KR20160101203A - Treatment method for electroless nickel plating solution - Google Patents

Abstract

A method of treating a chemical nickel plating solution provided by the present invention includes the following steps. Powder production using chemical nickel plating aging solution; Agitation of the chemical nickel plating aging solution with the powder continuously during the powder coating process and the solution containing sodium hypophosphite added is heated so that the chemical nickel aging solution changes from a blue to a white transparent solution rich in nickel Stir again and heat. Highly oxidized, produced nickel hydroxide white precipitate is filtered and precipitated, then dissolved in the next chemical nickel plating aging solution and reused. Continue the advanced oxidation of the treated solution through the previous step. The amount of nickel in the aged waste liquid treated through the process of the present invention is reduced to 1 mg / L or less so that 99.9% or more of nickel can be recycled and a functional powder material having relatively high added value can be produced. Pollution can also be prevented.

Description

TECHNICAL FIELD [0001] The present invention relates to a nickel plating solution,

The present invention belongs to the surface treatment and wastewater treatment technology areas, and in particular, relates to a method for treating an aging liquid for electroless nickel plating.

Conventional chemical nickel plating process is mainly for regenerating the aging liquid, and the treatment method is as follows.

1. The main chemical pump, the calcium carbonate treatment bed, the settling tank, and the filter pump included in the regeneration treatment device of the chemical nickel plating solution are connected in order through the pipe, ammonia is added to the precipitation tank in the ammonia supplement tank, The nickel plating solution in the plating tank is pumped to the calcium carbonate filter bed, and the chemical nickel plating solution after the filter pump treatment is returned to the chemical nickel plating tank.

2. A regenerated chemical nickel plating solution is obtained by crystallizing sodium sulfate and sodium phosphite, which are by-products of chemical nickel plating solution, in a solution by cooling the chemical nickel plating solution in which nickel sulfate is the main salt and the reducing agent is sodium hypophosphite, The chemical nickel plating solution obtained by the action contains an abundance of byproducts such as sodium sulfate and sodium phosphite, thereby restoring the deposition rate of the aged chemical nickel plating solution.

3. After adjusting the pH value of the chemical nickel plating aging solution and electrodialysis for 1 to 8 hours at a constant temperature and current density, the aging solution can be used immediately after replenishing the components. The concentrate after the electrodialysis treatment is subjected to a chemical precipitation treatment, and the material is agitated for 1 to 8 hours with stirring at an appropriate ratio.

The above is a technical method for treating the old chemical nickel plating aging waste liquid. When the above method is used, the aged chemical nickel plating solution can be reused after regenerating. However, first, the chemical nickel plating solution regenerated by this method is a nickel plating layer The quality of the coating layer can not be guaranteed due to a certain influence on the quality of the coating layer, and it can not be utilized in production fields with high plating layer technology requirements. Second, this processing method generates new waste and still causes environmental pollution.

An object of the present invention is to solve the problem that the quality of the plating layer of the chemical nickel plating existing in the conventional method of treating chemical nickel plating with aging wastes can not be guaranteed by providing a method of treating the chemical nickel plating solution.

It is another object of the present invention to solve the problem of causing environmental pollution due to the generation of new wastes existing in the conventional method of treating chemical nickel plating aging waste liquid.

In order to achieve the above object, the present invention uses the following technique.

The method of treating the chemical nickel plating solution includes the following steps.

a. Chemical Nickel Plating Powder production using aging liquid: chemical nickel plating The aging liquid is pumped into a container capable of stirring and heating continuously, and the surface chemical vapor deposition is carried out using a chemical nickel plating aging solution as a raw material and using a chemical nickel plating aging solution Coating is applied to the surface of the powder that can be processed to produce a nickel-coated powder.

b. During the powder coating process, the chemical nickel plating aging solution with the powder is continuously stirred and heated to maintain the temperature at 80 to 92 ° C., and the pH value is stably controlled between 4.5 and 7.5 by adding an alkali solution, and sodium hypophosphite After the solution containing the nickel nickel plating solution was replenished, the nickel nickel plating solution was changed from a blue to white transparent solution containing nickel, stirred again and heated for 2 hours or longer to reduce the nickel ion concentration in the solution to 20 mg / L or less, The powder is separated, washed with water and dried.

c. After cooling the solution treated in step b, the solution is continuously oxidized continuously for 1 hour or more, the pH value is adjusted between 8 and 9 by adding an alkali solution, and the produced nickel hydroxide white precipitate is filtered to obtain the next chemical nickel plating aging solution And reuse it. Through this process, the nickel ion content in the treated solution is reduced to 1 mg / L or less.

d. Continue advanced oxidation of the treated solution through step c until the pH value stabilizes between 6.5 and 7.5 without adding the alkali solution.

Preferably, the powder capable of undergoing the surface chemical vapor deposition is one kind of ceramic powder which has been subjected to iron powder, iron alloy powder and nonmetal surface metallization pretreatment.

Preferably, in step a, the nickel ion concentration in the chemical nickel plating aging solution is first analyzed prior to the powder coating process, and the weight of the nickel contained in the solution is determined through volume determination of the chemical nickel plating aging solution. The powders can be weighed to produce powders with optional setting ratios of 0.1% to 80% nickel content, if desired.

Preferably, the powder particle size in step a is between 1 nanometer and 200 microns.

Preferably, the process of treating the ceramic powder with the non-metal surface metallization pretreatment in step a is one of harmonizing, sensitizing, activating or coordinating, sensitizing and activating.

Preferably, the ceramic powder in step a is a ceramic powder containing one or more of aluminum oxide, zirconium dioxide, titanium dioxide, and silicon dioxide.

Specifically, when the powder capable of performing the surface chemical vapor deposition is iron or iron alloy powder, the nickel-coated powder to be produced can be used as a raw material in the fields of powder metallurgy and the like. When the powder capable of surface chemical vapor deposition is a ceramic powder , The nickel-coated powder produced can be used as a raw material for functional materials such as conductive and absorbent materials.

Preferably, the advanced oxidation in steps c, d is one or more of the H ₂ O ₂ + UV system, the O ₃ + UV system, and the O ₃ + catalyst water treatment method.

Specifically, if the alkali solution of step b, c or d is a potassium hydroxide or potassium carbonate solution, the aged solution after the treatment is used as a raw material for the liquid composite fertilizer, or the alkali solution may be sodium hydroxide or sodium carbonate solution or the alkali solution may be calcium hydroxide Or calcium oxide powder, the precipitate formed is used as a raw material for the phosphoric acid fertilizer after the separation, and the waste water can be sent to the sewage treatment plant for further treatment.

Specifically, the liquid that comes with the parts of the chemical nickel plating is supplemented as evaporation water through the second recovery of the side of the barrel, the rinsing water is reused as clear water through the membrane separation, and the concentrate is mixed with the aging liquid and treated.

The nickel in the aged waste solution can be lowered to 1 mg / L or less, so that more than 99.9% of the nickel can be recycled and the functional powder material having a relatively high added value can be produced. Pollution can also be prevented. Hyphophosphates and phosphites contained in the remaining aging waste solution are formed into phosphates through a high-grade oxidation process and can be conveniently used as raw materials for fertilizer. The present invention realizes comprehensive utilization of resources and also prevents environmental pollution.

The following is a detailed description of the present invention through a concrete implementation method.

A method of treating a kind of chemical nickel plating solution, comprising the following steps.

a. Production of powder using chemical nickel plating aging solution: First, the nickel ion concentration in the chemical nickel plating aging solution is analyzed, and the weight of the nickel contained in the solution is determined through the volume determination of the chemical nickel plating aging solution. The powders can be weighed to produce powders having an arbitrary set ratio of nickel content of 0.1% to 80%, if necessary. The chemical nickel plating aging solution is pumped into a container capable of stirring and continuously heated, and a chemical nickel plating aging solution is used as a raw material and coated on the surface of a powder capable of performing surface chemical vapor deposition using a chemical nickel plating aging solution, Nickel-coated powder. Preferred particle sizes are between 1 nanometer and 200 microns. Preferred powders capable of undergoing surface chemical vapor deposition are ceramic powders that have been subjected to an iron powder, an iron alloy powder, and a nonmetal surface metal pretreatment, and the ceramic powder is a ceramic powder containing one or more of aluminum oxide, zirconium dioxide, titanium dioxide, Powder. Nonmetallic surfaces The processing of ceramic powders that have undergone metal pretreatment is one of harmonizing, sensitizing, activating or coordinating, sensitizing and activating.

The nickel-coated powder produced when the powder capable of conducting the surface chemical vapor deposition is made of iron powder or iron alloy powder is used as a raw material for powder metallurgy and the nickel coating produced when the powder capable of surface chemical vapor deposition is a ceramic powder Powders are used as raw materials for functional materials such as conductive and absorbing materials.

b. During the powder coating process, the chemical nickel plating aging solution with the powder is continuously stirred and heated to maintain the temperature at 80 to 92 ° C., and the pH value is stably controlled between 4.5 and 7.5 by adding an alkali solution, and sodium hypophosphite The solution containing the nickel nickel plating solution was replenished so that the nickel nickel plating solution was changed from a blue to a white transparent solution containing nickel, stirred again and heated for 2 hours or more to reduce the nickel ion concentration in the solution to 20 mg / L or less, The powder is separated, washed with water and dried.

c. After cooling the solution treated in step b, the solution is continuously oxidized continuously for 1 hour or more, the pH value is adjusted between 8 and 9 by adding an alkali solution, and the produced nickel hydroxide white precipitate is filtered to obtain the next chemical nickel plating aging solution And reuse it. Through this process, the nickel ion content in the treated solution is reduced to 1 mg / L or less.

d. The treated solution is continuously advanced oxidized through step c until the pH value is stabilized between 6.5 and 7.5 without addition of an alkali solution, and the treated solution can be sold as a raw material for liquid compound fertilizer.

Advanced oxidation in steps c and d is one or several of water treatment methods of H ₂ O ₂ + UV system, O ₃ + UV system and O ₃ + catalyst, Free radicals to oxidize phosphorus in a low valence state to a high valence state and rapidly decompose the organic matter in the solution.

If the alkali solution in steps b, c, and d is a potassium hydroxide or potassium carbonate solution, the aged solution after the treatment is used as a raw material for the liquid composite fertilizer. Or if the alkali solution is sodium hydroxide or sodium carbonate solution, or if the alkali solution is calcium hydroxide or calcium oxide powder, the precipitate formed is used as a source of phosphoric acid fertilizer after separation and the wastewater can be sent to the sewage treatment plant for further treatment.

The liquid which comes with the parts of the chemical nickel plating is supplemented as evaporation water through the secondary recovery of the side of the barrel, the rinsing water is reused as clear water through the membrane separation, and the concentrate is mixed and mixed with the aging liquid.

Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention can be more fully understood by reference to the following examples. However, it will be readily understood by those skilled in the art that the description set forth in the examples is merely an illustration of the invention and is not intended to limit the invention to the detailed description of the claims.

Example 1

A 500 L acidic chemical nickel plating solution of 6 circulation cycles was pumped into a container larger than 500 L and the nickel ion concentration was chemically analyzed at 0.075 M to calculate the total nickel contained in the solution = 58.69 * 0.075 * 500 = 2200.875 g, Nickel-coated iron powder containing about 75% of iron is prepared, and the solution is heated and stirred. 7 kg of 500 mesh iron is added, the pH value is adjusted to about 7 with 20% potassium hydroxide solution, When 10 kg of sodium hypophosphite is released, slowly add the sodium hypophosphite solution into the solution. If the solution turns into a transparent white clear solution, continue stirring for more than 2 hours and maintain the temperature at 85 to 90 ° C. After cooling, the solution is filtered to rinse the powder When dried and packaged, it becomes a nickel-phosphorus alloy coated iron powder weighing 9.3 kg, which can be sold and used as part of a nickel powder in the powder metallurgy industry.

Analysis of the filtered solution can be used continuously for circulation treatment of one "more" sewage treatment plant with a nickel content of 13 mg / L and model NR150 / 4-240P12. The instrument uses four catalytic reactors, Model R150, with an ozone generator of 120 g / h and a circulating flow rate of 12 m ³ / h. Adjusting the pH value to 8 to 9 with a 20% potassium hydroxide solution can maintain the ozone catalytic oxidation time of the NR150 / 4-120P10 "more" sewage treatment system to 2 to 3 hours, Once the white precipitate has been separated, the ozone catalyzed oxidation can proceed until the pH value is no longer maintained at about 7 by adding it to the next chemical nickel plating aging solution. If the content of P and K in the solution exceeds 5%, it can be used as a raw material after being cooled to the compound fertilizer producer.

In this embodiment, the same effect can be obtained by replacing the iron powder with the iron alloy powder and replacing the potassium hydroxide solution with the potassium carbonate solution.

The ozone catalytic oxidation method may be one of or a combination of the H ₂ O ₂ + UV system, the O ₃ + UV system, and the water treatment method of the O ₃ + catalyst.

Example 2

A 300 L acidic chemical nickel plating solution of 6 circulation cycles was pumped into a vessel larger than 300 L and the nickel ion concentration was chemically analyzed at 0.06 M to calculate the total nickel contained in the solution = 58.69 * 0.06 * 300 = 1056.42 g, Nickel-coated ceramic powder containing about 35% nickel-phosphorus alloy is planned and manufactured. 2.1kg of 200-mesh aluminum oxide powder is put into the powder. 50% H ₂ SO ₄ + 5% HF solution for 20 minutes - Water wash - 15 g / L SnCl ₂ + 50 ml / L HCl solution for 10 minutes - Water wash - 1 g / L PdCL solution for 2 minutes - Water wash.

Heat the mixed solution and keep the pH value at 6.5 by using 20% potassium hydroxide solution. If a large amount of bubbles are released in the solution, a total of 5.5 kg of sodium hypophosphite is slowly added to the solution. When the solution turns into a clear white transparent solution, stirring is continued for 2 hours or more and the mixture is stirred at 85 to 90 ° C. Keep the temperature. After cooling, the solution is filtered to rinse the powder and dry to provide a 3.2 kg weight nickel-phosphorus alloy ceramic coating powder. If the powder has a measured volume resistivity of 0.015 Ω m, an antistatic coating may be added to replace the nickel powder.

Analyzing the filtered solution, the nickel content is 11 mg / L and can be used continuously for the circulation treatment of one "more" wastewater treatment machine with model NR150 / 2-60P5. The instrument uses two catalytic reactors, model R150, with an ozone generator of 60 g / h and a circulation pump flow of 5 m ³ / h. Adjusting the pH to 8 to 9 with a 20% potassium hydroxide solution can maintain the ozone catalytic oxidation time for the NR150 / 2-60P5 "more" wastewater treatment solution to 3 hours, and the white precipitate Can be added to the next chemical nickel plating aging solution, and the content analysis on the solution is 0.7 mg / L. Continuous ozone catalytic oxidation is carried out and the calcium hydroxide solution is used to hold the solution until the pH value exceeds 7 and the pH value is no longer dropped so that a large amount of precipitate is formed in the solution. The filtered water is sent to the drain pipe, Dispose of solid.

In this embodiment, when the aluminum oxide powder is replaced with a ceramic powder containing one or more of aluminum oxide, zirconium dioxide, titanium dioxide and silicon dioxide, and sodium hydroxide is replaced with sodium carbonate, the same technical effect as that of the present embodiment is obtained .

The ceramic powder is obtained through one pretreatment process such as harmonization, sensitization, activation, co-ordination, sensitization and activation.

Example 3

The potassium hydroxide solution of Example 1 can be replaced with a calcium hydroxide solution or calcium oxide to separate the precipitate formed and then used as a raw material for the phosphoric acid fertilizer, and the waste water can be sent to the sewage treatment plant for further treatment.

The liquid which comes out with the parts of the chemical nickel plating is supplemented as evaporation water through the secondary recovery of the side of the barrel, the rinse water is reused as clear water through the membrane separation, and the concentrate is treated by mixing with the aging liquid.

Claims (10)

A method of treating a chemical nickel plating solution, comprising:
a. Production of powder using chemical nickel plating aging solution: Chemical nickel plating The aging solution is pumped into a container capable of being stirred and continuously heated, and subjected to surface chemical vapor deposition (CVD) using chemical nickel plating aging solution as a raw material, To produce a nickel-coated powder;
b. During the powder coating process, the chemical nickel plating aging solution with the powder is continuously stirred and heated to maintain the temperature at 80 to 92 ° C., and the pH value is stably controlled between 4.5 and 7.5 by adding an alkali solution, and sodium hypophosphite The solution containing the nickel nickel plating solution is replenished so that the nickel nickel plating solution is changed from a blue to white transparent solution containing nickel and then stirred again and heated for 2 hours or longer to reduce the nickel ion concentration in the solution to 20 mg / Separating, washing and drying the powdered product;
c. After cooling the treated solution in step b, the solution is continuously oxidized for 1 hour or more, the pH value is adjusted to 8 to 9 by adding an alkali solution, and the produced nickel hydroxide white precipitate is filtered to obtain the next chemical nickel plating aging solution And reducing the nickel ion content in the treated solution to 1 mg / L or less through the process; And
d. Continuously advanced oxidation of the treated solution through step c until the pH value stabilizes between 6.5 and 7.5 without the addition of an alkali solution. The method according to claim 1,
Wherein the powder capable of performing the surface chemical vapor deposition is one of iron powder, iron alloy powder, and ceramic powder subjected to pretreatment of non-metal surface metallization. The method according to claim 1,
In step a, before the powder coating process, the nickel ion concentration in the chemical nickel plating aging solution is first analyzed, and the nickel weight contained in the solution is calculated by determining the chemical nickel plating aging liquid volume, and the weight of the powder to be added is calculated To produce a powder having an arbitrary set ratio of nickel content of 0.1% to 80%, if necessary. 3. The method according to claim 1 or 2,
Wherein a powder particle size in step (a) is from 1 nanometer to 200 microns. 3. The method of claim 2,
Wherein the step of treating the ceramic powder subjected to the pretreatment of the non-metal surface metal in step (a) is one of harmonization, sensitization, activation or harmonization, sensitization and activation. 6. The method according to claim 2 or 5,
Wherein the ceramic powder in step (a) is a ceramic powder containing one or more of aluminum oxide, zirconium dioxide, titanium dioxide, silicon dioxide, and the like. 3. The method according to claim 1 or 2,
In step a, the nickel-coated powder produced when the powder capable of surface chemical vapor deposition is iron powder or iron alloy powder can be used as a raw material in powder metallurgy,
Wherein the nickel-coated powder produced when the powder capable of performing surface chemical vapor deposition is a ceramic powder can be used as a raw material for a functional material such as a conductive or absorbent material. The method according to claim 1,
Characterized in that said advanced oxidation in steps c and d is one or several of the water treatment processes of the H ₂ O ₂ + UV system, the O ₃ + UV system, and the O ₃ + catalyst. The method according to claim 1,
When the alkali solution in steps b, c and d is a potassium hydroxide or potassium carbonate solution, the aging solution after the treatment is used as a raw material for the liquid composite fertilizer, or
Characterized in that when the alkali solution is sodium hydroxide or sodium carbonate solution or when the alkali solution is calcium hydroxide or calcium oxide powder, the formed precipitate can be used as a raw material for the phosphoric acid fertilizer after the separation, and the waste water can be continuously sent to the sewage treatment plant METHODS FOR PROCESSING AGING LIQUIDS OF CHEMICAL. The method according to claim 1,
Characterized in that the liquid with the components of the chemical nickel plating is supplemented as evaporation water through the secondary recovery of the side of the tube and the rinsing water is reused as clear water through the membrane separation and the concentrate is mixed and mixed with the aging liquid A method for treating a nickel plating solution.