CN110724964A - Preparation method of nickel sulfamate solution - Google Patents
Preparation method of nickel sulfamate solution Download PDFInfo
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- CN110724964A CN110724964A CN201911141166.4A CN201911141166A CN110724964A CN 110724964 A CN110724964 A CN 110724964A CN 201911141166 A CN201911141166 A CN 201911141166A CN 110724964 A CN110724964 A CN 110724964A
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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
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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
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- 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
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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- 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
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Abstract
The preparation method of the nickel sulfamate solution takes industrial-grade nickel sulfate or nickel chloride as a raw material, adopts an electrolytic deposition method to prepare a high-purity electrolytic nickel plate, the high-purity nickel plate is used as an anode plate in the preparation of nickel sulfamate by a second diaphragm electrolysis method, the voltage fluctuation range of the whole electrolysis process is small by periodically supplementing solid sulfamic acid in the cathode region in the electrolysis process, no side reaction occurs, and the ion membrane adopts an anion heterogeneous exchange membrane, so that sulfamic acid can enter an anode region through the ion membrane to ensure the smooth proceeding of electrochemical reaction, and the electrolyzed nickel sulfamate solution has low sulfate content, no organic matter residue and no sodium ion introduction.
Description
Technical Field
The invention belongs to the field of nickel salt preparation methods, and particularly relates to a preparation method of a nickel sulfamate solution.
Background
With the establishment and implementation of the national new energy strategic plan, the development and utilization of solar energy become more and more important, the new installation amount of the photovoltaic market in 2017 is expected to break through 100GW for the first time, and the annual growth rate exceeds 25%. Among them, china stably lives on market taps with a loading capacity of about 50GW, and demand of photovoltaic power generation for large-area silicon wafers is increasing. Due to the maturity of semiconductor manufacturing technology, the manufacturing cost of silicon wafers in other aspects is continuously reduced, but the cutting cost of the silicon wafers for solar cells is always high and accounts for about 30% of the total manufacturing cost. The electroplated diamond cutting wire is a linear cutting tool which is manufactured by using electroplated metal as a bonding agent and solidifying diamond grinding materials on a core wire substrate through the electro-deposition action of the metal, wherein the size of the diamond grinding materials is generally several micrometers to dozens of micrometers.
The high-quality nickel sulfamate solution nickel plating has the characteristics of low internal stress of a plating layer, high electroplating speed, good wear resistance, precise plating layer, environmental friendliness and the like, is widely applied to precise electroplating (diamond cutting line electroplating), Printed Circuit Board (PCB) electroplating, connector electroplating and the like, and has very large market demand, but the traditional nickel sulfamate production process has long production flow and high product impurity content, and enterprises producing high-quality nickel sulfamate solutions are very few.
The presently disclosed methods for preparing nickel sulfamates are: (1) synthesizing nickel sulfamate solution from high-purity nickel powder and sulfamic acid solution at low temperature under the catalysis of hydrogen peroxide or ozone; (2) chinese patent CN101704517B provides a preparation method of an electronic grade nickel sulfamate solution, which comprises the following process steps of firstly dissolving an industrial grade nickel sulfate raw material in pure water, filtering, concentrating and crystallizing the solution to obtain refined nickel sulfate crystals; then preparing the prepared nickel sulfate crystal into a solution, reacting the solution with an ammonium carbonate solution to prepare a basic nickel carbonate precipitate, and finally reacting the washed and impurity-removed basic nickel carbonate with a sulfamic acid solution to synthesize a nickel sulfamate solution; (3) chinese patent CN102092694B provides a preparation method of nickel sulfamate: a, mixing the nickel-containing solution after impurity removal to a concentration of 45-80 g/L to be used as an extraction stock solution; b, in the extraction box, mixing the components in a ratio of 1: 3.5-1: 4, taking P507 and kerosene as organic phases to carry out saponification reaction with sodium hydroxide solution to prepare sodium soap; c, extracting nickel ions in the stock solution by using the prepared sodium soap, and controlling the phase ratio and the clarification time of a water phase and an oil phase in a box body to ensure that the nickel content of the discharged raffinate is lower than 0.01 g/l; d, acid washing the organic phase loaded with nickel by using aqueous solution of persulfuric acid or sulfamic acid to remove impurities, and discharging the washed organic phase into a stock solution tank; e, carrying out back extraction on the nickel-loaded organic phase subjected to acid washing and impurity removal to produce a nickel sulfamate solution, and washing the regenerated organic phase subjected to back extraction by deionized water and then entering an extraction system again for recycling.
The three methods have the common defects of long operation period, more impurity ions and difficult treatment, for example, the residual hydrogen peroxide in the method (1) is difficult to eliminate, and the damage to the diamond wire nickel plating liquid medicine is very large. The method (2) has long production period, large waste water production amount and is not environment-friendly. The trace amount of extractant remained in the nickel sulfamate solution prepared by the extraction method in the method (3) is difficult to remove, a large amount of activated carbon is needed for adsorption treatment, in addition, the waste water generated by saponification is very large, the environment is not friendly, and the nickel sulfamate prepared by the three methods has higher frequency of quality accidents in the nickel plating application of the diamond cutting line (the product is unqualified due to the large internal stress of a plating layer caused by the standard exceeding of organic matters, sulfate and the like).
Disclosure of Invention
The invention aims to provide a preparation method of nickel sulfamate solution, which has the advantages of short production process, high product purity and low production cost.
The invention provides a preparation method of nickel sulfamate solution, which comprises the following steps:
s1, preparing an acidic nickel solution: preparing an acidic nickel solution containing nickel ions with the weight fraction of 3-8 wt% in a first liquid preparation tank;
s2, preparing a nickel plate: then putting the acidic nickel solution prepared in the step S1 into a first diaphragm electrolytic cell, wherein the anode of the first diaphragm electrolytic cell is a titanium plate, the cathode of the first diaphragm electrolytic cell is a nickel plate with the thickness of 2-3 mm, the anode and the cathode of the first diaphragm electrolytic cell are separated by an ion exchange membrane, then carrying out first electrolytic deposition, stopping electrolysis after the thickness of the nickel plate of the cathode is increased to 8-20 mm, and then cleaning the nickel plate with the thickness of 8-20 mm for later use;
s3, preparing an aminosulfonic acid solution: preparing an sulfamic acid solution containing 8-14 wt% of sulfamic acid in a second liquid preparation tank;
s4, preparing a nickel sulfamate solution: placing a nickel plate with the thickness of 8-20 mm prepared in the step S2 on the anode of a second diaphragm electrolytic cell, placing a nickel plate with the thickness of 5mm on the cathode of the second diaphragm electrolytic cell, injecting the sulfamic acid solution prepared in the step S3 into the second diaphragm electrolytic cell, separating the positive electrode and the negative electrode of the second diaphragm electrolytic cell by an anion heterogeneous exchange membrane, performing second electrolytic deposition, stopping electrolysis when the anode area of the second diaphragm electrolytic cell contains 5-10 wt% of nickel ions, releasing the nickel sulfamic acid solution obtained by the electrolysis of the anode area of the second diaphragm electrolytic cell, adjusting the pH value of the nickel sulfamic acid solution to 4.0-5.0, and preparing the nickel sulfamic acid solution with the nickel ion concentration of 70-180 g/L.
In some embodiments of the present invention, the acidic nickel solution in step S1 is one of a nickel sulfate solution and a nickel chloride solution.
In some embodiments of the present invention, the additional technical grade nickel sulfate or nickel chloride is added when the weight fraction of nickel ions in the acidic nickel solution is less than 3 wt% in step S2.
In some embodiments of the present invention, the conditions of the first electrolytic deposition in step S2 are as follows: the temperature of electrolysis is 10-40 ℃, and the current density is 1.0-5.0A/dm2。
In some embodiments of the present invention, the weight fraction of sulfamic acid in the sulfamic acid solution in step S3 is 10 to 13 wt%.
In some embodiments of the present invention, the method for pretreating the anion heterogeneous exchange membrane in step S4 comprises: and (3) installing an anion heterogeneous exchange membrane in the second isolated electrolytic tank, then filling pure water into a cathode region of the second isolated electrolytic tank, filling the sulfamic acid solution prepared in the step S3 into an anode region, standing for 12 hours, detecting the content of acid radical ions in the cathode region and the anode region, if the concentration of the acid radical ions is greater than 10ppm, discharging the solution in the anode region and the cathode region in the isolated electrolytic tank, adding the pure water and the sulfamic acid solution again, and standing for 12 hours for detection until the concentration of the acid radical ions in the solution in the anode region and the cathode region is reduced to below 10ppm, namely finishing the treatment of the anion heterogeneous exchange membrane.
In some embodiments of the present invention, the pH adjusting agent for adjusting the nickel sulfamate solution in step S4 is one of analytically pure nickel carbonate or nickel hydroxide.
In some embodiments of the invention, the step S4 releases the nickel sulfamate solution in the anode region of the second diaphragm electrolytic cell, and then reinjects the nickel sulfamate solution.
In some embodiments of the present invention, the step S4 is repeated to use the cathode region in the step S1 after replacing the anode nickel plate.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relates to a method for preparing nickel sulfamate solution, which takes industrial-grade nickel sulfate or nickel chloride as raw materials and adopts an electrolytic deposition method to prepare a high-purity electrolytic nickel plate, the high-purity nickel plate is used as an anode plate in the nickel sulfamate prepared by a second diaphragm electrolytic method, solid sulfamic acid is periodically replenished in a cathode area in the electrolytic process to ensure that the voltage fluctuation amplitude of a tank in the whole electrolytic process is very small and no side reaction occurs, an anion heterogeneous exchange membrane is adopted as an ion membrane, the sulfamic acid can enter an anode area through the ion membrane to ensure the smooth proceeding of electrochemical reaction, the nickel sulfamate solution obtained by electrolysis has low sulfate content, no organic matter residue and no sodium ion introduction, has high product purity, meets the quality requirement of nickel sulfamate for electroplating diamond, and has short production process compared with the traditional nickel sulfamate production method, no impurity is introduced in the production process, and particularly compared with an extraction method or a method for converting sulfuric acid into nickel carbonate, the method has no wastewater discharge and is environment-friendly.
2. The invention enables the nickel anode residual polar plate in the production process of the second diaphragm electrolytic nickel sulfamate to be subjected to electrolytic deposition again in the industrial-grade nickel sulfate or nickel chloride solution, realizes the recycling of the polar plate, generates no corner nickel material and greatly reduces the production cost.
Detailed Description
In the following embodiment, the cathode plate of the first electrolytic nickel plate deposition process is a pure nickel plate, the anode plate is a titanium plate, and the acidic nickel solution is a nickel sulfate solution or a nickel chloride solution; the sulfamic acid used in the preparation process of nickel sulfamate is analytically pure with 99 percent of content, the cathode plate and the anode plate are cathode plates obtained in the second electrolytic deposition process, the ion exchange membrane of the second diaphragm electrolytic cell adopts an anion heterogeneous exchange membrane, and after pretreatment, the elution amount of chloride ions and sulfate ions is less than 10 ppm.
The technical solutions in the embodiments of the present invention will be clearly and completely described below so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention will be more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art without inventive faculty based on the embodiments described herein are intended to fall within the scope of the present invention.
Example 1
A preparation method of nickel sulfamate solution comprises the following steps:
s1, preparing an acidic nickel solution: preparing an acidic nickel solution containing 8 wt% of nickel ions in a first solution preparation tank;
s2, preparing a nickel plate: then putting the acidic nickel solution prepared in the step S1 into a first diaphragm electrolytic cell, wherein the anode of the first diaphragm electrolytic cell is a titanium plate, the cathode of the first diaphragm electrolytic cell is a nickel plate with the thickness of 3mm, the cathode and the anode of the first diaphragm electrolytic cell are separated by adopting an ion exchange membrane, then carrying out first electrolytic deposition, stopping electrolysis after the thickness of the nickel plate of the cathode is increased to 20mm, and then cleaning the nickel plate with the thickness of 20mm for later use;
s3, preparing an aminosulfonic acid solution: preparing an sulfamic acid solution containing 13 wt% of sulfamic acid in a second solution preparation tank;
s4, preparing a nickel sulfamate solution: placing a nickel plate with the thickness of 20mm prepared in the step S2 on the anode of a second diaphragm electrolytic cell, placing a nickel plate with the thickness of 5mm on the cathode, then injecting the sulfamic acid solution prepared in the step S3 into the second diaphragm electrolytic cell, separating the positive electrode and the negative electrode of the second diaphragm electrolytic cell by an anion heterogeneous exchange membrane, then carrying out second electrolytic deposition, stopping electrolysis when the anode area of the second diaphragm electrolytic cell contains 10 wt% of nickel ions, releasing the nickel sulfamic acid solution obtained by the electrolysis of the anode area of the second diaphragm electrolytic cell, adjusting the pH value of the nickel sulfamic acid solution to 4.8, and then preparing the nickel sulfamic acid solution with the nickel ion concentration of 180 g/L.
Wherein, the acidic nickel solution in step S1 is nickel sulfate.
Wherein, in step S2, when the weight fraction of nickel ions in the acidic nickel solution is less than 3 wt%, additional industrial-grade nickel sulfate is added.
Wherein, the conditions of the first electrolytic deposition in the step S2 are as follows: the temperature of electrolysis was 40 ℃ and the current density was 4.0A/dm2。
Wherein the pH regulator for regulating the nickel sulfamate solution in the step S4 is analytically pure nickel hydroxide.
Wherein, in step S4, the sulfamic acid solution is reinjected after the nickel sulfamic acid solution in the anode area of the second diaphragm electrolytic cell is released.
Wherein the step S4 is repeated to utilize the cathode region in the step S1 under the condition of replacing the anode nickel plate.
Example 2
A preparation method of nickel sulfamate solution comprises the following steps:
s1, preparing an acidic nickel solution: preparing an acidic nickel solution containing 5 wt% of nickel ions in a first solution preparation tank;
s2, preparing a nickel plate: then putting the acidic nickel solution prepared in the step S1 into a first diaphragm electrolytic cell, wherein the anode of the first diaphragm electrolytic cell is a titanium plate, the cathode of the first diaphragm electrolytic cell is a nickel plate with the thickness of 2mm, the cathode and the anode of the first diaphragm electrolytic cell are separated by adopting an ion exchange membrane, then carrying out first electrolytic deposition, stopping electrolysis after the thickness of the nickel plate of the cathode is increased to 10mm, and then cleaning the nickel plate with the thickness of 10mm for later use;
s3, preparing an aminosulfonic acid solution: preparing an sulfamic acid solution containing 10 wt% of sulfamic acid in a second solution preparation tank;
s4, preparing a nickel sulfamate solution: placing a nickel plate with the thickness of 10mm prepared in the step S2 on the anode of a second diaphragm electrolytic cell, placing a nickel plate with the thickness of 5mm on the cathode, then injecting the sulfamic acid solution prepared in the step S3 into the second diaphragm electrolytic cell, separating the positive electrode and the negative electrode of the second diaphragm electrolytic cell by an anion heterogeneous exchange membrane, then carrying out second electrolytic deposition, stopping electrolysis when the anode area of the second diaphragm electrolytic cell contains 8 wt% of nickel ions, releasing the nickel sulfamic acid solution obtained by the electrolysis of the anode area of the second diaphragm electrolytic cell, adjusting the pH value of the nickel sulfamic acid solution to 4.5, and then preparing the nickel sulfamic acid solution with the nickel ion concentration of 90 g/L.
Wherein, the acidic nickel solution in step S1 is a nickel chloride solution.
Wherein, in step S2, when the weight fraction of nickel ions in the acidic nickel solution is less than 3 wt%, additional industrial-grade nickel chloride is added.
Wherein, the conditions of the first electrolytic deposition in the step S2 are as follows: the temperature of electrolysis is 10 ℃, and the current density is 2.0A/dm2。
Wherein the pH regulator for regulating the nickel sulfamate solution in the step S4 is analytically pure nickel hydroxide.
Wherein, in step S4, the sulfamic acid solution is reinjected after the nickel sulfamic acid solution in the anode area of the second diaphragm electrolytic cell is released.
Wherein the step S4 is repeated to utilize the cathode region in the step S1 under the condition of replacing the anode nickel plate.
Example 3
The preparation method of the nickel sulfamate solution comprises the following steps:
s1, preparing an acidic nickel solution: preparing an acidic nickel solution containing nickel ions with the weight fraction of 3 wt% in a first solution preparation tank;
s2, preparing a nickel plate: then putting the acidic nickel solution prepared in the step S1 into a first diaphragm electrolytic cell, wherein the anode of the first diaphragm electrolytic cell is a titanium plate, the cathode of the first diaphragm electrolytic cell is a nickel plate with the thickness of 2mm, the cathode and the anode of the first diaphragm electrolytic cell are separated by adopting an ion exchange membrane, then carrying out first electrolytic deposition, stopping electrolysis after the thickness of the nickel plate of the cathode is increased to 8mm, and then cleaning the nickel plate with the thickness of 8mm for later use;
s3, preparing an aminosulfonic acid solution: preparing sulfamic acid solution containing 8 wt% of sulfamic acid in a second solution preparation tank;
s4, preparing a nickel sulfamate solution: placing a nickel plate with the thickness of 8mm prepared in the step S2 on the anode of a second diaphragm electrolytic cell, placing a nickel plate with the thickness of 5mm on the cathode, then injecting the sulfamic acid solution prepared in the step S3 into the second diaphragm electrolytic cell, separating the positive electrode and the negative electrode of the second diaphragm electrolytic cell by an anion heterogeneous exchange membrane, then carrying out second electrolytic deposition, stopping electrolysis when the anode area of the second diaphragm electrolytic cell contains 6 wt% of nickel ions, releasing the nickel sulfamic acid solution obtained by the electrolysis of the anode area of the second diaphragm electrolytic cell, adjusting the pH value of the nickel sulfamic acid solution to 4.0, and then preparing the nickel sulfamic acid solution with the nickel ion concentration of 70 g/L.
Wherein, the acidic nickel solution in step S1 is a nickel sulfate solution.
Wherein, in step S2, when the weight fraction of nickel ions in the acidic nickel solution is less than 3 wt%, additional industrial-grade nickel sulfate is added.
Wherein, the conditions of the first electrolytic deposition in the step S2 are as follows: the temperature of electrolysis was 25 ℃ and the current density was 1.0A/dm2。
Wherein the pH regulator for regulating the nickel sulfamate solution in the step S4 is analytically pure nickel carbonate.
Wherein, in step S4, the sulfamic acid solution is reinjected after the nickel sulfamic acid solution in the anode area of the second diaphragm electrolytic cell is released.
Wherein the step S4 is repeated to utilize the cathode region in the step S1 under the condition of replacing the anode nickel plate.
Test examples
The nickel sulfamate solution obtained by the preparation method of example 1-3 was subjected to quality detection, and the results are shown in table 1:
TABLE 1
From table 1, it can be seen that the nickel sulfamate solutions prepared in examples 1 to 3 are all superior products, and the product prepared by the method is high in purity, environment-friendly in production process and low in production cost, and is worthy of popularization.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A preparation method of a nickel sulfamate solution is characterized by comprising the following steps:
s1, preparing an acidic nickel solution: preparing an acidic nickel solution containing nickel ions with the weight fraction of 3-8 wt% in a first liquid preparation tank;
s2, preparing a nickel plate: then putting the acidic nickel solution prepared in the step S1 into a first diaphragm electrolytic cell, wherein the anode of the first diaphragm electrolytic cell is a titanium plate, the cathode of the first diaphragm electrolytic cell is a nickel plate with the thickness of 2-3 mm, the anode and the cathode of the first diaphragm electrolytic cell are separated by an ion exchange membrane, then carrying out first electrolytic deposition, stopping electrolysis after the thickness of the nickel plate of the cathode is increased to 8-20 mm, and then cleaning the nickel plate with the thickness of 8-20 mm for later use;
s3, preparing an aminosulfonic acid solution: preparing an sulfamic acid solution containing 8-14 wt% of sulfamic acid in a second liquid preparation tank;
s4, preparing a nickel sulfamate solution: placing a nickel plate with the thickness of 8-20 mm prepared in the step S2 on the anode of a second diaphragm electrolytic cell, placing a nickel plate with the thickness of 5mm on the cathode of the second diaphragm electrolytic cell, injecting the sulfamic acid solution prepared in the step S3 into the second diaphragm electrolytic cell, separating the positive electrode and the negative electrode of the second diaphragm electrolytic cell by an anion heterogeneous exchange membrane, performing second electrolytic deposition, stopping electrolysis when the anode area of the second diaphragm electrolytic cell contains 5-10 wt% of nickel ions, releasing the nickel sulfamic acid solution obtained by the electrolysis of the anode area of the second diaphragm electrolytic cell, adjusting the pH value of the nickel sulfamic acid solution to 4.0-5.0, and preparing the nickel sulfamic acid solution with the nickel ion concentration of 70-180 g/L.
2. The method for preparing a nickel sulfamate solution according to claim 1, wherein: the acidic nickel solution in step S1 is one of a nickel sulfate solution and a nickel chloride solution.
3. The method for preparing a nickel sulfamate solution according to claim 1, wherein: and in the step S2, when the weight fraction of nickel ions in the acidic nickel solution is lower than 3 wt%, additional industrial-grade nickel sulfate or nickel chloride is added.
4. The method for preparing a nickel sulfamate solution according to claim 1, wherein: the conditions of the first electrolytic deposition in the step S2 are as follows: the temperature of electrolysis is 10-40 ℃, and the current density is 1.0-5.0A/dm2。
5. The method for preparing a nickel sulfamate solution according to claim 1, wherein: the weight fraction of sulfamic acid in the sulfamic acid solution in the step S3 is 10-13 wt%.
6. The method for preparing a nickel sulfamate solution according to claim 1, wherein: the method for pretreating the anion heterogeneous exchange membrane in the step S4 comprises the following steps: and (3) installing an anion heterogeneous exchange membrane in the second isolated electrolytic tank, then filling pure water into a cathode region of the second isolated electrolytic tank, filling the sulfamic acid solution prepared in the step S3 into an anode region, standing for 12 hours, detecting the content of acid radical ions in the cathode region and the anode region, if the concentration of the acid radical ions is greater than 10ppm, discharging the solution in the anode region and the cathode region in the isolated electrolytic tank, adding the pure water and the sulfamic acid solution again, and standing for 12 hours for detection until the concentration of the acid radical ions in the solution in the anode region and the cathode region is reduced to below 10ppm, namely finishing the treatment of the anion heterogeneous exchange membrane.
7. The method for preparing a nickel sulfamate solution according to claim 1, wherein: the pH adjusting agent for adjusting the nickel sulfamate solution in step S4 is one of analytically pure nickel carbonate or nickel hydroxide.
8. The method for preparing a nickel sulfamate solution according to claim 1, wherein: and step S4, after the nickel sulfamate solution in the anode area of the second diaphragm electrolytic cell is released, the nickel sulfamate solution is reinjected.
9. The method for preparing a nickel sulfamate solution according to claim 1, wherein: the step S4 is repeated to use the cathode region in the step S1 under the replacement of the anode nickel plate.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB576650A (en) * | 1943-06-12 | 1946-04-12 | Mond Nickel Co Ltd | Improvements relating to the production of massive nickel for use as anodes |
| US4310395A (en) * | 1979-10-08 | 1982-01-12 | Sep Gesellschaft Fur Technische Studien Entwicklung Planung Mbh | Process for electrolytic recovery of nickel from solution |
| CN101265589A (en) * | 2007-03-12 | 2008-09-17 | 张建玲 | Method for producing electrolytic nickel by using various nickel-containing raw materials |
| CN101704517A (en) * | 2009-10-28 | 2010-05-12 | 广东光华化学厂有限公司 | Preparation method of electronic grade high-purity nickel sulfamic acid solution |
| CN101880888A (en) * | 2009-05-06 | 2010-11-10 | 宜兴方晶科技有限公司 | Preparation method of nickel aminosulfonate |
| CN102828205A (en) * | 2011-08-26 | 2012-12-19 | 兰州交通大学 | Novel metal electro-deposition refining technology |
| CN103388161A (en) * | 2013-08-20 | 2013-11-13 | 兰州交通大学 | Membrane electrode device for refining metal sulfate solution |
| CN108018582A (en) * | 2017-12-19 | 2018-05-11 | 广东光华科技股份有限公司 | A kind of preparation method of electron level sulfamic acid stannous |
-
2019
- 2019-11-20 CN CN201911141166.4A patent/CN110724964A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB576650A (en) * | 1943-06-12 | 1946-04-12 | Mond Nickel Co Ltd | Improvements relating to the production of massive nickel for use as anodes |
| US4310395A (en) * | 1979-10-08 | 1982-01-12 | Sep Gesellschaft Fur Technische Studien Entwicklung Planung Mbh | Process for electrolytic recovery of nickel from solution |
| CN101265589A (en) * | 2007-03-12 | 2008-09-17 | 张建玲 | Method for producing electrolytic nickel by using various nickel-containing raw materials |
| CN101880888A (en) * | 2009-05-06 | 2010-11-10 | 宜兴方晶科技有限公司 | Preparation method of nickel aminosulfonate |
| CN101704517A (en) * | 2009-10-28 | 2010-05-12 | 广东光华化学厂有限公司 | Preparation method of electronic grade high-purity nickel sulfamic acid solution |
| CN102828205A (en) * | 2011-08-26 | 2012-12-19 | 兰州交通大学 | Novel metal electro-deposition refining technology |
| CN103388161A (en) * | 2013-08-20 | 2013-11-13 | 兰州交通大学 | Membrane electrode device for refining metal sulfate solution |
| CN108018582A (en) * | 2017-12-19 | 2018-05-11 | 广东光华科技股份有限公司 | A kind of preparation method of electron level sulfamic acid stannous |
Non-Patent Citations (2)
| Title |
|---|
| REN XIU-LIAN等: "Electrodeposition conditions of metallic nickel in electrolytic membrane reactor", 《TRANS. NONFERROUS MET. SOC. CHINA》 * |
| 乔英杰: "《材料合成与制备》", 30 April 2010, 国防工业出版社 * |
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Application publication date: 20200124 |