阅读说明：本技术 一种无钠化制备电解镍厚板的方法 (Method for preparing electrolytic nickel thick plate without sodium treatment ) 是由 王佳东 邓晓玲 张�杰 韦聪飞 王海 于 2021-09-14 设计创作，主要内容包括：本发明属于湿法冶金技术领域,具体涉及一种无钠化制备电解镍厚板的方法,所述方法中,阴极液以镍盐作为镍源,加入硼酸作为缓冲剂,再加入低浓度的某种金属硫酸盐作为导电剂,并用酸调节溶液pH。在电解槽内,用镍始极片作为阴极,铅板作为阳极,连接电源进行通电电解,电解后可取出,并用热水处理后烘干即可得到镍厚板,生产得到的镍厚板纯度达99.996％。本发明无需引入钠离子,降低了阳极液的后期处理流程和处理成本；同时少量的金属硫酸盐加入,可增大电解液的导电性以及使电解液具有一定黏度,使其在电解过程中保持一定的液位差,可以减弱氢气在板面附着,以此减少板面气孔的产生,从而制备得到电镀级电解镍厚板,生产过程简单,具有良好的经济效益。(The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for preparing an electrolytic nickel thick plate without sodium treatment. In the electrolytic bath, a nickel starting sheet is used as a cathode, a lead plate is used as an anode, a power supply is connected for electrifying electrolysis, the nickel starting sheet can be taken out after electrolysis, hot water is used for treatment, and then the nickel starting sheet is dried to obtain a nickel thick plate, wherein the purity of the produced nickel thick plate reaches 99.996%. According to the method, sodium ions are not required to be introduced, so that the post-treatment process and the treatment cost of the anolyte are reduced; meanwhile, a small amount of metal sulfate is added, so that the conductivity of the electrolyte can be increased, the electrolyte has certain viscosity, a certain liquid level difference is kept in the electrolytic process, the adhesion of hydrogen on the plate surface can be weakened, and the generation of pores on the plate surface is reduced, so that the electroplating-grade electrolytic nickel thick plate is prepared, and the production process is simple and has good economic benefit.)

1. The method for preparing the electrolytic nickel thick plate without sodium treatment is characterized by comprising the following steps of:

preparation of S1 catholyte: taking nickel salt as a nickel source, adding boric acid as a buffering agent, adding low-concentration metal sulfate as a conductive agent, and adjusting the pH value of a system solution to 1-5 by using acid;

s2 preparation of a nickel thick plate: adopting an electrolytic method, wherein a nickel starting sheet is used as a cathode, and a lead plate is used as an anode; and (3) putting the nickel starting sheet into an electrolytic cell diaphragm bag, heating the catholyte obtained in the step S1 to 50-80 ℃, adding the catholyte into the electrolytic cell diaphragm bag, connecting a power supply to perform electrifying electrolysis, taking out the catholyte after electrolysis for 10-20 days, washing with hot water, and drying to obtain the nickel thick plate with a flat surface and no air holes.

2. The method for preparing electrolytic nickel thick plate without sodium modification as claimed in claim 1, wherein the nickel salt is selected from NiSO₄·6H₂O and/or NiCl₂·6H₂O。

3. The method for preparing thick electrolytic nickel plate without sodium modification as claimed in claim 1, wherein the metal sulfate is selected from MgSO₄And/or Al₂(SO₄)₃。

4. The method for preparing electrolytic nickel slab without sodium treatment as claimed in claim 1, wherein the acid is selected from HCl, HNO₃Or H₂SO₄。

5. The method for preparing the electrolytic nickel thick plate without sodium treatment according to claim 1, comprising the following steps:

preparation of S1 catholyte: after preparation, in the catholyte: the concentration of nickel ions is 90-120 g/L, the concentration of metal ions of metal sulfate is less than 5g/L, the concentration of boric acid is 2-10 g/L, the concentrations of cobalt, iron, lead, calcium, zinc and copper elements are all less than 0.001g/L, the concentration of sodium element is less than 1.0g/L, and the pH value of the catholyte is 1-5;

s2 preparation of a nickel thick plate: adopting an electrolytic method, wherein a nickel starting sheet is used as a cathode, and a lead plate is used as an anode; and (3) putting the nickel starting sheet into an electrolytic bath diaphragm bag, heating the catholyte obtained in the step S1 to 50-80 ℃, putting the catholyte into the electrolytic bath diaphragm bag, connecting a power supply, setting electrolysis parameters, electrifying for electrolysis, taking out after the electrolysis is carried out for 15 days, cleaning with hot water at 50-70 ℃, and drying to obtain the nickel thick plate with a flat surface and no air holes.

6. The method for preparing the electrolytic thick nickel plate without sodium modification as claimed in claim 5, wherein in the step S2 of preparing the nickel thick plate, the parameters of the electrolysis are as follows: the area ratio of the cathode to the anode is 1-2, the electrolysis temperature is 50-70 ℃, the nickel fall is 15-25 g/L, and the liquid level difference is 1-2 cm; the homopolar distance is 12-14 cm; the current density is 150 to 220A/m²。

Technical Field

The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for preparing an electrolytic nickel thick plate without sodium treatment.

Background

Electrolytic nickel, mainly prepared by an electrodeposition method. The electrolytic nickel has the excellent characteristics of high mechanical strength, good ductility, high refractoriness, difficult oxidation in the air and the like, and the stainless steel and various alloy steels manufactured by the electrolytic nickel are widely used in the fields of manufacturing of airplanes, tanks, naval vessels, radars, missiles, spaceships and civil industries, ceramic pigments, permanent magnetic materials, electronic remote control and the like. In the chemical industry, nickel is often used as a hydrogenation catalyst. In recent years, the use of nickel has been rapidly increasing in new energy battery materials, tape recorders, communication devices, and the like. In addition, nickel plating is a species with a wide application because of its excellent corrosion resistance, and has led to the production of nickel anode plates (electrolytic thick nickel).

The thickness of the electrolytic nickel produced by domestic manufacturers is mainly 5 mm-12 mm, and the larger the thickness is, the higher the price is. It is known that electrolytic nickel 10mm thick costs 3000 yuan per ton more than electrolytic nickel 5mm thick. However, in practice, the thicker the plate, the higher the technical requirements. At present, sodium sulfate is generally adopted in the production process of a nickel thick plate to increase the conductivity of the solution, sodium ions are introduced, then the sodium ions enter into an anolyte, a high-sodium electrolyte is generated, expensive processing equipment and a large-occupied working place are required to be invested for processing the sodium ions, and meanwhile, enough professional operators are required to be equipped, so that a large amount of labor, material resources and financial cost are increased.

Disclosure of Invention

The invention aims to provide a method for preparing an electrolytic nickel thick plate without sodium treatment, which aims to overcome the defects of the prior art, and the method is characterized in that a small amount of metal sulfate is added to increase the conductivity of the electrolyte and enable the electrolyte to have certain viscosity, so that a certain liquid level difference is kept in the electrolytic process, the adhesion of hydrogen on the plate surface can be weakened, and the generation of air holes on the plate surface is reduced, so that the electroplating-grade electrolytic nickel thick plate is prepared, sodium ions are not required to be added in the electrolytic process, the problem of high content of sodium ions in the electrolytic nickel anode solution in the prior art is solved, and the production process flow is optimized.

In order to achieve the purpose, the invention is realized by the following technical scheme:

a method for preparing an electrolytic nickel thick plate without sodium treatment comprises the following steps:

preparation of S1 catholyte: taking nickel salt as a nickel source, adding boric acid as a buffering agent, adding low-concentration metal sulfate as a conductive agent, and adjusting the pH value of a system solution to 1-5 by using acid;

s2 preparation of a nickel thick plate: adopting an electrolytic method, wherein a nickel starting sheet is used as a cathode, and a lead plate is used as an anode; and (3) putting the nickel starting sheet into an electrolytic cell diaphragm bag, heating the catholyte obtained in the step S1 to 50-80 ℃, adding the catholyte into the electrolytic cell diaphragm bag, connecting a power supply to perform power-on electrolysis, taking out the catholyte after electrolysis for 10-20 days, washing with hot water, and drying to obtain the nickel thick plate with a flat surface and no air holes.

Preferably, the nickel salt is selected from NiSO₄·6H₂O and/or NiCl₂·6H₂O。

Preferably, the metal sulfate is selected from MgSO₄And/or Al₂(SO₄)₃。

Preferably, the acid is selected from HCl, HNO₃Or H₂SO₄。

Further, the method comprises the following steps:

preparation of S1 catholyte: after preparation, in the catholyte: the concentration of nickel ions is 90-120 g/L, the concentration of metal ions of metal sulfate is less than 5g/L, the concentration of boric acid is 2-10 g/L, the concentrations of cobalt, iron, lead, calcium, zinc and copper elements are all less than 0.001g/L, the concentration of sodium element is less than 1.0g/L, and the pH value of the catholyte is 1-5;

s2 preparation of a nickel thick plate: adopting an electrolytic method, wherein a nickel starting sheet is used as a cathode, and a lead plate is used as an anode; and (3) putting the nickel starting sheet into an electrolytic bath diaphragm bag, heating the catholyte obtained in the step S1 to 50-80 ℃, putting the catholyte into the electrolytic bath diaphragm bag, connecting a power supply, setting electrolysis parameters, electrifying for electrolysis, taking out after the electrolysis is carried out for 15 days, cleaning with hot water at 50-70 ℃, and drying to obtain the nickel thick plate with a flat surface and no air holes.

Preferably, in the step S2 of preparing the thick nickel plate, the parameters of the electrolysis are: the area ratio of the cathode to the anode is 1-2, the electrolysis temperature is 50-70 ℃, the nickel fall is 15-25 g/L, and the solutionThe potential difference is 1-2 cm; the homopolar distance is 12-14 cm; the current density is 150 to 220A/m²。

Due to the adoption of the technical scheme, the invention has the beneficial effects that:

the invention provides a method for preparing an electrolytic nickel thick plate without sodium treatment, the prepared electrolytic nickel thick plate has good electrochemical activity, and the product quality can reach the national nickel standard special for electroplating; meanwhile, in the production process, sodium ions do not need to be introduced, so that the post-treatment flow and the treatment cost of the anolyte are reduced; moreover, a small amount of metal sulfate is added, so that the conductivity of the electrolyte can be increased, the electrolyte has certain viscosity, a certain liquid level difference can be kept in the electrolytic process, the adhesion of hydrogen on the plate surface can be weakened, and the generation of pores on the plate surface is reduced, so that the electroplating-grade electrolytic nickel thick plate is prepared, the production process is simple, and the electroplating-grade electrolytic nickel thick plate has good economic benefit.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

With NiSO₄·6H₂O is a nickel source, MgSO₄Boric acid and sulfuric acid are used as auxiliary materials, and the prepared catholyte comprises the following components: ni²⁺：120g/L，H₃BO₃：10g/L，Mg²⁺：3.2g/L，Co²⁺≤0.0001g/L，Na⁺≤0.45g/L，Fe²⁺≤0.0006g/L，Pb²⁺≤0.0002g/L，Zn²⁺≤0.0001g/L，Cu²⁺≤0.0006g/L，Cl^-Less than or equal to 0.037g/L, oil<0.50mg/L，pH＝1.27。

Then, 14L of solution is added into an electrolytic cell, the electrolyte is heated to 60 ℃, a power supply is connected, a nickel starting sheet is used as a cathode, two lead plates are used as anodes, the flow rate of the feed liquid is adjusted to be 2.6ml/min, and the current density is adjusted to be 180A/m²And starting electrolysis, wherein the area ratio of the cathode to the anode is 1.5, the electrolysis temperature is 60 ℃, the nickel fall is 20g/L, the liquid level difference is 1.5cm, and the homopolar distance is 13 cm. Continuously electrolyzing for 15 days, taking out the nickel plate from the tank, cleaning the nickel plate by using hot water at 60 ℃, and drying the nickel plate to obtain the nickel plate with a flat surface and no air holes. The purity reaches 99.9921%, and the components and the product quality meet the standard specified by the standard special nickel for electroplating (Q/YSJCCP 00502016).

Example 2

With NiSO₄·6H₂O is a nickel source, MgSO₄Boric acid and sulfuric acid are used as auxiliary materials, and the prepared catholyte comprises the following components: ni²⁺：115g/L，H₃BO₃：8g/L，Mg²⁺：3.0g/L，Co²⁺≤0.0001g/L，Na⁺≤0.45g/L，Fe²⁺≤0.0006g/L，Pb²⁺≤0.0002g/L，Zn²⁺≤0.0001g/L，Cu²⁺≤0.0006g/L，Cl^-Less than or equal to 0.037g/L, oil<0.50mg/L，pH＝4。

Then, 14L of the solution is added into an electrolytic cell, the electrolyte is heated to 50 ℃, a power supply is connected, a nickel starting sheet is used as a cathode, two lead plates are used as anodes, the flow rate of the feed liquid is adjusted to be 2.6ml/min, and the current density is 150A/m²And starting electrolysis, wherein the area ratio of the cathode to the anode is 1, the electrolysis temperature is 50 ℃, the nickel fall is 15g/L, the liquid level difference is 1cm, and the homopolar distance is 12 cm. Continuously electrolyzing for 15 days, taking out the nickel plate from the tank, cleaning the nickel plate by using hot water at 50 ℃, and drying the nickel plate to obtain the nickel plate with a flat surface and no air holes. The purity reaches 99.9963%, and the components and the product quality meet the standard specified by the standard special nickel for electroplating (Q/YSJCCP 00502016).

Example 3

With NiCl₂·6H₂O is a nickel source, Al₂(SO₄)₃Boric acid and sulfuric acid are used as auxiliary materials, and the prepared catholyte comprises the following components: ni²⁺：90g/L，H₃BO₃：2g/L，Al³⁺：3.7g/L，Co²⁺≤0.0001g/L，Na⁺≤0.45g/L，Fe²⁺≤0.0006g/L，Pb²⁺≤0.0002g/L，Zn²⁺≤0.0001g/L，Cu²⁺≤0.0006g/L，Cl^-Less than or equal to 0.037g/L, oil<0.50mg/L，pH＝5。

Then, 14L of the solution is added into an electrolytic cell, the electrolyte is heated to 70 ℃, a power supply is connected, a nickel starting sheet is used as a cathode, two lead plates are used as anodes, the flow rate of the feed liquid is adjusted to be 2.6ml/min, and the current density is 220A/m²And starting electrolysis, wherein the area ratio of the cathode to the anode is 2, the electrolysis temperature is 70 ℃, the nickel fall is 25g/L, the liquid level difference is 2cm, and the homopolar distance is 14 cm. Continuously electrolyzing for 15 days, taking out the nickel plate, cleaning the nickel plate by using hot water at 70 ℃, and drying the nickel plate to obtain the nickel plate with a flat surface and no air holes. The purity reaches 99.9905%, and the components and the product quality meet the standard specified by the standard special nickel for electroplating (Q/YSJCCP 00502016).

Example 4

Example 4 differs from example 1 in that the catholyte was prepared without the addition of MgSO₄. The method specifically comprises the following steps:

with NiSO₄·6H₂O is a nickel source, boric acid and sulfuric acid are auxiliary materials, and the prepared catholyte comprises the following components: ni²⁺：120g/L，H₃BO₃：10g/L，Co²⁺≤0.0001g/L，Na⁺≤0.45g/L，Fe²⁺≤0.0006g/L，Pb²⁺≤0.0002g/L，Zn²⁺≤0.0001g/L，Cu²⁺≤0.0006g/L，Cl^-Less than or equal to 0.037g/L, oil<0.50mg/L，pH＝1.27。

Then, 14L of solution is added into an electrolytic cell, the electrolyte is heated to 60 ℃, a power supply is connected, a nickel starting sheet is used as a cathode, two lead plates are used as anodes, the flow rate of the feed liquid is adjusted to be 2.6ml/min, and the current density is adjusted to be 180A/m²And starting electrolysis, wherein the area ratio of the cathode to the anode is 1.5, the electrolysis temperature is 60 ℃, the nickel fall is 20g/L, the liquid level difference is 0.6cm, and the homopolar distance is 13 cm. After continuously electrolyzing for 15 days, taking out the plate, cleaning the plate by hot water at 60 ℃, drying the plate, and checking that the lower part of the plate has serious vertical line bulges, and the plate has many air holes and is very dense. More than 5 air holes are formed in the thickness of 25mm multiplied by 25mm, the purity is 89.8956%, and the standard specified by standard electroplating special nickel (Q/YSJCCP 00502016) is not met.

As can be seen from the above examples, the present invention is achieved by adding a small amount of metal sulfate (MgSO)₄And/or Al₂(SO₄)₃) The conductivity of the electrolyte is increased, the electrolyte has certain viscosity, certain liquid level difference is kept in the electrolytic process, and the adhesion of hydrogen on the plate surface can be weakened, so that the generation of plate surface air holes is reduced, the electroplating-grade electrolytic nickel thick plate is prepared, sodium ions do not need to be added in the electrolytic process, the problem of high sodium ion content in the electrolytic nickel anode solution in the prior art is solved, the subsequent steps of removing sodium from the anode solution are reduced, and the production process flow is optimized.