JP2009228030A - Method for recovering residual nickel in electroless plating waste solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for recovering a nickel ion from an electroless plating waste solution as nickel compound, whose phosphorus content is ≤100 mg/Kg and which is recyclable as resources. <P>SOLUTION: This method for recovering the nickel source comprises: a regenerating process (A) of the selective heavy metal chelate resin filled up into a column; an adjusting process (B) of the electroless nickel plating waste solution; an adsorption-eluting process (C) for eluting the nickel with inorganic acid after absorbing the nickel ion to the chelate resin by bringing the nickel plating waste solution adjusted in the process (B) into contact with the chelate resin regenerated in the process (A); and a nickel recycling process (D), in which non-soluble nickel compound is precipitated by adding carbonate or alkali hydroxide or oxalic acid of ≥1 equivalent to the nickel salt water solution eluted in the process (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a method for recovering nickel ions remaining in a plating bath waste liquid discharged from an electroless nickel plating process as nickel resources.

  Since the electroless nickel plating bath consists of a reducing agent phosphate and a complexing agent such as malic acid, as the nickel plating reaction proceeds, these components of the plating bath age and the plating reactivity decreases. In order to continue the plating reaction, it is necessary to replace it with a new plating bath. As a result, the resulting aged plating waste liquid is rendered harmless and discarded.

  However, nickel ions still remain in the nickel plating waste liquid, and the concentration thereof is several thousand mg / l in 1 liter of the waste liquid.

  Thus, various methods for recovering residual nickel ions in the electroless nickel plating waste liquid have been studied.

  For example, after an electroless nickel plating waste solution is brought into contact with a chelate resin to adsorb nickel ions to the resin and separated from the waste solution, nickel is eluted with hydrochloric acid or sulfuric acid, and excess acid in the eluted nickel solution is prepared separately. A method of neutralizing with nickel hydroxide or the like, recovering as nickel chloride or nickel sulfate (in the case of sulfuric acid elution), and reusing (column [0011] in Patent Document 1), contact between electroless nickel plating aging solution and nickel powder A method of separating and recovering nickel ions in the aging solution as nickel metal by performing an electroless plating reaction (Claim 1 of Patent Document 2) or a hypophosphite as a reducing agent and a complexing agent To the chemical nickel plating aging waste liquid using organic acid, oxalic acid is added to make it acidic at pH 1 to 3, and the nickel ions complexed with the organic acid in the aging waste liquid are insoluble. There is a method of recovering nickel from a waste solution of a chemical nickel plating bath characterized in that it is precipitated as nickel oxalate and simultaneously recovered as nickel oxalate with a low phosphorus content (claim 1 of Patent Document 3), etc. .

JP-A-11-226596 [0011] column JP-A-9-176861 Claim 1 JP-A-59-185770 Claim 1

  In the above-mentioned Patent Document 3, “In the method of recovering nickel from nickel plating aging waste liquid, it is a problem and important to make it easy to filter the precipitate and to reduce the inclusion of phosphorus component in the recovered nickel as much as possible. It is important to separate and recover nickel by eliminating the contamination of the phosphorus component, as described in “3. Columns 31 to 35 of Patent Document 3”. The reason is that if a phosphorus component is mixed in the recovered nickel compound, it is difficult to regenerate it as a nickel resource.

  However, it is difficult to say that the conventional method is sufficient as a method for recovering nickel ions in the waste liquid by eliminating the mixing of phosphorus components.

  That is, the method of the above-mentioned patent document 1 is a method of reusing "the nickel adsorbed by the chelate resin is recovered as nickel chloride or nickel sulfate by dissolution with an acid" (Patent Document 1 [0011] column). The method of Patent Document 2 describes that “electroless plating reaction is performed by contacting an electroless nickel plating aging solution and nickel powder, and nickel ions in the aging solution are separated and recovered as nickel metal” (Patent Document 2). Claim 1) A method, and any method describes a method of recovering nickel. However, since the purpose of recovering nickel is to detoxify the plating aging waste liquid, there is no description or suggestion about recovering nickel by eliminating the inclusion of phosphorus components.

  On the other hand, the above-mentioned patent document 3 is a method of recovering nickel from nickel plating waste liquid as a resource. However, the phosphorus content in the nickel oxalate that can be recovered by this method is “the phosphorus concentration in nickel oxalate (percentage of P / Ni) is 0.8% in the state of filtration and 100 ml per gram of nickel oxalate. What is washed with water is about 0.1%, and about 200% with 200 ml "(Patent Document 3: upper left column, page 9, lines 9 to 13), which can reduce the phosphorus content. Is 0.05% (500 mg / Kg), which is still not enough.

  Therefore, an object of the present invention is to provide a method for recovering resources of residual nickel ions in a nickel plating waste liquid as a nickel compound having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg.

  The technical problem can be achieved by the present invention as follows.

  That is, the present invention relates to a method for recovering residual nickel ions from an electroless nickel plating waste liquid, a regeneration step (A) of the selective heavy metal chelate resin packed in the column, and an adjustment step (B) of the electroless nickel plating waste liquid. Then, the nickel plating waste solution adjusted in the step (B) is brought into contact with the chelate resin regenerated in the step (A) to adsorb nickel ions to the chelate resin, and then nickel is eluted with a mineral acid. By a method comprising the step (C) and a nickel recovery step (D) for precipitating an insoluble nickel compound by adding carbonate, alkali hydroxide or oxalic acid to the nickel salt aqueous solution eluted in the step (C), Recovering an insoluble nickel compound having a phosphorus content of 0.1 mg / kg to 100 mg / kg from the electroless nickel plating waste solution A recovery method of electroless plating waste liquid residual nickel, wherein (present invention 1).

  Further, in the present invention, in the step (A), after the selective heavy metal chelate resin is converted to H type with sulfuric acid, 30 to 50% of the H type is replaced with Na type using an aqueous sodium hydroxide solution and mixed. Thus, the recovery method according to the first aspect of the present invention is a chelating resin regeneration step in which 30 to 50% of the total resin amount is an Na-type HNa mixed bed type chelating resin (Invention 2).

  Further, in the present invention, in step (B), after adding water to the raw waste liquid to dilute it into an aqueous solution having a nickel concentration of 500 mg / l to 1000 mg / l, the pH value is set to 4.0 using a mineral acid or alkali. It is the collection | recovery method of this invention 1 which is the adjustment process of the nickel plating waste liquid adjusted to thru | or 6.0 (this invention 3).

  Further, in the present invention, after step (C), nickel is adsorbed on the chelate resin at 20 to 30 g / l per liter of resin, and then extruded until the residual phosphate ion concentration in the washing waste water is 1.0 mg / l or less. It comprises a nickel ion adsorption step for washing with water and an elution step for eluting nickel into the chelate resin adsorbing nickel using a mineral acid to obtain a nickel salt aqueous solution. The chelate resin after elution is a resin regeneration step (A). This is a recovery method according to the first aspect of the present invention, which is an adsorption and elution step of nickel to be recycled (Invention 4).

  In the present invention, the nickel salt aqueous solution obtained in step (D) is weighed in step (D), and 1 to 2 equivalents of sodium carbonate is added to the nickel salt aqueous solution to precipitate nickel carbonate. This is a recovery method according to the present invention 1, which is a step of recovering nickel as nickel carbonate powder having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg by filtration, washing with water and drying (Invention 5).

  In the present invention, the step (D) measures the nickel salt aqueous solution obtained in the step (C), adds 1 to 2 equivalents of sodium hydroxide to the nickel salt aqueous solution, and adds nickel hydroxide. After precipitation, 1-2 equivalents of sodium carbonate, sodium hydrogen carbonate or carbon dioxide gas is added to the nickel hydroxide precipitate to convert the nickel hydroxide into nickel carbonate. The recovery method according to the first aspect of the present invention, wherein the nickel is recovered as nickel carbonate powder having a content of 0.1 mg / Kg to 100 mg / Kg (Invention 6).

  In the present invention, the nickel hydroxide is obtained by measuring the nickel salt aqueous solution obtained in step (C) in step (D) and adding 1 to 2 equivalents of sodium hydroxide to the nickel salt aqueous solution. Is a recovery method according to the first aspect of the present invention, in which nickel is recovered as nickel hydroxide powder having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg by precipitation, filtration, washing with water and drying (the present invention) 7).

  Further, in the present invention, the step (D) measures the nickel salt aqueous solution obtained in the step (C) and precipitates nickel oxalate by adding 1 to 2 equivalents of oxalic acid to the nickel salt aqueous solution. The recovery method according to the first aspect of the present invention, wherein the nickel is recovered as nickel oxalate powder having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg by filtration, washing with water and drying (Invention 8).

  According to the method of the present invention, since residual nickel ions can be recovered from the electroless nickel plating waste liquid as a nickel compound having a phosphorus content of 0.1 to 100 mg / kg, the recovered nickel compound has a low phosphorus content. Can be easily converted to metallic nickel. The present invention also contributes to the recycling of the electroless nickel plating waste liquid that was the source of environmental pollution.

  The configuration of the present invention will be described in more detail as follows.

  FIG. 1 is a flow chart of a method for recovering residual nickel in electroless plating waste liquid according to the present invention.

  The step of regenerating the selective heavy metal chelate resin packed in the column (A: PRK), the step of adjusting the electroless nickel plating waste liquid (B: PCW), and the chelate resin regenerated in the step (A) to the step ( The nickel plating waste solution prepared in B) is brought into contact with the chelating resin to adsorb nickel ions, and then the nickel is eluted with a mineral acid (C: PNR). The nickel eluted in the step (C) Electroless nickel plating waste liquid by a method comprising a nickel recovery and resource recovery step (D: PMR) in which an insoluble nickel compound is precipitated by adding 1 to 2 equivalents of carbonate, alkali hydroxide or oxalic acid to an aqueous salt solution. Is used to recover an insoluble nickel compound having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg.

  The phosphorus content of the insoluble nickel compound to be recovered is set to 0.1 mg / Kg to 100 mg / Kg. When phosphorus is present as a component when the insoluble nickel compound is recycled as metallic nickel, the recycling is hindered (Patent Document 3). This is because the phosphorus content is required to be reduced as much as possible.

  According to the present invention, the phosphorus content of the insoluble nickel compound can be reduced to 100 mg / Kg or less. If the phosphorus content of the insoluble nickel compound exceeds 100 mg / Kg, the resource is adversely affected, and if it is less than 0.1 mg / Kg, the cost is too high, which is not preferable. A more preferable range of the phosphorus content of the insoluble nickel compound is 1 mg / Kg to 50 mg / Kg.

  FIG. 2 shows the regeneration step (A) of the selective heavy metal chelate resin. First, the entire selective heavy metal chelate resin (PRK1) packed in the column is regenerated to H type with sulfuric acid (PRK2), extruded with water and washed with water (PRK3), and then H type 30 with sodium hydroxide. Up to 50% is converted to Na type (PRK4), extruded with water, washed with water (PRK5), and then mixed and homogenized to regenerate HNa mixed bed type chelate resin (PRK6).

  The reason for regenerating the HNa mixed bed type is to increase the selective absorption of nickel ions. If the Na type exceeds 50% in the mixing ratio of the H type and the Na type, the nickel adsorptivity decreases, which is not preferable. If the Na type is less than 30%, the acidity in the resin decreases and the nickel regeneration region This is not preferable because A more preferable mixing ratio is 40 to 50%.

  FIG. 3 shows the electroless nickel plating waste liquid adjustment step (B). The nickel concentration of the electroless nickel plating waste liquid (WNM) is about 3000 to 6000 mg / l. Water is added to the raw waste solution (PCW1) to dilute it into an aqueous solution having a nickel concentration of 500 to 1000 mg / l (PCW2), and the pH value of the diluted solution is adjusted to 4.0 to 6. with sulfuric acid or sodium hydroxide. Adjust to 0 (PCW3).

If the concentration of nickel in the diluent exceeds 1000 mg / l, uniform adsorption of nickel ions becomes difficult, which is not preferable. A concentration of less than 500 mg / l is not preferable because the equipment becomes large. A preferred range for the nickel concentration of the diluent is 800 to 1000 mg / l.
The reason for adjusting the pH of the diluted solution to 4.0 to 6.0 is to efficiently adsorb nickel ions to the chelate resin. A more preferable range of the pH value of the diluted aqueous solution is 4.5 to 5.5.

  FIG. 4 shows the nickel ion adsorption and elution step (C). A nickel ion adsorption process in which 20 to 30 g of nickel is adsorbed per liter of the chelate resin (PNR1), and then the extruded phosphate rinse is performed until the residual phosphate ion concentration in the washing wastewater is 1.0 mg / l or less (PNR2) And an elution step (PNR3) in which nickel is eluted from the chelate resin adsorbing nickel using mineral acid to form a nickel salt aqueous solution, and the chelate resin after elution is recycled to the resin regeneration step (A) (PNR4). ).

In the present invention, 20 to 30 g of nickel is adsorbed to the HNa mixed bed chelate resin regenerated in the step (A) per 1 liter of resin because the adsorbed amount near 30 g is close to the adsorption saturation point of the chelate resin. Since efficiency falls, it is not preferable. A preferred adsorption amount is 20 to 25 g per liter of resin.
In addition, after the nickel is adsorbed, the concentration of phosphate ions remaining in the washing waste water is extruded to 1.0 mg / l or less, and is washed with water in order to reduce the phosphorus content and recover the nickel resources. The range is a phosphate ion concentration of 0.1 to 1.0 mg / l.
Moreover, the mineral acid used when eluting nickel from the chelate resin adsorbing nickel is preferably sulfuric acid or hydrochloric acid, more preferably sulfuric acid. This is because the chelate resin after elution of nickel is suitable for recycling to the regeneration step (A) to regenerate the H-type.

  FIG. 5 shows a step (D) of recovering nickel resources. The nickel salt aqueous solution obtained in step (C) is weighed (PMR1), and a predetermined amount of a precipitant (carbonate, alkali hydroxide or oxalic acid) is added to the nickel salt aqueous solution to precipitate insoluble nickel compounds. The nickel compound is recovered (PRD) through (PMR2), filtration (FT), water washing (WP), pasting (CP), and drying (DR).

  In the step (D) of the present invention 5, the nickel salt aqueous solution obtained in the step (C) is weighed, and 1 to 2 equivalents of sodium carbonate is added to the solution. The residual mineral acid in the nickel salt aqueous solution This is because the total amount of nickel ions is precipitated and recovered as nickel carbonate. Further, since nickel carbonate has excellent filterability, it is suitable for recovering resources of nickel compounds having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg by filtration, washing and drying by a conventional method.

  In the step (D) of the present invention 6, the nickel salt aqueous solution obtained in the step (C) is weighed, and after adding 1-2 equivalents of sodium hydroxide to the solution to precipitate nickel hydroxide, Furthermore, the addition of 1 to 2 equivalents of sodium carbonate, sodium hydrogen carbonate or carbon dioxide gas to the nickel hydroxide precipitate is because the nickel carbonate particles produced by conversion from the colloidal precipitate of nickel hydroxide are a nickel salt aqueous solution. It is larger than nickel carbonate particles produced directly from an aqueous solution by adding carbonate to it, and it is found that the crystallinity and particle size uniformity of the particles are good, and is suitable for the purpose of the present invention to reduce the phosphorus content. It is.

  In the step (D) of the present invention 7, the nickel salt aqueous solution obtained in the step (C) is weighed, and 1 to 2 equivalents of sodium hydroxide is added to the nickel salt aqueous solution. In (C), since the content of the phosphorus component is adjusted to 1.0 mg / l or less, if the produced nickel hydroxide is filtered, washed and dried by a conventional method, the phosphorus content is 0.1 mg / Kg. This is because nickel can be recovered and recovered as 100 to 100 mg / Kg nickel hydroxide powder.

  In the step (D) of the present invention 8, the nickel salt aqueous solution obtained in the step (C) is weighed, and 1 to 2 equivalents of oxalic acid is added to the nickel salt aqueous solution. ), The content of the phosphorus component is adjusted to 1.0 mg / l or less. Therefore, if the produced nickel oxalate is filtered, washed, and dried by a conventional method, the phosphorus content is 0.1 mg / Kg to 100 mg / l. This is because nickel can be recovered and recovered as Kg nickel oxalate powder.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.

  Phosphorus analysis was performed using an ion chromatograph (Dionex).

  The electroless nickel plating waste liquid discharged | emitted from the printed circuit board manufacturing process shown in following Table 1 was used for the Example.

  Moreover, Bayer (Levacit TP-207) was used for the selective heavy metal chelate resin.

<Example 1>
Chelating resin regeneration process (A)
The column is filled with 5 liters of selective heavy metal chelate resin (diameter 10 cm, height 64 cm), and 10 liters of sulfuric acid with a concentration of 10 wt. Replayed. Next, the extruded water was washed with 35 liters of pure water, and it was confirmed that the passing waste liquid became neutral. Next, using sodium hydroxide having a concentration of 4% by weight, the water flow rate was 25 liters / hr, and 5 liters were passed through to replace 50% of the H-type resin with Na-type. Next, after extruding and washing with 25 liters of pure water, both regenerated resins were stirred and mixed to form an HNa mixed bed type, and a selective heavy metal chelate resin tower was prepared.

Electroless nickel plating waste liquid adjustment process (B)
25 liters of waste liquid having the composition shown in Table 1 was collected, diluted 5 times with pure water, adjusted to pH value 5.5 with 5% by weight sodium hydroxide solution, and 125 liters of diluted aqueous solution. Got ready.

Nickel ion adsorption / elution process (C)
(Nickel ion adsorption process)
Using the selective heavy metal chelate resin tower prepared in the step (A), the diluted waste solution of the nickel plating waste solution prepared in the step (B) is passed at a rate of 25 liters / hr and after passing through the selective heavy metal chelate resin. Was maintained at 1 mg / l or less. After passing the entire amount of the liquid to be treated, the water is further passed using 35 liters of pure water, the liquid to be treated is extruded and the resin is washed, and PO ₂ ions, PO ₃ ions, malic acid, etc. The organic acid was discharged. After confirming that the phosphorus concentration in the washing solution was 1 mg / l or less, the water washing was terminated.
Drainage of the diluent and extrusion washing water that passed through the resin was discarded.

(Nickel elution process)
Nickel was eluted by passing water at a rate of 25 liters / hr using 10 liters of sulfuric acid having a concentration of 10% by weight to the chelate resin adsorbing nickel obtained in the nickel ion adsorption step. . After passing sulfuric acid, the mixture was further extruded and washed with 35 liters of pure water.
Water flow from the start of elution of nickel with sulfuric acid until the end of the extrusion water washing with pure water was collected, and a total amount of 50 liters of nickel sulfate aqueous solution was prepared using pure water.

Nickel resource recovery process (D)
To a 10 liter solution collected from the nickel sulfate aqueous solution obtained in the nickel elution step, 2.7 liter of a 10% by weight aqueous sodium carbonate solution was added and stirred at a temperature of 20 ° C. for 60 minutes. The solution had a pH value of about 8.3 and a green precipitate was obtained. The precipitate was filtered using a No5A filter paper, filtered and washed with pure water until no sulfate ion was observed using a barium chloride solution as an indicator, and then dried at a temperature of 80 ° C. The amount produced was 74 grams. As a result of analysis, the green product was nickel carbonate having a phosphorus content of 5 mg / Kg.

<Example 2> Nickel resource recovery step (D)
1.7 liters of sodium hydroxide having a concentration of 10% by weight was added to 10 liters of solution extracted from the nickel sulfate aqueous solution obtained in the nickel elution step of Example 1, and stirred at a temperature of 20 ° C. for 60 minutes. The solution had a pH value of about 10 and a green precipitate was obtained.
Next, while stirring this green colloid aqueous solution, carbon dioxide gas was blown at a rate of 1 liter per minute until the pH value reached 7.0. After about 60 minutes, since the pH value reached 7.0, the blowing of carbon dioxide gas was stopped. The green colloid turned into a green precipitate. The green precipitate was filtered using a No5A filter paper, filtered and washed with pure water until no sulfate ion was observed using a barium chloride solution as an indicator, and dried at a temperature of 80 ° C. The amount produced was 72 grams. As a result of analysis, the green product was nickel carbonate having a phosphorus content of 1 mg / Kg. As a result of observation, the crystal particles were large and had good filterability.

<Example 3> Nickel resource recovery step (D)
To a 10 liter solution collected from the nickel sulfate aqueous solution obtained in the nickel elution step of Example 1, 1.7 liter of sodium hydroxide having a concentration of 10% by weight was added and stirred at a temperature of 20 ° C. for 60 minutes. The solution had a pH value of about 10 and a green precipitate was obtained. The green precipitate was then filtered using No5A filter paper, filtered and washed with pure water until no sulfate ion was observed using a barium chloride solution as an indicator, and dried at a temperature of 100 ° C. The amount produced was 51 grams. As a result of analysis, the green product was nickel hydroxide having a phosphorus content of 6 mg / Kg.

<Example 4> Nickel resource recovery step (D)
To 10 liters of the solution extracted from the nickel sulfate aqueous solution obtained in the nickel elution step of Example 1, 1.2 liters of sodium hydroxide having a concentration of 10% by weight was added to adjust the pH to 2. While stirring at a temperature of 40 ° C., 0.7 liter of 5 wt% oxalic acid solution was added and stirred for 4 hours. A greenish white precipitate was obtained. Next, this greenish white precipitate was filtered using No5A filter paper, filtered and washed with pure water until no sulfate ions were observed using a barium chloride solution as an indicator, and then dried at a temperature of 100 ° C. The amount produced was 59 grams. As a result of the analysis, the greenish white product was nickel oxalate having a phosphorus content of 1 mg / Kg.

<Example 5>
10 g of nickel oxalate obtained in Example 4 was put in an airtight container and thermally decomposed in an electric furnace adjusted to 350 ° C. for 2 hours. As a result, 3.1 g of powdery off-white metallic nickel was obtained.

<Example 6>
Similar to <Example 1> except that 4 liters of sodium hydroxide was passed through 4 liters of water to replace 40% of the H-type resin with Na-type, and the chelate resin regeneration step (A), electroless nickel plating The waste liquid adjustment step (B) and the nickel ion adsorption / elution step (C) were sequentially performed to prepare a nickel sulfate aqueous solution having a total amount of 50 liters. The nickel resource recovery step (D) was performed in the same manner as in <Example 4> using 10 liters of the adjusted nickel sulfate aqueous solution. The amount of greenish white precipitate produced was 58 grams. As a result of the analysis, the greenish white product was nickel oxalate having a phosphorus content of 1.1 mg / Kg.

<Comparative Example 1>
5 liters of the waste liquid having the composition shown in Table 1 was sampled, and 0.05 liter of 10% by weight sulfuric acid was added to adjust the pH to 2. While stirring at a temperature of 40 ° C., 0.7 liter of 5 wt% oxalic acid solution was added and stirred for 4 hours. A greenish white precipitate was obtained. Next, this greenish white precipitate was filtered using No5A filter paper, filtered and washed with pure water using a barium chloride solution until no sulfate ions were observed, and then dried at a temperature of 100 ° C. The amount produced was 61 grams. As a result of the analysis, the greenish white product was nickel oxalate having a phosphorus content of 3500 mg / Kg.

<Comparative Example 2>
Five liters of the waste liquid having the composition shown in Table 1 was collected and diluted five-fold with pure water. The pH was adjusted to 2 by adding 0.05 liter of 10% by weight sulfuric acid. While stirring at a temperature of 40 ° C., 0.7 liter of 5 wt% oxalic acid solution was added and stirred for 4 hours. A greenish white precipitate was obtained. Next, this greenish white precipitate was filtered using No5A filter paper, filtered and washed with pure water using a barium chloride solution until no sulfate ions were observed, and then dried at a temperature of 100 ° C. The amount produced was 58 grams. As a result of analysis, the greenish white product was nickel oxalate having a phosphorus content of 710 mg / Kg.

  According to the method of the present invention, the residual nickel ions can be recovered from the electroless nickel plating waste liquid as a nickel compound having a phosphorus content of 1 mg / kg or less. There is an effect that can be easily converted to nickel. The present invention also contributes to the recycling of the electroless nickel plating waste liquid that was the source of environmental pollution.

Process chart showing an outline of the nickel recovery method of the present invention Process chart showing chelating resin regeneration process (A) Process diagram showing adjustment process (B) of electroless nickel plating waste liquid Process chart showing nickel adsorption and elution process (C) Process chart showing nickel resource recycling process (D)

Explanation of symbols

PRK: Chelate resin regeneration process PRK1: Chelate resin column PRK2: H type regeneration process PRK3: Extrusion and water washing process PRK4: Na type regeneration process PRK5: Extrusion and water washing process PRK6: Resin mixing process WWR: Waste water treatment process PCW: Electroless Nickel plating waste liquid adjustment process PCW1: Waste liquid receptacle PCW2: Nickel concentration adjustment process PCW3: pH value adjustment process PNR: Nickel adsorption / elution process PNR1: Nickel adsorption process PNR2: Extrusion and water washing process PNR3: Nickel elution process PNR4: Chelate resin recovery Process WWB: Phosphorus-containing waste liquid treatment process PMR: Nickel resource recycling process PMR1: Measuring tank for nickel salt aqueous solution PMR2: Reaction tank PRD: Nickel compound WNM: Electroless nickel plating waste liquid W: Water H: Mineral acid (sulfuric acid, hydrochloric acid)
S: Precipitant (sodium carbonate, sodium hydroxide, oxalic acid)
K: Sodium hydroxide KS: Selective heavy metal chelate resin FT: Filtration apparatus WP: Washing process CP: Paste DR: Drying apparatus

Claims (8)

In the method of recovering residual nickel ions from the electroless nickel plating waste liquid, the step of regenerating the selective heavy metal chelate resin packed in the column (A), the step of adjusting the electroless nickel plating waste liquid (B), and the step (A The nickel plating waste solution prepared in the step (B) is brought into contact with the chelate resin regenerated in step (B) to adsorb nickel ions to the chelate resin, and then the nickel adsorption and elution step (C) for eluting nickel with mineral acid; From the electroless nickel plating waste solution by a method comprising the nickel recovery step (D), in which an insoluble nickel compound is precipitated by adding carbonate, alkali hydroxide or oxalic acid to the nickel salt aqueous solution eluted in the step (C). An insoluble nickel compound having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg is recovered. Method for recovering the plating liquid waste remaining nickel. In step (A), the selective heavy metal chelate resin is converted to H-type with sulfuric acid, then 30 to 50% of H-type is replaced with Na-type using an aqueous sodium hydroxide solution, and mixed to obtain a total resin amount. 2. The recovery method according to claim 1, wherein the recovery step is a chelating resin regeneration step in which 30 to 50% is Na-type HNa mixed bed type chelating resin. In step (B), water is added to the raw waste solution to dilute it into an aqueous solution having a nickel concentration of 500 mg / l to 1000 mg / l, and then the pH value is adjusted to 4.0 to 6.0 using mineral acid or alkali. The recovery method according to claim 1, which is a step of adjusting the nickel plating waste liquid. In step (C), nickel is adsorbed to the chelate resin after 20 to 30 g / l of nickel is adsorbed per liter of resin, and then extruded and washed with water until the remaining phosphate ion concentration in the washing wastewater is 1.0 mg / l or less. And an elution step of eluting nickel into the chelate resin adsorbed with nickel using mineral acid to obtain a nickel salt aqueous solution, and the chelate resin after elution is adsorbed to recycle the resin to the resin regeneration step (A) The recovery method according to claim 1, which is an elution step. In step (D), the aqueous nickel salt solution obtained in step (C) is weighed, and 1 to 2 equivalents of sodium carbonate is added to the aqueous nickel salt solution to precipitate nickel carbonate, followed by filtration, washing with water and drying. The method according to claim 1, wherein the nickel is recovered as nickel carbonate powder having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg. In step (D), the aqueous nickel salt solution obtained in step (C) is weighed, and after adding 1-2 equivalents of sodium hydroxide to the aqueous nickel salt solution to precipitate nickel hydroxide, Phosphorus content is 0.1 mg by adding 1-2 equivalents of any one or more of sodium carbonate, sodium hydrogen carbonate or carbon dioxide gas to nickel hydroxide precipitation to convert nickel hydroxide to nickel carbonate. The recovery method according to claim 1, which is a step of recovering nickel as nickel carbonate powder of / Kg to 100 mg / Kg. In step (D), the aqueous nickel salt solution obtained in step (C) is weighed, and 1 to 2 equivalents of sodium hydroxide is added to the aqueous nickel salt solution to precipitate nickel hydroxide. The recovery method according to claim 1, which is a step of recovering nickel as nickel hydroxide powder having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg by washing with water and drying. In step (D), the aqueous nickel salt solution obtained in step (C) is weighed, and 1 to 2 equivalents of oxalic acid is added to the aqueous nickel salt solution to precipitate nickel oxalate, which is filtered, washed with water and dried. The recovery method according to claim 1, wherein the nickel is recovered as nickel oxalate powder having a phosphorus content of 0.1 mg / Kg to 100 mg / Kg.

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