KR101582554B1 - Manufacturing method of pure nickel plate from high fluorine containing nickel slime and treatment of acid washing and water washing solution of nickel slime - Google Patents

Abstract

The present invention relates to a method to manufacture pure nickel plates from high fluorine containing nickel slimes and treating acid washing and water washing solutions of nickel slimes and, more specifically, relates to the method to manufacture pure nickel plates from high fluorine containing nickel slime solutions and to treat acid washing and water washing solutions of nickel slime comprising: a step of adding one hydroxide solution selected from a group consisting of NaOH, Ca(OH)_2, and KOH after the solutions of nickel slime are acid washed and water washed, and the iron and fluorine contained in the nickel slime removed by solid-liquid separation; a step of melting the nickel slime by applying power after the nickel slime from which the iron and fluorine have been removed are inserted in a high-frequency induction furnace; and a step of pouring and cooling the melted nickel slime in a casting mold.

Description

Technical Field [0001] The present invention relates to a method of producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slurry and a method of treating a nickel slime with a nickel salt slurry,

The present invention relates to a method for producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slime, a pickling method for a nickel slime, and a method for recovering nickel from a wash liquor.

Nitrogen trifluoride gas (NF ₃ ) is a colorless gas having a boiling point of about -129 ° C and a melting point of about 208 ° C, and is generally used as a gas for plasma cleaning of a CVD apparatus and a gas for plasma cleaning such as silicon, polysilicon, Si ₃ N ₄ , WSi ₂ , MoSi _{2 and} other gases for semiconductor dry etching and excimer laser. Recently, demand for NF ₃ gas has been increasing due to the activation of the semiconductor industry.

Generally, the NF ₃ gas is produced by electrolyzing a molten salt of acid ammonium fluoride (NH ₄ HF ₂ ) in an electrolytic cell. At this time, the electrolytic cell has, and the electrodes of the positive and negative electrodes and a diaphragm for partitioning the anode and the cathode is provided, the diaphragm anode gas generated in the anode (NF _3, N, etc.) and the cathode gas generated in the anode (H ₂ ). NF ₃ gas is N in NH ₃ ^- ions and HF of F ^- is generated by combining the ion, a Ni ⁺ ions in the nickel electrode plate is separated from the positive electrode plate, and moving toward the negative electrode plate, some of which only adhere to the anode part is an electrolytic cell As shown in FIG. Repeating this process causes a large amount of nickel slime to accumulate on the bottom of the electrolytic cell, which is usually disposed of at the bottom of the electrolytic cell, Is being developed.

The nickel slime can be reused by recovering the nickel slime produced in the electrolysis process, melting it in a high-temperature furnace, and then casting it to regenerate it as a nickel electrode plate. However, There is a problem that the plate can not be produced with a high purity, the electrical characteristics are low, and the life time is short. There is a problem that the metal after the nickel slime treatment contains residual metals, thereby causing environmental pollution in the discharge process.

A prior art related to this is the nickel regeneration method described in Korean Patent No. 10-1086715 (issued on Nov. 24, 2011).

Accordingly, the present invention provides a method for producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slurry capable of producing a high-purity nickel plate by removing a large amount of impurities contained in a high-concentration fluorine-containing nickel slime, Which is capable of recovering nickel from the nickel slurry and capable of treating the impurities as much as possible and reusing or discharging the nickel slime.

The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.

In order to solve the above problems, the present invention provides a method for producing a nickel slurry, which comprises pickling and washing a nickel slurry, adding one hydroxide solution selected from the group consisting of NaOH, Ca (OH) ₂ and KOH, And removing fluorine; Melting the nickel slime by injecting the iron and fluorine-removed nickel slurry into a high frequency induction furnace and applying electric power; And a step of pouring the molten nickel slime into a casting mold and cooling the molten nickel slurry to a high purity nickel slime.

The present invention also provides a method for producing a nickel slurry, comprising the steps of adding calcium hydroxide to a solution obtained by pickling and washing a nickel slurry, stirring and then solid-liquid separation; Adding a carbonate to the solid-liquid separated solution, stirring the mixture, solid-liquid separation to recover nickel; And passing the solid-liquid separated solution through an ion exchange resin. The present invention also provides a method for treating a pickling solution for a nickel slime.

According to the present invention, most of the iron and fluorine contained in the nickel slime can be removed by adding hydroxide after the pickling and washing process. In addition, a high-purity nickel plate can be produced by a simple process of melting iron and fluorine-removed nickel slime.

In addition, by reprocessing the pickled and washed nickel slime solution, it is possible to remove most of the fluorine, iron and chromium contained in the pickling and washing liquid of the nickel slurry, and nickel can be further recovered, Can be reused, and there is no risk of causing environmental pollution, so that it can be discharged.

1 is a flowchart showing a method for producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slurry according to the present invention.
2 is a flowchart showing a pickling method of a nickel slime and a method of treating a washing liquid according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.

The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

The present invention relates to a method for removing iron and fluorine contained in a nickel slurry by pickling and rinsing a nickel slurry, adding a hydroxide solution selected from the group consisting of NaOH, Ca (OH) _2, and KOH and solid-

Melting the nickel slime by injecting the iron and fluorine-removed nickel slurry into a high frequency induction furnace and applying electric power; And

Pouring the molten nickel slurry into a casting mold and cooling the molten nickel slurry; and providing a high purity nickel plate from the high-concentration fluorine-containing nickel slurry.

The method for producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slurry according to the present invention can remove most of iron and fluorine contained in the nickel slurry by adding hydroxide after pickling and washing. In addition, a high-purity nickel plate can be produced by a simple process of melting iron and fluorine-removed nickel slime.

1 is a flowchart showing a method for producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slurry according to the present invention. Hereinafter, the present invention will be described in detail with reference to Fig.

The method for producing a high purity nickel plate from a high concentration fluorine-containing nickel slurry according to the present invention includes a step (S10) of pickling and washing a nickel slurry, adding a hydroxide solution, and solid-liquid separation to remove iron and fluorine contained in the nickel slime do.

In the method for producing a high purity nickel plate from a high concentration fluorine-containing nickel slurry according to the present invention, the nickel slime contains a high concentration of fluorine, the fluorine content is 10 to 12 wt%, and the iron content is 6 to 8 wt%. When such a high concentration of fluorine is contained in the nickel slime, removal of iron and fluorine is not easy, but in the present invention, iron and fluorine can be removed by adding pickling, water and hydroxide.

At this time, the pickling can be performed by adding distilled water to 2.5 to 3.5 L per 1 kg of nickel slurry, stirring the mixture, adding an acid, and filtering. When distilled water is added in an amount of less than 2.5 L per 1 kg of the nickel slime, iron contained in the nickel slurry is not removed. When the amount of distilled water is more than 3.5 L, iron is no longer removed, desirable.

The acid may be one selected from the group consisting of sulfuric acid, nitric acid, and hydrochloric acid. In consideration of cost and environmental pollution, sulfuric acid is most preferably used, and methanesulfonic acid is used as an acid other than sulfuric acid. Can be used.

Further, the pickling is preferably carried out at a pH of 3 to 5. When the pH is less than 3, nickel contained in the nickel slurry is lost. When the pH is more than 5, nickel pyrophosphate is generated and a high purity nickel plate can not be produced.

The washing can be performed by adding distilled water to 2.5 to 3.5 L per 1 kg of pickled nickel slime, stirring and filtering. When the distilled water is added in an amount of less than 2.5 L per 1 kg of the nickel slime, there is a problem in that the removal rate of iron and fluorine is low. When the distilled water is more than 3.5 L, iron and fluorine are not removed more than the amount of distilled water used. It is preferably 3.5 L or less.

The hydroxide may be one selected from the group consisting of NaOH, Ca (OH) ₂ and KOH, and the hydroxide solution is preferably added in an amount of 2.5 to 3.5 L per 1 kg of the washed nickel slime. When the amount of the hydroxide is less than 2.5 L, there is a problem of low fluorine removal rate. When the amount of the hydroxide is more than 3.5 L, the pH of the nickel slime is increased and nickel is precipitated and lost to increase the metal content of the hydroxide .

Next, a method for manufacturing a high-purity nickel slab from a high-concentration fluorine-containing nickel slurry according to the present invention comprises the steps of: (S20) injecting a nickel slime from which iron and fluorine have been removed into a high frequency induction furnace, .

At this time, the power is preferably applied in the range of 12 to 18 kW. When the power is applied less than 12 kW, there is a problem that the nickel slime is not melted. When the power is more than 18 kW, Fe and Cr are melted due to high temperature to increase impurities in the nickel plate.

The melting of the iron and fluorine-removed nickel slurry is preferably carried out by initially introducing a small amount of nickel slime into a high frequency induction furnace and melting the molten nickel slurry. This is because when the nickel slime is injected at once, only the portion to which the heat is applied is dissolved, the temperature is not transferred to the remaining portion, the remaining portion is not melted, and a space is formed between the portion where heat is applied and the portion where heat is not applied This is because there is a danger that the induction furnace can explode. In the present invention, 1 kg of the nickel slime was melted first, and then the nickel slime was continuously added thereto to put it to 2.5 kg or 2.79 kg.

Next, a method for producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slurry according to the present invention includes the step (S30) of pouring the molten nickel slime into a casting mold and cooling the molten nickel slurry.

The molten nickel slime can be poured into a casting mold, and the plate-like nickel can be produced through a cooling process such as water cooling and air cooling. At this time, the cooling can be cooled to room temperature.

The present invention also provides a method for producing a nickel slurry, comprising the steps of adding calcium hydroxide to a solution obtained by pickling and washing a nickel slurry, stirring and then solid-liquid separation;

Adding a carbonate to the solid-liquid separated solution, stirring the mixture, solid-liquid separation to recover nickel; And

And passing the solid-liquid separated solution through an ion exchange resin. The present invention also provides a method for treating a pickling and water washing liquid of a nickel slurry.

According to the present invention, the pickling of nickel slime and the treatment of the wash liquor can remove most of the fluorine, iron and chromium contained in the pickling and wash liquor of the nickel slime, and nickel can be further recovered, The tax amount can be reused and there is no risk of causing environmental pollution and discharge can be made.

2 is a flowchart showing a pickling method of a nickel slime and a method of treating a washing liquid according to the present invention. Hereinafter, the present invention will be described in detail with reference to Fig.

The pickling of nickel slime according to the present invention and the treatment method of the wash liquor include a step (S100) of adding calcium hydroxide to a solution obtained by pickling and washing the nickel slurry, stirring and then solid-liquid separation.

At this time, the solution containing the nickel slime pickled and washed contains 4700 ppm of nickel, 14300 ppm of fluorine, 3800 ppm of iron, and 158 ppm of chromium. Therefore, calcium hydroxide (Ca (OH) ₂ ) is added to remove fluorine contained in the solution obtained by pickling and washing the nickel slime, and the pH of the solution is increased due to OH of calcium hydroxide, so that iron and chromium can also be removed. The calcium hydroxide is preferably added in a molar ratio of 1: 1.0 to 2.0 with respect to fluorine (F ₂ ) contained in the pickled and washed solution. When the amount of the calcium hydroxide is less than 1.0 mol, the fluorine is not removed. When the amount of the calcium hydroxide is more than 2.0 mol, the nickel contained in the pickled and washed solution is liable to be lost when the pH is 8 or more .

The pH of the solution after the addition of calcium hydroxide is preferably 5 to 7, and when the pH of the solution rises above 7, nickel may precipitate and be lost as described above. Therefore, the concentration of sulfuric acid (H ₂ SO ₄ ) is added to adjust the pH.

Iron, and chromium contained in the pickling and wash liquor can be removed through a step of adding calcium hydroxide to the solution obtained by pickling and washing the nickel slime, stirring and then solid-liquid separation. In the solid-liquid separated solution, .

Next, the pickling of nickel slime according to the present invention and the treatment method of the washing liquid include a step (S200) of adding nickel carbonate to the solid-liquid separated solution, stirring the nickel carbonate slurry, and recovering nickel by solid-liquid separation.

Only the nickel is present in the solid-liquid separated solution, and the nickel is recovered as nickel carbonate (NiCO ₃ ) through the reaction with the carbonate.

The carbonate may be one selected from the group consisting of Na ₂ CO ₃ , CaCO ₃ and MgCO ₃ , and the carbonate is added in a molar ratio of 1.0 to 2.0 based on nickel (Ni) contained in the solid- . When the carbonate is added in an amount less than 1.0 mol, the nickel contained in the solid-liquid separated solution is insufficiently reacted, and the amount of nickel recovered is small. When the molar ratio exceeds 2.0, excess Na ions are present in the solution There is a problem in that a process of removing it must be additionally performed.

Next, the pickling and pickling solution treatment of the nickel slime according to the present invention includes passing the solid-liquid separated solution through the ion exchange resin (S300).

The solid-liquid separated solution contains a small amount of nickel, which can be removed through an ion exchange resin containing an iminodiacetic functional group, and the obtained solution can be reused as a solution for pickling and washing, Since the metal that can cause environmental pollution has been removed, it can be discharged.

Example 1: Preparation of high purity nickel plate 1

1. Removal of Fe and F

6.0 kg of nickel slime was added to 18 L of water and stirred, then the pH of the solution was adjusted to 3 to 5 by adding sulfuric acid, stirred for 1 hour and filtered. The filtered nickel slime was poured into 18 L of water, stirred for 1 hour, and then filtered. After water washing with water, the nickel slurry was added to 18 L of a 10 wt% NaOH solution, stirred for 1 hour, and then filtered. The filtered nickel slime was dried to give 5.29 kg of nickel slime.

2. Dry melting

1 kg of the dried nickel slime was put into a high frequency induction furnace and power was applied to 12 to 18 kW to melt the nickel slime. When the nickel slime started to be melted, the nickel slime was continuously supplied and the mixture was charged to 2.5 kg. The molten nickel slime was poured into a casting mold and cooled to prepare a high purity nickel plate.

Example 2: Preparation of high purity nickel plate 1

A high purity nickel plate was prepared in the same manner as in Example 1, except that the above-described dry-melting process was repeatedly performed to melt the nickel slurry to 2.79 kg to prepare a nickel plate.

Example 3 Recovery and Treatment of Nickel in Acidic and Aqueous Solutions

In Example 1, 18 L of an acidic solution containing sulfuric acid in distilled water and 18 L of a washing solution used in a washing process after the pickling were recovered.

Table 1 shows the kinds and contents of metals contained in 18 L of acid tax and 18 L of wash water. At this time, the pH of the 36 L acidic wash and wash solution was 2.90.

metal Ni F Fe Cr Content (ppm) 4700 14200 3800 158

1. F, Fe, Cr  remove

To remove the F contained in the 36 L of pickling and washing solution, 1327 g of F ₂ : Ca (OH) ₂ = 1: 1.5 molar ratio was added and stirred for 8 hours to obtain a final pH of 5 to 7. At this time, Fe and Cr could be removed when pH was increased due to OH of Ca (OH) ₂ and the pH became 5 or more. However, if the pH exceeds 7, nickel may precipitate and be lost, so that the pH is lowered by adding 10% H ₂ SO ₄ to adjust the pH to 7 or less.

The stirred pickling and washing solutions were separated by solid-liquid separation to remove impurities (F, Fe, Cr).

Table 2 shows the kinds and contents of metals contained in the pickling and washing liquid after solid-liquid separation.

metal Ni F Fe Cr Ca Content (ppm) 4500 One 2 0 570

As shown in Table 2, all of F, Fe, and Cr could be removed, and Ca could also be treated with sludge because of its low solubility.

2. Nickel Recovery

345.6 g of Na ₂ CO ₃ was added to the pickling and washing solution from which the impurities had been removed to a molar ratio of Ni: Na ₂ CO ₃ = 1: 1.3, stirred for 2 hours, and then subjected to solid-liquid separation to recover NiCO ₃ .

Table 3 shows the kinds and contents of metals contained in the filtrate remaining after recovery of recovered nickel carbonate and nickel carbonate.

metal Ni F Fe Cr Ca Nickel carbonate (ppm) 181500 15 79 0 570 Filtrate (ppm) 490 One 0 0 315

3. Filtration

The remaining filtrate after the recovery of NiCO ₃ was passed through an ion exchange resin with iminoacetic functional groups to remove remaining Ni in the filtrate and reused or discharged as a process solution.

Table 4 shows the kinds and contents of the metals remaining in the filtrate after passing through the ion exchange resin.

metal Ni F Fe Cr Ca Content (ppm) One One 0 0 217

Experimental Example 1: Analysis of kinds and contents of metals contained in the nickel slime and nickel plate produced in stages

The types and contents of the metals contained in the nickel slime, the water bath, the nickel slime after the pickling, and the nickel plate after the dry melting in the method of producing the high purity nickel plate from the nickel slime containing the high concentration fluorine according to the present invention were analyzed, Table 8 shows the results.

Table 5 shows the types and contents of the metals contained in the nickel slime. The weight of the nickel slime was 6000 g and Ni was 4920 g.

unit weight% ppm metal Ni F Fe Cr Other content 82.00 97474 75260 1276 12068

Table 6 shows the kinds and contents of metals contained in the nickel slime after pickling and water washing. After the pickling and washing, the weight of nickel slime was 5290 g and Ni was 4769 g.

unit weight% ppm metal Ni F Fe Cr Other content 90.15 20410 62130 489 15494

As shown in Table 6, the content of F was significantly lowered from 97474 ppm to 20410 ppm in the pickling and washing process.

Tables 7 and 8 below show the types and contents of metals contained in the nickel plate produced after dry-melting.

unit weight% ppm metal Ni F Fe Cr Other content 98.45 451 14380 0 600

2500 g of nickel slime was charged and dry-melted to prepare 2260 g of nickel plate, and the content of nickel contained in the nickel plate was 2225 g.

unit weight% ppm metal Ni F Fe Cr Other content 98.19 197 17300 0 635

2790 g of nickel slime was charged and dry melted to prepare 2556 g of nickel plate. The content of nickel contained in the nickel plate was 2509 g.

Experimental Example 2: Analysis of nickel recovery

The recovery rate of nickel in each step in the process for producing a high-purity nickel plate from the high-concentration fluorine-containing nickel slurry according to the present invention was examined, and the results are shown in Table 9 below.

Kinds Weight (g) Ni amount (g) Recovery rate (%) Nickel slime 6000 4920 100 Nickel carbonate 705 128 2.6 Nickel plate 4816 4734 96.2 Sum - 4862 (128 + 4734) 98.8

As shown in Table 9, 128 g of NiCO ₃ can be recovered by adding Na ₂ CO ₃ from the pickling and washing solution from which the impurities have been removed, and the nickel slime is dry-melted to recover 4734 g of nickel, The recovered nickel can be recovered to 96.2%, and nickel can be recovered as 98.8% from the nickel slime as a whole.

Although the present invention has been described with respect to the method for producing a high-purity nickel plate from a high-concentration fluorine-containing nickel slurry according to the present invention and the method for treating a nickel slime with a pickling agent and a water washing solution, It is evident that alternative embodiments are possible.

Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.

It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.

Claims (10)

The nickel slime containing 10 to 12 wt% of fluorine and 6 to 8 wt% of iron is picked and washed with water, and one kind of hydroxide solution selected from the group consisting of NaOH, Ca (OH) ₂ and KOH is added, Removing iron and fluorine contained in the nickel slurry;
The nickel slime from which the iron and fluorine are removed is put into a high frequency induction furnace, and then a power of 12 to 18 kW is applied to melt the nickel slime; And
And pouring the molten nickel slime into a casting mold and cooling the molten nickel slurry.
The method according to claim 1,
Wherein the pickling is carried out by adding distilled water to 2.5 to 3.5 L per 1 kg of nickel slurry, stirring the mixture, adding an acid, and filtering the nickel slurry.
The method according to claim 1,
Wherein the pickling is carried out at a pH of from 3 to 5. < RTI ID = 0.0 > 11. < / RTI >
The method according to claim 1,
Wherein the washing is carried out by adding distilled water to 2.5 to 3.5 L per 1 kg of pickled nickel slurry, stirring, and then filtering the nickel slurry.
The method according to claim 1,
Wherein the hydroxide solution is added in an amount of 2.5 to 3.5 L per 1 kg of the washed nickel slime.
delete Adding a calcium hydroxide to a solution obtained by pickling and washing a nickel slurry, stirring and then solid-liquid separation;
Adding a carbonate to the solid-liquid separated solution, stirring the mixture, solid-liquid separation to recover nickel; And
Passing the solid-liquid separated solution through an ion exchange resin,
Wherein the calcium hydroxide is added in a molar ratio of 1: 1.0 to 2.0 with respect to fluorine (F ₂ ) contained in the pickled and washed solution.
delete 8. The method of claim 7,
Wherein the carbonate is one selected from the group consisting of Na ₂ CO ₃ , CaCO ₃ and MgCO ₃ .
8. The method of claim 7,
Wherein the carbonate is added in a molar ratio of 1: 1.0 to 2.0 with respect to nickel (Ni) contained in the solid-liquid separated solution.

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