452 mother liquor Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- -1 hydrogen ions Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 80
- 210000004027 cell Anatomy 0.000 description 18
- 239000003011 anion exchange membrane Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 210000003040 circulating cell Anatomy 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
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 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
- 238000011109 contamination Methods 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
- 238000009713 electroplating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/02—Hydrogen or oxygen
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- 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
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- 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
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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 ion membrane electrolysis method. The method uses an ionic membrane to divide an electrolytic cell into an anode chamber and a cathode chamber, and a sulfuric acid solution is introduced into the electrolytic cell, a copper sheet is used as an anode, and an insoluble material is used as a cathode. At the temperature of 20-85 ℃, the temperature is 50A/m 2 ~8000A/m 2 The current density of the anode chamber is electrolyzed, hydrogen ions in the cathode chamber are reduced into hydrogen gas for recovery, a copper anode is oxidized to generate copper ions for dissolution, a copper sulfate solution is obtained in the anode chamber, and the voltage of the tank is 0.30V-2.00V. Filtering copper sulfate solution to remove impurities, cooling to-20-30 ℃, separating out copper sulfate crystals, and filtering mother liquorThe heat exchange device heats and returns to the anode chamber circulation tank, so that the continuous electrolysis of the solution is realized, and no waste liquid is generated. The method of the invention overcomes the problems of complex process, higher cost, longer time consumption and the like of the existing preparation method of the high-purity copper sulfate, 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 ion membrane electrolysis method.
Background
In recent years, the rapid development of the lithium battery industry drives the rapid growth of electrolytic copper foil, and the electrolyte used for producing the lithium battery copper foil is copper sulfate aqueous solution, which can be prepared by directly dissolving copper sulfate crystals in water or by dissolving high-purity cathode copper or standard cathode copper in a sulfuric acid medium after oxidizing the cathode copper by air. The purity of the copper sulfate for electroplating which is used for executing HG/T3592-2010 in the quality standard of products 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, in the actual production of electrolytic copper foil, the latter method is generally used, but this method has problems of slow copper dissolution rate, acid mist contamination, low efficiency, and the like.
At present, the copper sulfate on the market is mostly obtained from the purification of crude copper sulfate, the crude copper sulfate produced by taking copper ore as a raw material contains more impurities, and further purification is needed to prepare a copper sulfate product meeting the quality standard. Extraction method, ion exchange method and the like are mostly adopted in the purification process, and the process is complex, high in cost and long in 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 change 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 ion membrane electrolysis method. The invention has simple process and can realize continuous and large-scale production.
The invention relates to a method for continuously preparing copper sulfate crystals by an ionic membrane electrolysis method, which is characterized in that an electrolytic cell is divided into an anode chamber and a cathode chamber by an ionic membrane, a sulfuric acid solution is introduced into the electrolytic cell, a copper sheet is used as an anode, and an insoluble electrode material is used as a cathode. After the 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 ion membrane blocks the dissolved copper ions from entering the cathode chamber from the anode chamber, the copper ions are prevented from being separated out on the cathode again, and copper sulfate solution is obtained in the anode chamber. The copper sulfate solution is filtered to remove impurities and cooled to separate out copper sulfate crystals, and the filtered mother liquor is heated by a heat exchange device and then returns 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）
cathode:
（2）
the technical scheme of the invention comprises the following operation steps:
heating dilute sulfuric acid in a sulfuric acid storage tank to a certain temperature through a heat exchanger, respectively introducing the dilute sulfuric acid into a cathode chamber and an anode chamber of an ion membrane electrolytic cell through a cathode chamber circulating cell and an anode chamber circulating cell, respectively starting electrolyte circulation among the cathode chamber, the anode chamber and the cathode chamber circulating cell, switching on direct current, electrolyzing under certain sulfuric acid concentration, temperature and current density to obtain a copper sulfate solution in the anode chamber, and recovering hydrogen generated in the cathode chamber through a gas collecting device;
step (2), after the copper ions in the solution in the anode chamber circulating tank reach a certain concentration, filtering and removing impurities, and introducing into a copper-dissolving liquid 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), the mother liquor filtered in the step (3) is heated by a heat exchanger and then returns to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
In the step (1), an ionic membrane used by the ionic membrane electrolytic cell divides the electrolytic cell into an anode chamber and a cathode chamber, and further, the ionic membrane used is one of strong acid resistant commercial ionic 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 30-500 g/L, the conductivity of the solution is reduced by too low concentration, and the solubility of copper sulfate is reduced by too high concentration;
in the step (1), the electrolysis temperature is 20-85 ℃, the low temperature is not favorable for the conductivity of the electrolyte, the excessive temperature is easy to cause acid mist evaporation, waste raw materials and increase energy consumption, and the damage of the ionic membrane is easy to cause;
in the step (1), the current density is 50A/m 2 ~8000A/m 2 Too low current density slows the dissolution rate of copper, and too high current density increases cell voltage and increases energy consumption;
in the step (1), the voltage of the tank is 0.30-2.00V;
in the step (2), the concentration of copper ions is as follows: 12 g/L-180 g/L, too low copper ion concentration is not beneficial to cooling crystallization separation, and too high copper ion concentration increases tank voltage and energy consumption.
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 energy required by heating is increased when the mother liquor returns to the electrolyte due to the low cooling temperature;
in the step (4), the temperature of the solution heated by 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 influenced.
(2) The electrolysis by-product hydrogen is a green energy source and can be recycled, so that the high-efficiency utilization of resources is realized; the filtered mother liquor can be returned to electrolysis, no waste liquor is generated, and the method is environment-friendly.
(3) The invention has simple process and low cost, is easy to realize the assembly of each unit electrolytic cell, and can realize continuous production and large-scale industrial application.
Drawings
FIG. 1 is an ionic membrane electrolysis device of the present invention;
FIG. 2 is a schematic structural view of an ion membrane electrolyzer;
FIG. 3 is an XRD pattern of the prepared copper sulfate pentahydrate crystal;
in the figure: 1-electrolytic bath, 2-cathode chamber, 3-anode chamber, 4-ionic membrane, 5-sulfuric acid storage tank, 6-heat exchanger, 7-cathode chamber circulation tank, 8-anode chamber circulation tank, 9-circulating pump, 10-filtering device, 11-copper solution storage tank and 12-crystallizing device.
Detailed Description
The invention will be further elucidated by means of specific embodiments in conjunction with the accompanying drawings.
A device for continuously preparing copper sulfate crystals by an ion membrane electrolysis method comprises an electrolysis bath 1, an anion circulation bath 7, a cation circulation bath 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 circulating pump 9 and a connecting pipeline.
An electrolytic cell 1 connected with a pipeline, wherein the electrolytic cell 1 is divided into a cathode chamber and an anode chamber by using an ionic membrane 4, 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; heating the sulfuric acid solution in a sulfuric acid storage tank 5 to a certain electrolysis temperature through a heat exchanger 6, and introducing the sulfuric acid solution into a cathode chamber 2 and an anode chamber 3 of an electrolytic cell 1 through a cathode circulating tank 7 and an anode chamber circulating tank 8 respectively through pipelines; simultaneously, respectively starting 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 to circulate the solution; under certain current density, temperature and sulfuric acid concentration, the electrolyte is subjected to direct current electrolysis, a copper anode in the anode chamber 3 is dissolved, and hydrogen generated in the cathode chamber 2 is recovered through a recovery device; after the concentration of copper ions in the solution in the anode chamber circulation tank 8 reaches a target concentration, the solution is filtered by a filtering device 10 to remove impurities and then flows into a copper solution storage tank 11 at a certain flow rate; the solution in the copper solution storage tank 11 is directly cooled and crystallized by a crystallizing device 12, and then is filtered by a filtering device 10, the prepared copper sulfate crystal is obtained in a solid phase, and the liquid phase is low-concentration mother liquor. The mother liquor is heated to a certain temperature by the heat exchanger 6 and then returns to the anode chamber circulation tank 8, meanwhile, the sulfuric acid in the sulfuric acid storage tank 5 replenishes the solution to the anode chamber circulation tank 8 at a certain flow rate, and the solution volume and concentration in the anode chamber circulation tank 8 are kept stable.
Example 1 this example provides a method for continuous preparation of copper sulfate crystals by ion membrane electrolysis, comprising the steps of:
step 1: introducing 200g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion-exchange membrane electrolytic cell, using Cu-CATH-2 cathode copper as an anode, Cu-CATH-2 cathode copper as a cathode, the inter-polar distance is 25mm, using an anion-exchange membrane as an ion-exchange membrane, switching on direct current, and controlling the current density to be 500A/m 2 Electrolyzing at the reaction temperature of 55 ℃, recovering hydrogen generated in a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic bath is 0.90V;
step 2: when the concentration of copper ions in the anode chamber circulating tank reaches 90g/L, filtering and removing impurities from the solution, and introducing the solution into a copper-dissolving liquid storage tank;
and step 3: cooling the solution in the copper-dissolved solution storage tank to 20 ℃, separating out copper sulfate crystals, and filtering to prepare 180g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 55 ℃ by 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 replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
step 1: introducing 200g/L dilute sulfuric acid in a sulfuric acid storage tank into an ionic membrane electrolytic cell, using Cu-CATH-2 cathode copper as an anode, iridium tantalum titanium-based coating material as a cathode, the inter-polar distance is 25mm, using an anion exchange membrane as an ionic 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 in a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic bath is 0.79V;
and 2, step: when the concentration of copper ions in the anode chamber circulation tank reaches 140g/L, filtering and removing impurities from the solution, and introducing the solution into a copper-dissolving solution storage tank;
and step 3: cooling the solution in the copper-dissolved solution storage tank to 30 ℃, separating out copper sulfate crystals, and filtering to prepare 320g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 85 ℃ by 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 replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
step 1: introducing 500g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic cell, using Cu-CATH-2 cathode copper as an anode and Cu-CATH-2 cathode copper as a cathode, wherein the inter-polar distance is 25mm, and usingThe anion exchange membrane is an ionic membrane, direct current is switched on, and the current density is controlled to be 500A/m 2 Electrolyzing at the reaction temperature of 55 ℃, recovering hydrogen generated in the cathode chamber through a gas collecting device, and controlling the voltage of an electrolytic bath to be 0.78V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 40g/L, filtering and removing impurities from the solution, and introducing the solution into a copper-dissolving solution storage tank;
and step 3: cooling the solution in the copper-dissolved solution storage tank to 10 ℃, separating out copper sulfate crystals, and filtering to prepare 130g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 55 ℃ by 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 replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
step 1: introducing 500g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion exchange membrane electrolytic cell, using Cu-CATH-2 cathode copper as an anode, Cu-CATH-2 cathode copper as a cathode, wherein the inter-polar distance is 25mm, using an anion exchange membrane as an ion membrane, switching on direct current, and controlling the current density to be 8000A/m 2 Electrolyzing at the reaction temperature of 55 ℃, recovering hydrogen generated in a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic bath is 1.28V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 40g/L, filtering and removing impurities from the solution, and introducing the solution into a copper-dissolving solution storage tank;
and step 3: cooling the solution in the copper-dissolved solution storage tank to 10 ℃, separating out copper sulfate crystals, and filtering to prepare 130g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 55 ℃ by 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 replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
step 1: introducing 500g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion-exchange membrane electrolytic cell, using Cu-CATH-2 cathode copper as an anode, Cu-CATH-2 cathode copper as a cathode, the inter-polar distance is 25mm, using an anion-exchange membrane as an ion-exchange membrane, switching on direct current, and controlling the current density to be 500A/m 2 Electrolyzing at the reaction temperature of 20 ℃, recovering hydrogen generated in a cathode chamber through a gas collecting device, and controlling the voltage of an electrolytic bath to be 0.95V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 12g/L, filtering and removing impurities from the solution, and introducing the solution into a copper-dissolving solution storage tank;
and step 3: cooling the solution in the copper-dissolved solution storage tank to-20 ℃, separating out copper sulfate crystals, and filtering to prepare 40g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 20 ℃ by 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 replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
step 1: introducing 30g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion-exchange membrane electrolytic cell, using Cu-CATH-2 cathode copper as an anode, Cu-CATH-2 cathode copper as a cathode, the inter-polar distance is 25mm, using an anion-exchange membrane as an ion-exchange membrane, switching on direct current, and controlling the current density to be 50A/m 2 Electrolyzing at the reaction temperature of 55 ℃, recovering hydrogen generated in a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic bath is 2.00V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 120g/L, filtering and impurity removing are carried out on the solution, and then the solution is introduced into a copper-dissolving solution storage tank;
and step 3: cooling the solution in the copper solution storage tank to 20 ℃, separating out copper sulfate crystals, and filtering to prepare 195g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 55 ℃ by 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 replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
Example 7 this example provides a method for continuous preparation of copper sulfate crystals by ion 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 cell, using Cu-CATH-2 cathode copper as an anode, a commercial platinum electrode as a cathode, the inter-polar distance of 25mm, and an anion exchange membrane as an ion membrane, switching on direct current, and controlling the current density to be 50A/m 2 Electrolyzing at the reaction temperature of 85 ℃, and recovering hydrogen generated in a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic bath is 1.15V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 180g/L, filtering and removing impurities from the solution, and introducing the solution into a copper-dissolving solution storage tank;
and 3, step 3: cooling the solution in the copper-dissolved solution storage tank to 30 ℃, separating out copper sulfate crystals, and filtering to prepare 350g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 85 ℃ by 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 replenishes the solution to the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
step 1: introducing 400g/L dilute sulfuric acid in a sulfuric acid storage tank into an ion membrane electrolytic cell, using Cu-CATH-2 cathode copper as an anode, a commercial platinum electrode as a cathode, the inter-polar distance of 25mm, and an anion exchange membrane as an ion membrane, switching on direct current, and controlling the current density to be 50A/m 2 Electrolyzing at the reaction temperature of 85 ℃, and recovering hydrogen generated in a cathode chamber through a gas collecting device, wherein the voltage of an electrolytic bath is 0.30V;
step 2: when the concentration of copper ions in the anode chamber circulation tank reaches 100g/L, filtering and removing impurities from the solution, and introducing the solution into a copper-dissolving solution storage tank;
and 3, step 3: cooling the solution in the copper-dissolved solution storage tank to 30 ℃, separating out copper sulfate crystals, and filtering to prepare 220g of copper sulfate crystals per liter of solution;
and 4, step 4: heating the mother liquor filtered in the step 3 to 85 ℃ by 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 replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank 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 results of examining metal impurity elements of typical ultrapure 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 respectively 16ppm, 4ppm, 2ppm and 2ppm, which indicates that the purity of copper sulfate crystals continuously prepared by the ion-exchange membrane electrolysis method is very high, and is superior to the existing national copper sulfate standard HG/T3592-.
TABLE 1
| Element(s) | As | Bi | Fe | Pb | Sb | Sn | Ni | Zn |
| Content (%) | Not detected out | 0.0016 | 0.0004 | Undetected | Not detected out | 0.0002 | 0.0002 | Not detected out |
FIG. 3 is an XRD spectrum of the prepared blue copperas and a standard card PDF #72-2355 spectrum, and by comparison, main peaks basically correspond to one another and have no impurity peak, which indicates that the prepared product is high-purity blue copperas. The X-ray diffraction peak in the spectrum is quite sharp, which shows that the crystallinity of the copper sulfate after cooling crystallization is very high.
The above description is only an example of the embodiment of the present invention, and within the knowledge of those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for continuously preparing copper sulfate crystals by an ion membrane electrolysis method is characterized by comprising the following steps:
heating dilute sulfuric acid in a sulfuric acid storage tank to a certain temperature through a heat exchanger, respectively introducing the dilute sulfuric acid into a cathode chamber and an anode chamber of an ion membrane electrolytic cell through a cathode chamber circulating tank and an anode chamber circulating tank, respectively starting electrolyte circulation among the cathode chamber, the anode chamber, the cathode chamber circulating tank and the anode chamber circulating tank, switching on direct current, electrolyzing under certain sulfuric acid concentration, temperature and current density, obtaining a copper sulfate solution in the anode chamber, and recovering hydrogen generated in the cathode chamber through a gas collection device;
step (2), after the copper ions in the solution in the anode chamber circulating tank reach a certain concentration, filtering and removing impurities, and introducing into a copper-dissolving liquid 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), the mother liquor filtered in the step (3) is heated by a heat exchanger and then returns to the anode chamber circulation tank; meanwhile, the sulfuric acid in the sulfuric acid storage tank replenishes the anode chamber circulating tank at a certain flow rate, and the volume and the concentration of the solution in the anode chamber circulating tank are kept stable.
2. The method of claim 1, wherein the anode material in the anode chamber is high purity copper and the cathode chamber is insoluble material comprising any one or a mixture of copper, titanium, stainless steel, platinum, noble metal coatings.
3. The method according to claim 1, wherein the ionic membrane used in the ionic membrane electrolyzer is one of any commercial ionic membranes of strong acid resistance that do not allow copper ions to pass through.
4. The method of claim 1, wherein the concentration of sulfuric acid is 30-500 g/L.
5. The method of claim 1, wherein in step (1), the temperature is 20 ℃ to 85 ℃.
6. The method of claim 1, wherein in step (1), the temperature is 45 ℃ to 65 ℃.
7. The method according to claim 1, wherein the current density in step (1) is 50A/m 2 ~8000A/m 2 。
8. The method according to claim 1, wherein the concentration of copper ions in the step (2) is 12-180 g/L.
9. The method of claim 1, wherein the cooling temperature in the step (4) is-20 ℃ to 30 ℃, and the cell voltage in the step (1) is 0.30V to 2.00V.
10. The method of claim 1, wherein the heat exchanger in step (4) heats the solution to a temperature of 20 ℃ to 85 ℃.
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