JP4606951B2 - Multi-component nickel plating waste sludge recycling method - Google Patents

Description

The present invention relates to a processing method for recovering valuable resources such as nickel sulfate from a multi-component nickel plating waste liquid sludge mixed with a plating waste liquid sludge generated by nickel plating and a plating waste liquid sludge generated by other metal plating. .

To recover the nickel content in the nickel plating waste sludge, sulfuric acid is added to the nickel plating waste sludge to dissolve the solid, and a solution is prepared. From this solution, nickel sulfate crystals are crystallized by cooling crystallization. In order to further increase the recovery rate of nickel and the recovery rate of nickel, the nickel sulfate crystals are crystallized and recovered from the solution, and iron powder is added to the filtrate obtained by filtering the nickel sulfate crystals. There has been proposed a method in which a cooling crystallization process in which residual nickel ions are deposited and recovered on the iron powder surface and a cementation process are combined (for example, see Patent Document 1).

Alternatively, calcium carbonate is added to a solution obtained by adding sulfuric acid to nickel plating waste sludge to dissolve the solid content, and divalent iron ions in the solution are changed to trivalent iron ions, and then the pH is adjusted to remove iron. Form a nickel stock solution, add calcium hydroxide to this nickel stock solution, adjust the pH, add acid to the nickel-containing gypsum produced and recovered, dissolve it as nickel hydroxide, extract the nickel content, add sulfuric acid to this A method of cooling and crystallizing the nickel sulfate solution produced in this way to crystallize and recover nickel sulfate crystals has been proposed (see, for example, Patent Document 2).

JP 2004-284848 A JP 2005-15272 A

Generally, in a plating processing factory, the amount of plating waste liquid sludge generated when a single type of metal plating processing is performed is small, and more than two types of metal plating processing steps are often performed. The plating waste liquid sludge generated in the plating process is mixed, and the plating waste liquid sludge containing a multi-component metal component is taken out from the plating processing factory and disposed at the final disposal site. On the other hand, when trying to efficiently recover (recycle) valuable metals from plating waste sludge, the generated plating waste sludge is stored in, for example, a storage tank, and the plating waste sludge has reached a certain amount. From the viewpoint of economy, it is desirable to collect valuable metals by batch processing at the time.

Accordingly, the plating waste liquid sludge to be treated is not limited to the plating waste liquid sludge generated by nickel plating. For example, the plating waste liquid sludge generated when performing copper plating, chromium plating, and galvanization is mixed. It is in the state of component-containing nickel plating waste liquid sludge. Here, when the invention described in Patent Documents 1 and 2 is applied to, for example, a multicomponent-containing nickel plating waste liquid sludge containing copper, chromium, zinc, iron, and nickel, the recovered iron and nickel are respectively copper. , Chromium, and zinc will be mixed. For this reason, there exists a problem that the separate collection | recovery of each valuable metal cannot be performed accurately. And the problem that the purity of the nickel and iron collect | recovered falls and the utility value as a resource also arises arises.

The present invention has been made in view of such circumstances, and the plating waste liquid sludge generated in the nickel plating process is mixed with the plating waste liquid sludge generated in the other metal plating process. It is an object of the present invention to provide a method for recycling a multicomponent-containing nickel plating waste liquid sludge capable of collecting nickel sulfate while performing separate collection.

A recycling method for multi-component nickel plating waste liquid sludge according to the first invention in accordance with the above object is to add a mineral acid to a multi-component nickel plating waste liquid sludge containing copper, iron, and nickel to form a dissolved processed product. And an inorganic acid extraction step to remove the insoluble matter from the solution and obtain a solution.
Add copper powder to the solution to adjust the oxidation-reduction potential, replace the copper ion in the solution with iron, separate the copper-attached iron powder with copper deposited on the surface, and use it as a copper ion removal solution A removal step;
An oxidizing agent is added to the copper ion removing solution, an oxidation treatment is performed to oxidize divalent iron ions in the copper ion removing solution to trivalent iron ions, an alkaline agent is added to adjust the pH, and the trivalent iron ions are adjusted. A ferric hydroxide neutralization treatment to convert ferric hydroxide into ferric hydroxide, and a ferric hydroxide starch produced as a separated treatment solution,
A nickel fractionation and recovery step of adjusting the pH by adding an alkaline agent to the treatment liquid, performing nickel neutralization treatment to change nickel ions in the treatment liquid to nickel hydroxide, and generating nickel hydroxide starch;
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
The nickel sulfate solution is subjected to a cooling crystallization treatment to recover the crystallized nickel sulfate crystals.
Here, copper, iron, and nickel include these compounds in addition to copper, iron, and nickel metals.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first invention, the alkaline agent used in one or both of the ferric iron neutralization treatment and the nickel neutralization treatment is It is diluted with a part of the residual liquid after recovering the nickel hydroxide starch in the nickel fraction recovery step, and the remaining part of the residual liquid can be mixed with the multicomponent-containing nickel plating waste liquid sludge. Here, the last time is not limited to the case where batch processing is performed, but also includes the case where continuous processing is performed.
As a result, the amount of waste water discharged from each process of the recycling process can be suppressed. Furthermore, by diluting the alkali agent, it is possible to prevent a high pH region from being locally formed when the alkali agent is added.

The recycling method for multi-component nickel plating waste liquid sludge according to the second invention in accordance with the above object is to form a solution by adding an inorganic acid to the multi-component nickel plating waste liquid sludge containing chromium, iron and nickel. And an inorganic acid extraction step to remove the insoluble matter from the solution and obtain a solution.
A reducing agent is added to the solution to reduce the trivalent iron ions in the solution to divalent iron ions, an alkaline agent is added to adjust the pH, and the chromium ions in the solution are hydroxylated. Chromium ion removal process that performs chromium neutralization treatment to change to chromium, separates the generated chromium hydroxide starch and makes a chromium ion removal solution,
An oxidizing agent is added to the chromium ion removing solution, an oxidation treatment is performed to oxidize divalent iron ions in the chromium ion removing solution to trivalent iron ions, an alkaline agent is added to adjust the pH, and the trivalent iron ions are adjusted. A ferric hydroxide neutralization treatment to convert ferric hydroxide into ferric hydroxide, and a ferric hydroxide starch produced as a separated treatment solution,
A nickel fractionation and recovery step of adjusting the pH by adding an alkaline agent to the treatment liquid, performing nickel neutralization treatment to change nickel ions in the treatment liquid to nickel hydroxide, and generating nickel hydroxide starch;
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
The nickel sulfate solution is subjected to a cooling crystallization treatment to recover the crystallized nickel sulfate crystals.
Here, chromium includes these compounds in addition to the metal of chromium.

A recycling method for multi-component nickel plating waste liquid sludge according to the third aspect of the present invention, in which an inorganic acid is added to the multi-component nickel plating waste liquid sludge containing copper, chromium, iron, and nickel, is dissolved and processed. And an inorganic acid extraction step of removing an insoluble component from the dissolved processed product to obtain a solution.
Add copper powder to the solution to adjust the oxidation-reduction potential, replace the copper ion in the solution with iron, separate the copper-attached iron powder with copper deposited on the surface, and use it as a copper ion removal solution A removal step;
An alkaline agent is added to the copper ion removing solution to adjust the pH, and a chromium neutralization treatment is performed to change chromium ions in the copper ion removing solution into chromium hydroxide. A chromium ion removal step as an ion removal solution;
An oxidizing agent is added to the chromium ion removing solution, an oxidation treatment is performed to oxidize divalent iron ions in the chromium ion removing solution to trivalent iron ions, an alkaline agent is added to adjust the pH, and the trivalent iron ions are adjusted. A ferric hydroxide neutralization treatment to convert ferric hydroxide into ferric hydroxide, and a ferric hydroxide starch produced as a separated treatment solution,
A nickel fractionation and recovery step of adjusting the pH by adding an alkaline agent to the treatment liquid, performing nickel neutralization treatment to change nickel ions in the treatment liquid to nickel hydroxide, and generating nickel hydroxide starch;
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
The nickel sulfate solution is subjected to a cooling crystallization treatment to recover the crystallized nickel sulfate crystals.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the second and third inventions, any one or two of the chromium neutralization treatment, the ferric iron neutralization treatment, and the nickel neutralization treatment The alkaline agent used above is diluted by using the remaining part of the remaining liquid after recovering the nickel hydroxide starch in the previous nickel fraction recovery process, and the remaining liquid is the multi-component nickel Can be mixed with plating waste liquid sludge. Here, the last time is not limited to the case where batch processing is performed, but also includes the case where continuous processing is performed.
As a result, the amount of waste water discharged from each process of the recycling process can be suppressed. Furthermore, by diluting the alkali agent, it is possible to prevent a high pH region from being locally formed when the alkali agent is added.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first to third inventions, a calcium source is added to the remaining nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step. In addition, the produced gypsum is separated to remove sulfate radicals in the residual nickel sulfate solution to form a sulfate radical removal solution, and a part or all of the sulfate radical removal solution can be mixed with the treatment solution. .
Since the sulfate radical removal liquid contains nickel ions that could not be recovered by crystallization, the amount of nickel ions contained can be increased by adding the sulfate radical removal liquid to the treatment liquid. The amount of nickel hydroxide starch produced during the treatment can be increased.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first to third inventions, the residual nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step is used as the multicomponent It can be mixed with the nickel plating waste liquid sludge.
Thereby, each metal component remaining in the residual nickel sulfate solution can be recovered again.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first invention, when the multicomponent-containing nickel plating waste liquid sludge further contains zinc, in the nickel fractional recovery step, the nickel fractional recovery step An alkaline agent is added to the treatment liquid to be used to adjust the pH, and a zinc fraction recovery process is performed in which zinc hydroxide starch is generated and separated from zinc ions in the treatment liquid, and then the nickel neutralization treatment is performed. It is preferable.
Thereby, it is possible to prevent the zinc hydroxide starch from being co-precipitated when the nickel hydroxide starch is produced.

In addition, the alkaline agent used in the ferric iron neutralization treatment, the nickel neutralization treatment, and the zinc fraction collection treatment is a residual liquid after the nickel hydroxide starch is collected in the previous nickel fraction collection step. The remaining portion of the residual liquid can be mixed with the multi-component nickel plating waste liquid sludge.
As a result, the amount of waste water discharged from each process of the recycling process can be suppressed. Furthermore, by diluting the alkali agent, it is possible to prevent a high pH region from being locally formed when the alkali agent is added.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the second and third inventions, when the multicomponent-containing nickel plating waste liquid sludge further contains zinc, the nickel fractionation recovery step, The nickel neutralization is performed after a zinc fraction recovery process is performed in which an alkaline agent is added to the treatment liquid used in the recovery step to adjust the pH, and a zinc hydroxide starch is generated and separated from zinc ions in the treatment liquid. It is preferable to perform processing.
Thereby, it is possible to prevent the zinc hydroxide starch from being co-precipitated when the nickel hydroxide starch is produced.

Moreover, the alkaline agent used in any one or two or more of the chromium neutralization treatment, the ferric iron neutralization treatment, the nickel neutralization treatment, and the zinc fraction collection treatment is the previous nickel fraction collection step. A portion of the residual liquid after recovering the nickel hydroxide starch is diluted, and the remaining part of the residual liquid can be mixed with the multi-component nickel plating waste liquid sludge.
As a result, the amount of waste water discharged from each process of the recycling process can be suppressed. Furthermore, by diluting the alkali agent, it is possible to prevent a high pH region from being locally formed when the alkali agent is added.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first to third inventions, a calcium source is added to the remaining nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step. In addition, the generated gypsum was separated to remove sulfate radicals in the residual nickel sulfate solution to form a sulfate radical removal solution, and zinc ions were removed from the treatment solution by part or all of the sulfate radical removal solution. It can be mixed in the later nickel ion-containing liquid.
Since the sulfate radical removal liquid contains nickel sulfate that could not be recovered by crystallization, the sulfate radical removal liquid contains nickel ions, and the nickel contained by adding this liquid to the nickel ion-containing liquid The amount of ions can be increased, and the amount of nickel hydroxide starch produced during the nickel neutralization treatment can be increased.

Moreover, the residual nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step can be mixed with the multicomponent-containing nickel plating waste sludge.
Thereby, each metal component remaining in the residual nickel sulfate solution can be recovered again.

Further, for the separated zinc hydroxide starch, an inorganic acid extraction treatment in which the zinc hydroxide starch is dissolved in an inorganic acid to prepare a zinc-containing liquid;
A nickel ion-removed zinc-containing liquid in which iron powder is added to the zinc-containing liquid to adjust the oxidation-reduction potential to replace nickel ions and iron in the zinc-containing liquid and nickel is deposited on the surface. Nickel ion separation treatment to be formed;
An oxidizing agent is added to the nickel ion-removed zinc-containing liquid to oxidize divalent iron ions in the nickel-ion-removed zinc-containing liquid to trivalent iron ions, and then the pH is adjusted to generate hydroxyl from the trivalent iron ions. An iron ion separation process for separating ferric starch to form an iron ion-removed zinc-containing liquid;
Water for recovering starch having a high zinc hydroxide content by adjusting the pH by adding an alkaline agent to the iron ion-removed zinc-containing solution and changing zinc ions in the iron ion-removed zinc-containing solution to zinc hydroxide Zinc oxide re-recovery treatment is preferably performed.

The recycling method for multi-component nickel-plated waste liquid sludge according to the fourth aspect of the present invention that meets the above-mentioned object is to add a mineral acid to the multi-component-containing nickel-plated waste sludge containing copper, zinc, and nickel to form a dissolved treatment product And an inorganic acid extraction step for removing the insoluble matter from the solution and recovering the solution.
An alkaline agent is added to the solution to adjust the pH, and a copper neutralization treatment is performed in which the copper ions in the solution are changed to copper hydroxide, and the resulting copper hydroxide starch is separated into a copper ion removing solution. A copper ion removal step;
Zinc ions obtained by adjusting the pH by adding an alkaline agent to the copper ion removing liquid, and performing zinc neutralization treatment to change the zinc ions in the copper ion removing liquid to zinc hydroxide, and separating the generated zinc hydroxide starch A zinc ion removal step for forming a removal solution;
Nickel separation and recovery step of adjusting the pH by adding an alkaline agent to the zinc ion removing liquid, performing nickel neutralization treatment to change nickel ions in the zinc ion removing liquid into nickel hydroxide, and generating nickel hydroxide starch When,
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
The nickel sulfate solution is subjected to a cooling crystallization treatment to recover the crystallized nickel sulfate crystals.
In the recycling processing method of the multicomponent content nickel plating waste liquid sludge which concerns on 4th invention, it is used by any 1 or 2 or more of the said copper neutralization process, the said zinc neutralization process, and the said nickel neutralization process. The alkaline agent is diluted by using a part of the remaining liquid after the nickel hydroxide starch is recovered in the previous nickel separation and recovery step, and the remaining part of the residual liquid is added to the multicomponent-containing nickel plating waste sludge. Can be mixed.
As a result, the amount of waste water discharged from each process of the recycling process can be suppressed. Furthermore, by diluting the alkali agent, it is possible to prevent a high pH region from being locally formed when the alkali agent is added.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the fourth invention, the zinc hydroxide starch is dissolved in an inorganic acid with respect to the separated zinc hydroxide starch. An inorganic acid extraction treatment to be prepared;
A nickel ion-removed zinc-containing liquid in which iron powder is added to the zinc-containing liquid to adjust the oxidation-reduction potential to replace nickel ions and iron in the zinc-containing liquid and nickel is deposited on the surface. Nickel ion separation treatment to be formed;
An oxidizing agent is added to the nickel ion-removed zinc-containing liquid to oxidize divalent iron ions in the nickel-ion-removed zinc-containing liquid to trivalent iron ions, and then the pH is adjusted to generate hydroxyl from the trivalent iron ions. An iron ion separation process for separating ferric starch to form an iron ion-removed zinc-containing liquid;
Water for recovering starch having a high zinc hydroxide content by adjusting the pH by adding an alkaline agent to the iron ion-removed zinc-containing solution and changing zinc ions in the iron ion-removed zinc-containing solution to zinc hydroxide Zinc oxide re-recovery treatment is preferably performed.

In the recycling method for multi-component nickel plating waste liquid sludge according to the fourth invention, the alkali agent used in the zinc hydroxide re-recovery process recovers nickel hydroxide starch in the previous nickel fraction recovery process. It is preferable to dilute with a part of the remaining liquid after the treatment.
As a result, the amount of waste water discharged from each process of the recycling process can be suppressed. Furthermore, by diluting the alkali agent, it is possible to prevent a high pH region from being locally formed when the alkali agent is added.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the fourth aspect of the invention, it is generated by adding a calcium source to the residual nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step The gypsum is separated to remove sulfate radicals in the residual nickel sulfate solution to form a sulfate radical removal solution. A part of the sulfate radical removal solution is used as the solution, the copper ion removal solution, and the zinc ions. Any one or two or more of the removal liquids can be mixed.
Since the sulfate radical removal solution contains nickel sulfate that could not be recovered by crystallization, the sulfate radical removal solution contains nickel ions. This solution is used as a solution, copper ion removal solution, and zinc ion removal solution. By mixing any one or more of the liquids, the amount of nickel ions contained can be increased, and the amount of nickel hydroxide starch produced during the nickel neutralization treatment can be increased.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the fourth invention, the remaining nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step is used as the multicomponent-containing nickel plating. Can be mixed with waste sludge.
Thereby, each metal component remaining in the residual nickel sulfate solution can be recovered again.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first to fourth inventions, in the inorganic acid extraction step, a calcium source is added to the dissolved processed product to react with the sulfate radical in the dissolved processed product. It is preferable to form gypsum and remove the gypsum together with the insoluble matter.
As a result, gypsum can be present in the insoluble component, and the filtration resistance of the insoluble component layer can be reduced, and the solution can be easily moved in the insoluble component layer.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first to fourth inventions, in the inorganic acid extraction step, a calcium source is added after removing the insoluble matter from the dissolved processed product. It can also be made to react with a sulfate radical to produce gypsum, and the gypsum can be removed to obtain the solution.
By reducing the content of sulfate radicals, the range of usable alkali agents can be expanded. For example, even if an alkali agent containing calcium is used, the amount of gypsum mixed in the hydroxide is reduced. Can do.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the first to fourth inventions, the inorganic acid can be hydrochloric acid.
By using hydrochloric acid, each metal component can be present in a chloride state in the solution, and each metal component can be easily recovered in the hydroxide state.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to claims 1 to 23, each metal excluding nickel can be sequentially separated and recovered from the multicomponent-containing nickel plating waste liquid sludge, and the nickel content is sulfuric acid. It can be recovered as nickel. As a result, each recovered metal component can be effectively used as a resource, and the recovered nickel sulfate can be reused as it is in nickel plating.

In particular, in the recycling method of component-containing nickel plating waste liquid sludge according to claims 2, 5, 9, 11, 16, and 18, the amount of wastewater discharged from the system from each step of the recycling process is suppressed. It is possible to reduce the wastewater treatment cost and the load on the environment. Furthermore, since the alkaline agent is diluted and added to prevent a high pH region from being locally formed, it is possible to prevent the formation of a plurality of metal hydroxides simultaneously. As a result, the separation and collection accuracy of the metal component can be improved.

In the recycling method of the multi-component-containing nickel plating waste liquid sludge according to claim 6, 7, 12, 13, 19 and 20, the nickel ion content in the processing liquid is increased to produce nickel hydroxide starch. The amount can be increased, and the amount of nickel sulfate produced can be increased. As a result, it is possible to increase the amount of nickel sulfate crystals that crystallize.

In the recycling method of the multi-component-containing nickel plating waste liquid sludge according to claims 8 and 10, it is possible to prevent coprecipitation of zinc hydroxide starch when producing nickel hydroxide starch. Therefore, a nickel hydroxide starch having a high nickel hydroxide content can be obtained.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to claim 14 and 17, since the nickel component contained in the zinc hydroxide starch is separated and recovered, the purity of the recovered zinc hydroxide is adjusted. It is possible to increase the total nickel recovery rate while making it possible to use the recovered starch having a high zinc hydroxide content.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to claim 21, gypsum can be present in the insoluble matter, and the filtration resistance of the insoluble matter layer is lowered to reduce the insoluble content in the insoluble matter layer. Thus, the solution can be easily moved, and the solution can be easily obtained.

In the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to claim 22, an inexpensive alkaline agent containing calcium such as slaked lime can be used because the content of sulfate radical is reduced, and the treatment is inexpensive. Can be performed.

In the recycling method of the multi-component nickel plating waste liquid sludge according to claim 23, each metal component is present in a chloride state in the solution, and each metal component is easily recovered in a hydroxide state. It is possible to increase both the collection accuracy and the collection rate of each metal component.

Next, embodiments of the present invention will be described with reference to the accompanying drawings for understanding of the present invention.
Here, FIG. 1 is a process explanatory diagram of a recycling method for multi-component nickel plating waste liquid sludge according to the first embodiment of the present invention, and FIG. 2 is a recycling of the multi-component nickel plating waste liquid sludge. FIG. 3 is an explanatory view of the copper ion removal process in the recycling method of the multi-component nickel-plating waste liquid sludge, and FIG. 4 is a re-treatment of the multi-component nickel-plating waste liquid sludge. FIG. 5 is an explanatory view of the iron ion removal process in the recycling process method of the multicomponent-containing nickel plating waste liquid sludge, and FIG. 6 is the multicomponent-containing nickel plating waste liquid sludge. Fig. 7 is an explanatory diagram of the zinc separation and recovery process in the recycling process method of Fig. 7, and Fig. 7 shows the water in the recycling process method of the nickel component waste liquid sludge containing the same multi-component FIG. 8 is an explanatory view of refining zinc multi-component nickel plating waste liquid sludge, FIG. 8 is an explanatory view of a nickel separation and recovery process in the recycling process of the multi-component nickel plating waste liquid sludge, and FIG. FIG. 10 is an explanatory diagram of the sulfuric acid extraction step and nickel sulfate recovery step in the resource recycling method, and FIG. 10 is a process explanatory diagram of the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to the second embodiment of the present invention. 11 is an explanatory view of the sulfate radical removing process in the recycling method of the multicomponent-containing nickel plating waste liquid sludge, and FIG. 12 is the recycling of the multicomponent-containing nickel plating waste liquid sludge according to the third embodiment of the present invention. Process explanatory drawing of a processing method, FIG. 13 is explanatory drawing of the copper ion removal process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge.

As shown in FIG. 1, a recycling method for multi-component nickel plating waste liquid sludge according to the first embodiment of the present invention (hereinafter simply referred to as a waste liquid sludge recycling method) is, for example, copper Then, hydrochloric acid, which is an example of inorganic acid, is added to the multicomponent nickel-plated waste sludge in which all of chromium, zinc, iron, and nickel are present in the form of hydroxide to form a dissolved processed product. Inorganic acid extraction step to remove dissolved components to make a dissolved solution, and to adjust the oxidation-reduction potential by adding iron powder to the dissolved solution, to replace the copper ions and iron in the dissolved solution, copper deposited on the surface A copper ion removing step of separating the adhering iron powder to obtain a copper ion removing solution.

In addition, the waste sludge recycling treatment method was performed by adding an alkaline agent to the copper ion removal solution to adjust the pH, and performing a chromium neutralization treatment to change the chromium ions in the copper ion removal solution to chromium hydroxide. Chromium ion removal step that separates chromium hydroxide starch into a chromium ion removal solution, and hydrogen peroxide water, which is an example of an oxidizing agent, is added to the chromium ion removal solution to remove divalent iron ions in the chromium ion removal solution. After oxidizing to trivalent iron ions, an alkaline agent is added to adjust the pH, and ferric hydroxide neutralization treatment is performed to change the trivalent iron ions to ferric hydroxide, And an iron ion removing step as a separated treatment liquid.

Further, the waste sludge recycling treatment method includes adding an alkali agent to the treatment liquid to adjust the pH, performing a zinc neutralization treatment to change zinc ions in the treatment liquid to zinc hydroxide, and producing the generated zinc hydroxide starch. After the zinc fraction recovery process to separate the product, the pH is adjusted by adding an alkali agent, and the nickel neutralization process is performed to change the nickel ions to nickel hydroxide to produce nickel hydroxide starch. A sulfuric acid extraction step in which sulfuric acid is added to the recovered nickel hydroxide starch to form a nickel sulfate solution, a cooling crystallization treatment is performed on the nickel sulfate solution, and the crystallized nickel sulfate crystals are recovered and the remaining nickel sulfate solution A nickel sulfate recovery step for forming a residual nickel sulfate solution and a residual nickel sulfate solution circulation step for mixing the residual nickel sulfate solution with a multicomponent-containing nickel plating waste sludge There. Hereinafter, these will be described in detail.

As shown in FIG. 1, in the inorganic acid extraction step, first, a multicomponent-containing nickel plating waste liquid sludge is received and mixed with stirring to prepare a slurry having a solid content concentration of about 10% by weight (repulping). Subsequently, hydrochloric acid is added to this slurry, pH is adjusted to 2 or less, for example, about 0.8, and it agitates for 5 to 20 minutes. At this time, the temperature of the slurry is adjusted to 30 to 80 ° C., for example, 40 ° C. By the above operation, the solid content (hydroxide of each metal) in the slurry is dissolved as ions by the following reaction (hereinafter referred to as hydrochloric acid dissolution treatment).
Cr (OH) ₃ + 3H ⁺ + 3Cl ⁻ → Cr ³⁺ + 3Cl ⁻ + 3H ₂ O
Cu (OH) ₂ + 2H ⁺ + 2Cl ⁻ → Cu 2 ⁺ + 2Cl ⁻ + 2H ₂ O
Fe (OH) ₂ + 2H ⁺ + 2Cl ⁻ → Fe ²⁺ + 2Cl ⁻ + 2H ₂ O
Fe (OH) ₃ + 3H ⁺ + 3Cl ⁻ → Fe ³⁺ + 3Cl ⁻ + 3H ₂ O
Ni (OH) ₂ + 2H ⁺ + 2Cl ⁻ → Ni ²⁺ + 2Cl ⁻ + 2H ₂ O
Zn (OH) ₂ + 2H ⁺ + 2Cl ⁻ → Zn ²⁺ + 2Cl ⁻ + 2H ₂ O

Subsequently, slaked lime is added to the dissolved processed product, and gypsum (calcium sulfate) is generated by reacting with the sulfate radical contained in the dissolved processed product while adjusting the pH to 3 or less, for example, about 0.9. processing). Then, the processed product containing gypsum is treated with, for example, a filter press to separate the insoluble matter as a solid layer (hereinafter referred to as cake), and each of chromium, copper, iron, nickel, and zinc The dissolution treatment liquid containing ions is collected (solid-liquid separation treatment). The insoluble matter separated as cake is disposed as waste. At this time, since the produced gypsum moves to the cake side, the water permeability of the cake increases, and the recovery rate of the dissolution treatment liquid increases. Here, the separated cake is washed with washing water so that each metal ion remaining on the cake side is washed away. This further increases the recovery rate of each metal ion.

Next, as shown in FIG. 2, calcium carbonate, which is an example of a calcium source, is added to the recovered dissolution treatment liquid, and the temperature is kept at 30 to 80 ° C., for example, 60 ° C., and the pH is 1 or more and 3 or less, for example, 2 The sulfate radical in the dissolution treatment liquid is removed by reacting with the sulfate radical remaining in the dissolution treatment liquid to produce gypsum. And the dissolution processing liquid containing gypsum is solid-liquid separated with a filter press, for example, and gypsum is removed, and it is set as a solution (sulfuric acid radical removal process). The separated gypsum is washed with washing water so that each metal ion remaining on the gypsum side is washed away. Thereby, the recovery rate of each metal ion can be increased. In addition, calcium chloride can be used in place of calcium carbonate. The separated gypsum can be used as a raw material for gypsum products such as gypsum board.
Here, the amount of gypsum generated in the gypsum generation treatment is preferably limited to an amount necessary to improve the water permeability of the cake. This reduces the amount of gypsum produced and reduces the amount of cake generated (total of insoluble matter and gypsum), thereby reducing the burden of waste treatment and reducing the amount of gypsum generated in the sulfate removal process. Increasing the production of gypsum that can be effectively used can be achieved.

As shown in FIG. 3, iron powder is added to the recovered solution, hydrochloric acid is added so that the pH is 3 or less, and the temperature of the solution is kept at 30 to 80 ° C., for example, 40 ° C. The oxidation-reduction potential (ORP) is adjusted to −400 to −100 mV, for example, about −250 mV, and stirred for a predetermined time (for example, 15 to 30 minutes) (cementation treatment). Thereby, the chemical reaction shown below progresses between the copper ions and iron in the solution, copper-attached iron powder in which copper is deposited on the surface of the iron powder is formed, and the copper ions in the solution are removed. Here, as iron powder, atomized iron powder and converter dust refined iron powder can be used, for example.
2Fe ³⁺ + Fe → 3Fe ²⁺
Cu ²⁺ + Fe → Cu ↓ + Fe ²⁺ (cementation treatment)
Fe + 2H ⁺ + 2Cl ⁻ → Fe ²⁺ + 2Cl ⁻ + H ₂ ↑
Then, after a predetermined time has elapsed, the liquid in which the copper-adhered iron powder is suspended is subjected to, for example, a solid-liquid separation treatment with a filter press to separate the copper-adhered iron powder as a cake, and each of chromium, iron, nickel, and zinc A copper ion removing solution containing ions is collected (the copper ion removing step). The separated cake is washed with washing water so that chromium, iron, nickel and zinc ions adhering to the cake side are washed away. Here, the separated copper-attached iron powder can be used, for example, as a copper refining raw material.

As shown in FIG. 4, the temperature of the recovered copper ion removing solution is kept at 30 to 80 ° C., for example 60 ° C., and caustic soda diluted with water, which is an example of an alkali agent, is added to adjust the pH to 3 or more and 5 or less. Adjust to about 4.2 and stir for a predetermined time (for example, 15 to 30 minutes) (chromium neutralization treatment). Thereby, the chemical reaction shown below progresses between the chromium ions in the copper ion removing solution and caustic soda, and the chromium ions are changed to chromium hydroxide.
Cr ³⁺ + 3Cl ⁻ + 3Na ⁺ + 3OH ⁻ → Cr (OH) ₃ ↓ + 3Na ⁺ + 3Cl ⁻
Then, after a predetermined time has elapsed, the copper ion removing liquid containing the chromium hydroxide starch is subjected to solid-liquid separation treatment with, for example, a filter press to separate the chromium hydroxide starch as a cake, and iron, nickel, and zinc The chromium ion removing solution containing each ion is collected (the chromium ion removing step). Here, the separated cake is washed with washing water so that iron, nickel and zinc ions adhering to the cake side are washed away. Thereby, the recovery rate of each ion of iron, nickel, and zinc can be increased. The separated chromium hydroxide starch can be used, for example, as a chromium refining raw material.

As shown in FIG. 5, the temperature of the recovered chromium ion removing liquid is kept at 30 to 80 ° C., for example, 60 ° C., and hydrogen peroxide, which is an example of an oxidizing agent, is added to remove divalent iron ions in the chromium ion removing liquid. Oxidizes to trivalent iron ions (oxidation treatment). Next, caustic soda diluted with water, which is an example of an alkaline agent, is added to adjust the pH to 2.5 or more and 5 or less, for example, about 3.5, and stirred for a predetermined time (for example, 15 to 30 minutes) (No. 1). Ferric iron neutralization treatment). Thereby, the chemical reaction shown below progresses between the trivalent iron ions and the caustic soda in the chromium ion removing solution, and the trivalent iron ions are changed to ferric hydroxide.
2Fe ²⁺ + 2Cl ⁻ + H ₂ O ₂ → 2FeOCl + 2Cl ⁻ + 2H ⁺
FeOCl + Cl ⁻ + H ⁺ + 2Na ⁺ + 2OH ⁻
→ Fe (OH) ₃ ↓ + 2Na ⁺ + 2Cl ⁻
Fe ³⁺ + 3Cl ⁻ + 3Na ⁺ + 3OH ⁻ → Fe (OH) ₃ ↓ + 3Na ⁺ + 3Cl ⁻
Then, after a predetermined time has elapsed, the liquid containing ferric hydroxide starch is subjected to solid-liquid separation treatment with, for example, a filter press to separate the ferric hydroxide starch as a cake, and each ion of nickel and zinc Is recovered (the iron ion removing step). Here, the separated cake is washed with washing water so that nickel and zinc ions adhering to the cake side are washed away. Thereby, the recovery rate of each ion of nickel and zinc can be increased. The recovered ferric hydroxide starch can be used, for example, as an iron chloride raw material.

As shown in FIG. 6, the temperature of the recovered treatment liquid is kept at 30 to 80 ° C., for example, 60 ° C., and caustic soda diluted with water, which is an example of an alkaline agent, is added to adjust the pH to 4.0 or more and 7.0 or less. For example, it adjusts to about 5.7 and stirs for a predetermined time (for example, 50 to 80 minutes) (zinc neutralization). As a result, the chemical reaction shown below proceeds between the zinc ions in the treatment liquid and caustic soda, and the zinc ions change to zinc hydroxide.
Zn ²⁺ + 2Cl ⁻ + 2Na ⁺ + 2OH ⁻ → Zn (OH) ₂ ↓ + 2Na ⁺ + 2Cl ⁻
Then, after a predetermined time has passed, the liquid containing zinc hydroxide starch is separated into solid cake by, for example, a filter press to separate the zinc hydroxide starch as a cake, and a nickel ion-containing liquid containing nickel ions is obtained. Collect (Zinc fraction collection process). Here, the separated cake is washed with washing water so that nickel ions adhering to the cake side are washed away. Thereby, the recovery rate of nickel ions can be increased. The recovered zinc hydroxide starch can be used, for example, as a zinc raw material.

Further, zinc hydroxide is purified to increase the purity of zinc hydroxide with respect to the recovered zinc hydroxide starch. In the purification process of zinc hydroxide, as shown in FIG. 7, first, the recovered zinc hydroxide starch is added to form a slurry, and the temperature of the slurry is maintained at 30 to 80 ° C., for example, 60 ° C. Hydrochloric acid, which is an example of an acid, is added to adjust the pH to 1 or less. Thus, in the slurry, the zinc hydroxide starch and the nickel hydroxide starch co-precipitated with the zinc hydroxide starch are dissolved by the following reaction to form a zinc-containing liquid (inorganic acid extraction treatment).
Ni (OH) ₂ + 2H ⁺ + 2Cl ⁻ → Ni ²⁺ + 2Cl ⁻ + 2H ₂ O
Zn (OH) ₂ + 2H ⁺ + 2Cl ⁻ → Zn ²⁺ + 2Cl ⁻ + 2H ₂ O

Next, iron powder is added to the zinc-containing liquid and hydrochloric acid is added so that the pH is 3 or less. Further, the temperature of the zinc-containing liquid is kept at 30 to 80 ° C., for example, 60 ° C. The redox potential of is adjusted to a range of -400 to -600 mV and stirred. As a result, the chemical reaction shown below proceeds between nickel ions and iron in the zinc-containing liquid to form nickel-attached iron powder in which nickel is deposited on the iron powder surface, and the nickel ions are separated from the zinc-containing liquid. .
Ni ²⁺ + Fe → Ni ↓ + Fe ²⁺
Fe + 2H ⁺ + 2Cl ⁻ → Fe ²⁺ + 2Cl ⁻ + H ₂ ↑
Then, the liquid in which the nickel-adhered iron powder is suspended is subjected to, for example, a solid-liquid separation process using a filter press to separate the nickel-adhered iron powder as a cake to obtain a nickel ion-removed zinc-containing liquid (nickel ion separation process). The separated nickel iron powder can be used as an alloy raw material.

Subsequently, the temperature of the recovered nickel ion-removed zinc-containing liquid is kept at 30 to 80 ° C., for example 60 ° C., chlorine as an example of an oxidizing agent is added, and divalent iron in the nickel-ion-removed zinc-containing liquid is subjected to the following reaction. The ions are oxidized and oxidized to trivalent iron ions.
2Fe ²⁺ + 4Cl ⁻ + Cl ₂ → 2Fe ³⁺ + 6Cl ⁻
And calcium carbonate which is an example of an alkaline agent is added, and pH is adjusted to 2.5 or more and 5.0 or less, for example, about 3.5. As a result, the chemical reaction shown below proceeds between the trivalent iron ions and calcium carbonate in the nickel ion-removed zinc-containing liquid, and ferric iron neutralization occurs in which the trivalent iron ions are changed to ferric hydroxide. .
2Fe ³⁺ + 6Cl ⁻ + 3CaCO ₃ + 3H ₂ O → 2Fe (OH) ₃ ↓ + 3Ca ²⁺ + 6Cl ⁻ + 3CO ₂
Furthermore, the liquid containing ferric hydroxide starch is subjected to solid-liquid separation treatment with a filter press, for example, to separate the ferric hydroxide starch as a cake, and to obtain an iron ion-removed zinc-containing liquid (iron ion Separation process). As a result, iron added during nickel recovery can be removed. In addition, when ferric chloride solution is produced by adding hydrochloric acid to the separated ferric hydroxide starch, it can be used as a flocculant.

The temperature of the recovered iron ion-removed zinc-containing liquid is kept at 30 to 80 ° C., for example, 60 ° C., and caustic soda as an example of an alkali agent is added to adjust the pH to a range of 7 to 12. As a result, the chemical reaction shown below proceeds between the zinc ions in the iron ion-removed zinc-containing liquid and caustic soda, and the zinc ions change to zinc hydroxide.
Zn ²⁺ + 2Cl ⁻ + 2Na ⁺ + 2OH ⁻ → Zn (OH) ₂ ↓ + 2Na ⁺ + 2Cl ⁻
And the liquid containing zinc hydroxide is solid-liquid separated by a filter press, for example, and zinc hydroxide starch is recovered as a cake to separate the liquid (zinc hydroxide re-recovery process). The recovered zinc hydroxide starch (starch having a high zinc hydroxide content) can be used, for example, as a zinc raw material, and the separated liquid is transported to a water treatment facility and then discharged.

As shown in FIG. 8, the temperature of the nickel ion-containing liquid obtained by performing the zinc separation and recovery treatment is kept at 30 to 80 ° C., for example, 60 ° C., and caustic soda diluted with water, which is an example of an alkali agent, is added to adjust pH Is adjusted to 7 to 12 and stirred for a predetermined time (for example, 20 to 50 minutes) (nickel neutralization treatment). As a result, the following chemical reaction proceeds between the nickel ions and the caustic soda, and the nickel ions change to nickel hydroxide.
Ni ²⁺ + 2Cl ⁻ + 2Na ⁺ + 2OH ⁻ → Ni (OH) ₂ ↓ + 2Na ⁺ + 2Cl ⁻
And after predetermined time progress, the liquid containing nickel hydroxide starch is solid-liquid separated by, for example, a filter press to collect nickel hydroxide starch as a cake, and the remaining liquid is separated (nickel fraction collection step) ). Here, the recovered cake is washed with washing water, and the remaining liquid adhering to the cake side is washed away. Thereby, the residual liquid adhering to a cake can be decreased and the amount of impurities contained in nickel hydroxide can be reduced. A part of the recovered nickel hydroxide starch can be used as a nickel raw material, for example.

Here, a part of the residual liquid is used instead of water for diluting caustic soda used in the chromium neutralization treatment, the ferric iron neutralization treatment, and the zinc neutralization treatment, respectively. Furthermore, the remaining part of the remaining liquid is used as a part of water used when preparing a slurry from the multicomponent-containing nickel plating waste liquid sludge, and the remaining part is drained. As a result, the amount of water used for diluting caustic soda and the amount of water used when preparing the slurry from the multicomponent-containing nickel plating waste liquid sludge can be reduced to reduce the processing cost. Furthermore, since the use of water is reduced, the absolute amount of residual liquid generated in the nickel fraction recovery process can be reduced.

As shown in FIG. 9, sulfuric acid is added to the recovered nickel hydroxide starch to adjust the pH to 1 or less, and the temperature is kept at 30 to 80 ° C., for example, 60 ° C. The chemical reaction shown is caused to form a nickel sulfate solution (sulfuric acid extraction step).
^{_{Ni (OH) 2 + 2H +}} + SO 4 2- → Ni 2+ + SO 4 2+ 2H 2 O
At this time, calcium ions brought into the nickel hydroxide starch react with sulfuric acid to form gypsum. For this reason, for example, gypsum produced by solid-liquid separation treatment of the nickel sulfate solution with a filter press is separated as a cake, and the primary filtrate containing nickel sulfate is recovered. Further, the recovered cake is washed with washing water and subjected to filter press again, and the nickel sulfate adhering to the cake side is used as a secondary filtrate, which is circulated for use in the sulfuric acid extraction process, or is used as a primary filtrate. Add. As a result, calcium ions adhering to the nickel hydroxide starch can be separated as gypsum. In addition, this solid-liquid separation process can be abbreviate | omitted when calcium ion does not remain substantially in nickel hydroxide starch.

Subsequently, the primary filtrate is heated in a vacuum, for example, to evaporate water, and concentrated, for example, until the specific gravity becomes 1.4 or more. The concentrated primary filtrate is then subjected to a cooling crystallization treatment while maintaining a temperature range of -20 to 20 ° C, for example, 0 ° C. The following reaction proceeds during the cooling crystallization treatment, and nickel sulfate crystals are crystallized. The crystallized nickel sulfate crystals are recovered, for example, by centrifuging to separate the remaining nickel sulfate solution. Nickel recovery process).
Ni ²⁺ + SO ₄ ^2- + 6H ₂ O → NiSO ₄・ 6H ₂ O ↓

Then, the content of soda and calcium in the separated residual nickel sulfate solution is measured, and the residual nickel sulfate solution is mixed with the nickel hydroxide starch while the content of soda and calcium is small. Further, when the contents of soda and calcium increase, the residual nickel sulfate solution is mixed with the multicomponent-containing nickel plating waste sludge. As a result, it is possible to prevent soda and calcium from being concentrated in the nickel sulfate recovery step, and to suppress the amount of soda and calcium mixed in the recovered nickel sulfate crystals. Further, by using the residual nickel sulfate solution as a part of water when preparing a slurry from the multicomponent-containing nickel plating waste sludge, the amount of water used can be reduced and the processing cost can be reduced. Furthermore, since the use of water is reduced, the absolute amount of residual liquid generated in the nickel fraction recovery process can be reduced.

As shown in FIG. 10, the recycling process method for the multicomponent-containing nickel plating waste liquid sludge according to the second embodiment of the present invention (hereinafter simply referred to as the waste liquid sludge recycling process method) is a residual nickel sulfate. Calcium carbonate, which is an example of a calcium source, is added to the solution to remove sulfate radicals in the remaining nickel sulfate solution to form a sulfate radical removal solution, and this sulfate radical removal solution is mixed with a nickel ion-containing solution for use. It is characterized by the provision of a filter aid mixing process that mixes the sulfate radical removal treatment of the nickel sulfate solution and the gypsum generated when the sulfate radical removal liquid is formed in the dissolved treatment product in the inorganic acid extraction step. The process is substantially the same as the waste sludge recycling treatment method according to the first embodiment. For this reason, only the sulfate radical removal process and the filter aid mixing process of the residual nickel sulfate solution will be described.

As shown in FIG. 11, the sulfate radical removal treatment for the residual nickel sulfate solution is performed by adding calcium carbonate to the separated residual nickel sulfate solution and maintaining the temperature at 30 to 80 ° C., for example, 60 ° C., at a pH of 1 or more. Hereinafter, for example, it is adjusted to about 2, and reacted with sulfate radicals in the residual nickel sulfate solution to produce gypsum. Thereby, the sulfate radical in the residual nickel sulfate solution can be removed. Then, the liquid in which the generated gypsum is suspended is separated into solid and liquid by a filter press, for example, and the gypsum is removed to recover the sulfate radical removing liquid. Since the recovered sulfate radical removal solution contains nickel ions, the nickel hydroxide starch recovery rate can be increased by mixing with the nickel ion-containing solution and performing nickel neutralization again. it can. Here, the separated cake is washed with washing water, and nickel ions adhering to the cake are washed away and mixed with a sulfate radical removing solution. Thereby, the amount of nickel ions to be recovered can be increased. In place of calcium carbonate, calcium chloride can be used.

In addition, the efficiency of solid-liquid separation treatment can be achieved even if the amount of gypsum produced in the gypsum production treatment is reduced by adding gypsum produced by the sulfate radical removal treatment to the residual nickel sulfate solution to the dissolved product and then performing the gypsum production treatment. Can be maintained at a high level. Further, by reducing the amount of gypsum generated during the gypsum generation treatment, it is possible to prevent the amount of sulfate radical from being lowered, and it is possible to increase the amount of gypsum produced by the sulfate radical removal treatment. For this reason, the amount of gypsum which can be used effectively can be increased.

As shown in FIG. 12, a recycling method for multi-component nickel plating waste liquid sludge according to the third embodiment of the present invention (hereinafter simply referred to as a waste liquid sludge recycling method) is, for example, copper , Zinc, and nickel are all present in the form of hydroxide. Addition of hydrochloric acid, which is an example of inorganic acid, to a nickel component waste sludge containing multiple components forms a dissolved product, and removes the insoluble matter from the dissolved product. An inorganic acid extraction step that removes gypsum generated by adding slaked lime to the dissolved solution and reacting with the sulfate radicals in the solution to make a solution, and adding an alkaline agent to the solution A copper neutralization process that adjusts the pH and converts the copper ions in the solution to copper hydroxide, and separates the produced copper hydroxide starch to form a copper ion removal solution. ing.

In addition, the waste sludge recycling treatment method was performed by adding an alkali agent to the copper ion removal solution to adjust the pH, and performing zinc neutralization treatment to change the zinc ions in the copper ion removal solution to zinc hydroxide. A zinc ion removal process that separates zinc hydroxide starch to make a zinc ion removal solution, and an alkaline agent is added to the zinc ion removal solution to adjust the pH, and the nickel ions in the zinc ion removal solution are changed to nickel hydroxide. A nickel fractionation recovery process for performing nickel neutralization treatment to produce the generated nickel hydroxide starch, a sulfuric acid extraction process for forming a nickel sulfate solution by adding sulfuric acid to the recovered nickel hydroxide starch, and a nickel sulfate solution A nickel sulfate recovery step of performing cooling crystallization treatment, recovering the crystallized nickel sulfate crystals and separating the residual nickel sulfate solution, and adding calcium to the residual nickel sulfate solution An example of slaked lime is added to remove sulfate radicals in the remaining nickel sulfate solution to form a sulfate radical removal solution, and this sulfate radical removal solution is mixed with the zinc ion removal solution (mixed with the solution and copper ion removal solution) The residual nickel sulfate solution used for the removal of sulfate radicals.
Here, since the inorganic acid extraction step can have substantially the same processing content as the hydrochloric acid extraction step in the waste liquid sludge recycling method according to the first embodiment, detailed description thereof is omitted. .

And as shown in FIG. 13, the temperature of the solution collect | recovered at the inorganic acid extraction process is kept at 30-80 degreeC, for example, 60 degreeC, and the pH is set to 4 or more by adding the caustic soda diluted with the water which is an example of an alkaline agent. And adjusted to 6 or less, for example, about 5, and stirred for a predetermined time (for example, 20 to 50 minutes) (copper neutralization treatment). Thereby, the chemical reaction shown below progresses between the copper ion and the caustic soda in the solution, and the copper ion changes to copper hydroxide.
Cu ²⁺ + 2Cl ⁻ + 2Na ⁺ + 2OH ⁻ → Cu (OH) ₂ ↓ + 2Na ⁺ + 2Cl ⁻
And after predetermined time progress, the liquid containing a copper hydroxide starch is separated into a cake by, for example, solid-liquid separation treatment with a filter press, and copper containing nickel and zinc ions is separated. The ion removing solution is collected (the copper ion removing step). Here, the separated cake is washed with washing water so that nickel and zinc ions adhering to the cake side are washed away. Thereby, the recovery rate of each ion of nickel and zinc can be increased. The recovered copper hydroxide starch can be used, for example, as a copper refining raw material.

In addition, the zinc fraction recovery process, the nickel fraction recovery process, the sulfuric acid extraction process, and the nickel sulfate recovery process that follow the copper ion removal process are the zinc fraction recovery process in the waste sludge recycling process method according to the first embodiment. The nickel fraction recovery step, the sulfuric acid extraction step, and the nickel sulfate recovery step can be substantially the same, and the zinc hydroxide purification step performed on the separated zinc hydroxide starch is the first step. The waste water sludge recycling treatment method according to the embodiment of the present invention can be substantially the same as the zinc hydroxide purification treatment step, and the sulfate radical removal treatment of the residual nickel sulfate solution is the second embodiment. Since it can be made into the processing content substantially the same as the sulfate radical removal process of the residual nickel sulfate solution in the recycling process method of the waste liquid sludge which concerns on a form, it is detailed Akira will be omitted.
In addition, a part of residual liquid obtained by recovering nickel hydroxide starch as a cake from a solution containing nickel hydroxide starch is used in copper neutralization treatment, zinc neutralization treatment and nickel neutralization treatment, respectively. Caustic soda is used in place of the diluting water, and the remaining portion of the remaining liquid is mixed with the multi-component nickel plating sludge. As a result, the amount of water used for diluting caustic soda can be reduced to reduce the processing cost.

Next, examples carried out for confirming the effects of the present invention will be described.
Example 1
Copper, chromium, iron, and nickel were separately collected in order from the multicomponent-containing nickel plating waste liquid sludge containing copper, chromium, iron, and nickel. FIG. 14 is a process explanatory diagram of a recycling method for multi-component nickel plating waste liquid sludge, and FIGS. 15 to 17 are detailed process explanatory diagrams of a multi-component nickel plating waste liquid sludge recycling method.
As shown in FIG. 15, water is added to the multicomponent-containing nickel plating waste sludge (315.6 g, solid content is 100.0 g) to prepare a slurry so that the slurry concentration is about 10% by weight (repulping). (S-1). The composition of the used multi-component nickel plating waste liquid sludge is shown in Table 1.

Here, clean water is used at the start of the treatment, but when the residual liquid obtained by recovering the nickel hydroxide starch and the residual nickel sulfate solution can be obtained, the residual liquid and Use residual nickel sulfate solution. When the steady state is reached, the remaining liquid 508.4 g and the residual nickel sulfate solution 287.0 g are used in combination. Table 2 shows the composition of the residual liquid and the residual nickel sulfate solution used. When such an operation is performed, 4.2 g of nickel is added to the multicomponent-containing nickel plating waste liquid sludge.

Subsequently, while heating the slurry to 40 ° C., 529.1 g of 15% hydrochloric acid was added so that the pH was about 0.8, and the mixture was stirred for 10 minutes to dissolve the solid content ( S-2) was performed. The pH of the slurry during the hydrochloric acid dissolution treatment was 0.8, and the temperature was 39 ° C.
Next, 97.6 g of slaked lime is added so that the pH is about 2 while heating so that the temperature of the dissolution treatment product obtained after completion of the hydrochloric acid dissolution treatment is 60 ° C., and stirred for 20 minutes to dissolve. It was made to react with the sulfate radical in a processed material, the gypsum was produced | generated, and the sulfate radical removal process was performed (S-3). At the start of the sulfate radical removal treatment, the pH was 1.1 and the temperature was 65 ° C. When the sulfate radical removal treatment was completed, the pH was 1.2 and the temperature was 57 ° C. And the dissolution treatment thing was left still and the produced gypsum was settled as an insoluble residue with the insoluble matter in a dissolution treatment thing (S-4).

The supernatant of the dissolved processed product is recovered, the insoluble residue is squeezed using a filter press to recover the liquid adhering to the insoluble residue, and 150 g of washing water is supplied to the cake-like insoluble residue. It was squeezed again with a filter press, and the washing water was collected and mixed with the supernatant to perform a solid-liquid separation process to obtain a solution (S-5). The compositions of insoluble residue and solution are shown in Tables 1 and 2, respectively (inorganic acid extraction step).

While adding 18.0 g of iron powder to the recovered solution (1471.2 g), the pH of the solution is adjusted to 3 or less, the temperature of the solution is kept at 40 ° C., and the redox potential of the solution is increased. It stirred for 20 minutes so that it might become about -250mV, and the copper collection | recovery process which precipitates copper on the iron powder surface and forms copper adhesion iron powder was performed (S-6). In addition, the oxidation-reduction potential of the liquid when iron powder is charged is −270 mV, the pH is 0.9, the temperature of the liquid is 45 ° C., and the oxidation-reduction potential of the liquid when the copper recovery process is completed is −305 mV, and the pH is 1.1. The temperature was 43 ° C. Next, after the copper recovery process is completed, the liquid is separated into solid and liquid with a filter press to recover the squeezed liquid, and 50 g of washing water is supplied to the cake-like copper-adhered iron powder and again squeezed with a filter press to obtain the washing water The solid-liquid separation process which collect | recovered and mixed with squeezed liquid and makes it a copper ion removal liquid was performed (S-7). The compositions of the copper-adhered iron powder and the copper ion removing solution are shown in Tables 1 and 2, respectively (the copper ion removing step).

While heating the recovered copper ion removal liquid (1481.3 g) to 60 ° C., add 409.2 g of 10% caustic soda to adjust the pH to about 4.2 and stir for 30 minutes to make chromium ions. The chromium neutralization process which changes to chromium hydroxide was performed (S-8). The pH at the start of the chromium neutralization treatment was 4.4, the temperature was 61 ° C., the pH at the end of the chromium neutralization treatment was 3.9, and the temperature of the solution was 61 ° C. Here, 10% caustic soda is prepared using clean water at the start of the treatment, but when the residual liquid is obtained, the residual liquid is used.
Next, the liquid after the chrome neutralization treatment is separated into solid and liquid by a filter press to collect the squeezed liquid, and 50 g of washing water is supplied to the cake-like chromium hydroxide starch and is again squeezed by the filter press and washed. Water was collected and mixed with the squeezed liquid to perform a solid-liquid separation process to obtain a chromium ion removing liquid (S-9). The compositions of the chromium hydroxide starch and the chromium ion removing solution are shown in Tables 1 and 2, respectively.

As shown in FIG. 16, while heating the recovered chromium ion removal solution 1667.4 g to 40 ° C., 6.7 g of hydrogen peroxide water was added and stirred for 10 minutes, An oxidation treatment was carried out to convert ferrous iron to ferric iron (S-10). The oxidation-reduction potential at the start of the oxidation treatment of ferrous iron is 662 mV, the pH is 2.6, the temperature is 24 ° C., the oxidation-reduction potential after the oxidation treatment is 673 mV, the pH is 2.6, and the temperature is 26 ° C.
Next, 14.5 g of 48% caustic soda and 15% hydrochloric acid for pH adjustment are added for 30 minutes so that the pH becomes about 3.5 while heating the temperature of the liquid after the oxidation treatment to 60 ° C. Stirring was performed, and ferric iron neutralization treatment was performed to change ferric ions to ferric hydroxide (S-11). In addition, pH at the time of a ferric iron neutralization process was 3.5, the temperature of the liquid was 63 degreeC, pH after the completion of a ferric iron neutralization process was 3.5, and temperature was 62 degreeC.
Then, the liquid after the ferric iron neutralization treatment is separated into solid and liquid with a filter press to collect the squeezed liquid, and 50 g of washing water is supplied to the cake-like ferric hydroxide starch and again with the filter press. Solid-liquid separation was performed by collecting the washing water and mixing with the squeezed liquid to obtain a treatment liquid (S-12). The compositions of ferric hydroxide starch and the treatment liquid are shown in Tables 1 and 2, respectively (the iron ion removal step).

While heating the recovered processing solution to 60 ° C., add 56.2 g of 48% sodium hydroxide so that the pH is about 10 and stir for 30 minutes to change nickel ions into nickel hydroxide. Sum processing was performed (S-13). The pH at the start of the nickel neutralization treatment was 10, and the temperature was 58 ° C. The pH after the completion of the nickel neutralization treatment was 10, and the temperature was 61 ° C.
Next, the liquid after the nickel neutralization treatment is separated into solid and liquid with a filter press to recover the squeezed liquid, and 200 g of washing water is supplied to the cake-like nickel hydroxide starch and again squeezed with a filter press to wash the washing water. A solid-liquid separation process was performed by mixing the recovered squeezed liquid with the recovered squeezed liquid (S-14). The compositions of the nickel hydroxide starch and the residual liquid are shown in Tables 1 and 2, respectively (Nickel fraction recovery step).

211.0 g of water was added to the recovered nickel hydroxide starch (211.1 g, solid content 43.0 g), and a slurry was prepared (repulped) so that the slurry concentration was about 10% by weight (S-15). ). Next, as shown in FIG. 17, while heating so that the temperature of the nickel hydroxide starch slurry is 60 ° C., 196.7 g of 70% sulfuric acid is added so that the pH becomes about 0.7. The mixture was stirred for 5 minutes, and a sulfuric acid extraction treatment for dissolving the nickel hydroxide starch in sulfuric acid was performed (S-16). The pH at the start of the sulfuric acid extraction treatment was 0.8 and the temperature was 62 ° C. The pH of the liquid at the end of the sulfuric acid extraction treatment was 0.9 and the temperature was 62 ° C.
In addition, when nickel hydroxide starch reacts with sulfuric acid to produce nickel sulfate, calcium ions brought together with the nickel hydroxide starch react with sulfuric acid to produce gypsum. For this reason, the liquid after the sulfuric acid extraction treatment is separated into solid and liquid by a filter press to collect the squeezed liquid, and 50 g of washing water is supplied to the insoluble residue mainly composed of cake-like gypsum and squeezed again by the filter press. Then, the washing water was collected and mixed with the squeezed liquid to perform a solid-liquid separation process to obtain a nickel sulfate solution (S-17). Tables 1 and 2 show the compositions of the insoluble residue mainly composed of gypsum and the nickel sulfate solution, respectively.

Subsequently, 644.7 g of the recovered nickel sulfate solution was heated to evaporate 346.2 g of water and concentrated (S-18) to prepare a nickel sulfate concentrate. The resulting nickel sulfate concentrate is indirectly cooled to maintain the temperature at 0 ° C. to crystallize nickel sulfate crystals (S-19), and the nickel sulfate crystals are recovered by centrifugation and the remaining nickel sulfate solution. Was separated (S-20). The compositions of the nickel sulfate crystals and the remaining nickel sulfate solution are shown in Tables 1 and 2, respectively (the nickel sulfate recovery step). The recovered nickel sulfate was 66.8 g, and the total nickel recovery rate was 62.6%.

(Example 2)
From the same multicomponent-containing nickel plating waste liquid sludge used in Example 1, copper, chromium, iron, and nickel were separately collected in order. At this time, in the inorganic acid extraction step, a gypsum generation process in which slaked lime is added to the dissolved processed product and reacted with the sulfate radicals in the dissolved processed product to generate gypsum, and the generated gypsum is removed together with the insoluble matter to be dissolved. A solid-liquid separation process for forming a solution and a sulfate radical removal process for adding a slaked lime to the dissolution treatment liquid and reacting with the remaining sulfate radical to form and remove gypsum to obtain a solution. FIG. 18 is an explanatory diagram of the inorganic acid extraction step of the recycling method for multicomponent-containing nickel plating waste liquid sludge in Example 2.
As shown in FIG. 18, water was added to the multicomponent-containing nickel plating waste liquid sludge to prepare (repulp) the slurry so that the slurry concentration was about 10% by weight (T-1). Here, clean water is used at the start of the treatment, but when the residual liquid and the residual nickel sulfate solution can be obtained, the residual liquid and the residual nickel sulfate solution are used instead of the clean water. When the steady state is reached, 601.2 g of the remaining liquid and 194.2 g of the remaining nickel sulfate solution are used in combination.

Subsequently, while heating the slurry to 40 ° C., first add 952.7 g of 15% hydrochloric acid so that the pH is about 0.8, then add 205.0 g and stir for 10 minutes. Hydrochloric acid dissolution treatment for dissolving the solid content was performed (T-2). The pH of the slurry during the hydrochloric acid dissolution treatment was 0.9, and the temperature was 58 ° C. Next, 56.1 g of slaked lime is added so that the pH becomes about 1 while heating so that the temperature of the dissolution treatment product obtained after completion of the hydrochloric acid dissolution treatment is 60 ° C., and stirred for 20 minutes to dissolve. It reacted with the sulfate radical in the treated product to produce a gypsum for filter aid (T-3). When the gypsum was produced, the solution treated product had a pH of 0.9 and a temperature of 72 ° C. And when gypsum production | generation was complete | finished, pH was 0.9 and temperature was 62 degreeC. Subsequently, the dissolved processed product after the gypsum production is separated into solid and liquid by a filter press to collect the squeezed liquid, 150 g of washing water is supplied to the insoluble residue containing cake-like gypsum, and the squeezed water is again squeezed by the filter press. Was recovered. Then, the squeezed solution and the recovered washing water were collectively used as a dissolution treatment solution (T-4). Table 3 shows the composition of the insoluble residue and the dissolution treatment liquid.

Next, 113.1 g of slaked lime and 14.1 g of 48% caustic soda are added so that the pH becomes about 2 while heating so that the temperature of the dissolution treatment liquid becomes 60 ° C., and stirred for 20 minutes. Reaction with the remaining sulfate radicals produced gypsum, and the sulfate radicals in the solution were removed (T-5). The pH at the start of the sulfate radical removal treatment was 1.5, and the temperature was 77 ° C. And pH at the time of a sulfate radical removal process being complete | finished was 2.0, and temperature was 65 degreeC. Subsequently, the solution obtained by removing the sulfate radical is solid-liquid separated with a filter press to recover the squeezed solution, and 150 g of washing water is supplied to the cake-like gypsum and again squeezed with the filter press to obtain the washing water. The solid-liquid separation process which collect | recovered and mixed with squeezed solution to make a solution was performed (T-6). Table 3 shows the composition of gypsum and the solution.

While heating so that the temperature of the recovered solution (2225.2 g) is 40 ° C., 19.8 g of iron powder is added so that the redox potential is about −250 mV while the pH is 3 or less. And it stirred for 20 minutes, copper was deposited on the iron powder surface, and copper collection | recovery was performed (T-7). Here, the processing in each step after the chromium ion removing step sequentially performed on the copper ion removing solution recovered after the copper recovery is completed is substantially the same as in the case of the first embodiment, and thus detailed description thereof is omitted. In the case of Example 2, the total nickel recovery rate was 57.0%.

(Example 3)
From the same multicomponent-containing nickel plating waste liquid sludge used in Example 1, copper, chromium, iron, and nickel were separately collected in order. FIG. 19 is a process explanatory diagram of a method for recycling a multicomponent-containing nickel plating waste liquid sludge, and FIGS. 20 to 23 are detailed process explanatory diagrams of a method for recycling a multicomponent-containing nickel plating waste liquid sludge.
As shown in FIG. 20, 20.3 g of gypsum produced by adding slaked lime to the remaining nickel sulfate solution in the previous treatment is added to the multicomponent-containing nickel plating waste sludge, and the pH is adjusted to 0.8. 34.0 g of% hydrochloric acid was diluted and added to 684.5 g of the residual liquid generated during the previous treatment to prepare (repulp) a slurry having a slurry concentration of about 10% by weight (U-1).

Subsequently, hydrochloric acid dissolution treatment (U-) in which 346.9 g of 15% hydrochloric acid is added so that the pH becomes about 1 while heating so that the temperature of the slurry becomes 40 ° C., and the solid content is dissolved by stirring for 30 minutes. 2) was performed to form a dissolved product. The pH of the slurry at the start of the hydrochloric acid dissolution treatment was 1.0 and the temperature was 47 ° C. The pH of the slurry at the end of the hydrochloric acid dissolution treatment was 1.0 and the temperature was 42 ° C. Next, 9.8 g of slaked lime is added so that the pH becomes about 2 while heating so that the temperature of the dissolution treatment product obtained after the hydrochloric acid dissolution treatment is 60 ° C., and stirred for 15 minutes to dissolve. It was made to react with the sulfate radical in a processed material, the gypsum was produced | generated, and the sulfate radical removal process in a melt | dissolution processed material was performed (U-3). The pH of the dissolution treatment product at the start of the sulfate radical removal treatment was 2.1 and the temperature was 43 ° C. The pH at the time of completion of the sulfate radical removal treatment was 2.7 and the temperature was 41 ° C. Then, the dissolved processed product after the sulfate radical removal treatment is solid-liquid separated using a filter press and recovered by squeezing, and 150 g of washing water is supplied to the undissolved residue containing cake-like gypsum and the filter press again. A solid-liquid separation process was performed by collecting the washing water and mixing with the squeezed solution to obtain a solution (U-4). The compositions of the insoluble residue and the solution are shown in Table 4 and Table 5, respectively.

While heating so that the temperature of the recovered solution (1348.1 g) is 40 ° C., 3.8 g of iron powder is added so that the pH is 3 or less and the redox potential is about −250 mV. And it stirred for 10 minutes, copper was deposited on the iron powder surface, and copper collection | recovery was performed (U-5). The redox potential of the solution at the start of copper recovery was −310 mV, the pH was 2.9, the temperature was 41 ° C., the redox potential at the time of completion of copper recovery was −311 mV, and the pH was 2.9. The temperature was 45 ° C.
Next, the liquid after completion of copper recovery is solid-liquid separated with a filter press to recover the squeezed liquid, and 50 g of washing water is supplied to the cake-like copper-attached iron powder with copper deposited on the surface of the iron powder, and the filter press again. The solid was subjected to solid-liquid separation treatment by collecting the washing water and mixing with the squeezed liquid to obtain a copper ion removing liquid (U-6). The compositions of the copper-adhered iron powder and the copper ion removing solution are shown in Tables 4 and 5, respectively.

As shown in FIG. 21, while heating the recovered copper ion removal liquid (1345.3 g) to 60 ° C., add 146.1 g of 10% sodium hydroxide so that the pH is about 4.2. Then, the mixture was stirred for 10 minutes to perform chromium neutralization treatment to change chromium ions to chromium hydroxide (U-7). The pH of the copper ion removing solution at the start of the chromium neutralization treatment was 4.2 and the temperature was 63 ° C. The pH at the end of the chromium neutralization treatment was 4.2 and the temperature was 62 ° C. Here, 10% caustic soda is prepared using the residual liquid generated during the previous treatment.
Next, the copper ion removal solution after the chromium neutralization treatment is completed is separated into solid and liquid by a filter press to collect the squeezed solution, and 50 g of washing water is supplied to the cake-like chromium hydroxide starch and again by the filter press. The solid was subjected to solid-liquid separation treatment by collecting the washing water by pressing and mixing with the squeezed liquid to obtain a chromium ion removing liquid (U-8). Tables 4 and 5 show the compositions of the chromium hydroxide starch and the chromium ion removing solution, respectively.

As shown in FIG. 21, while heating the recovered chromium ion removing solution (1337.1 g) to 40 ° C., 2.2 g of hydrogen peroxide was added and stirred for 10 minutes to remove chromium ions. Ferrous ions in the liquid were oxidized to change to ferric ions (U-9). Here, 20.0 g of ferric hydroxide starch generated during the previous treatment was added as a filter aid. The oxidation-reduction potential of the chromium ion removing solution at the start of the ferrous ion oxidation treatment is 613 mV, the pH is 2.3, and the temperature is 41 ° C. The oxidation-reduction when the ferrous ion oxidation treatment is completed. The potential was 617 mV, the pH was 2.1, and the temperature was 50 ° C.

Next, 6.4 g of 48% caustic soda is added to the pH of about 3.5 while stirring so that the temperature of the liquid after the oxidation treatment of ferrous ions is 60 ° C., and the mixture is stirred for 30 minutes. Ferric iron neutralization treatment was performed to change ferric ions to ferric hydroxide (U-10). The pH of the solution during ferric iron neutralization was 2.8 and the temperature was 64 ° C. The pH of the solution after ferric iron neutralization was 3.4 and the temperature was 62 ° C. It was. Then, the liquid after the ferric iron neutralization treatment is separated into solid and liquid by a filter press to collect the squeezed liquid, and 50 g of washing water is supplied to the cake-like ferric hydroxide starch and pressed again by the filter press. Then, the washing water was collected and mixed with the squeezed liquid to carry out a solid-liquid separation treatment to obtain a treatment liquid (U-11). The compositions of ferric hydroxide starch and the treatment liquid are shown in Table 4 and Table 5, respectively.

As shown in FIG. 22, while heating the recovered processing solution to 60 ° C., 488.1 g of 48% caustic soda so as to have a pH of about 10 was obtained by 428.6 g of residual liquid generated during the previous processing. Then, the mixture was stirred for 30 minutes, and nickel neutralization treatment was performed to change nickel ions to nickel hydroxide (U-12). The pH of the solution at the start of the nickel neutralization treatment was 10.5 and the temperature was 56 ° C. The pH of the solution at the end of the nickel neutralization treatment was 10.2 and the temperature was 62 ° C.
Next, the liquid after completion of the nickel neutralization treatment is separated into solid and liquid with a filter press to collect the squeezed liquid, and 200 g of washing water is supplied to the cake-like nickel hydroxide starch and again squeezed with a filter press to obtain washing water. Was collected and mixed with the squeezed liquid to perform a solid-liquid separation process to obtain a residual liquid (U-13). The compositions of nickel hydroxide starch and residual liquid are shown in Table 4 and Table 5, respectively.

225.0 g of water was added to the recovered nickel hydroxide starch (225.1 g, solid content 35.5 g), and a slurry was prepared (repulped) so that the slurry concentration was about 10% by weight (U-14). ). Next, while heating so that the temperature of the nickel hydroxide starch slurry is 60 ° C., 82.4 g of 70% sulfuric acid is added so that the pH is about 0.7, and the mixture is stirred for 15 minutes. The sulfuric acid extraction process which dissolves a starch in a sulfuric acid was performed (U-15). The pH of the slurry at the start of the sulfuric acid extraction treatment was 0.7, and the temperature was 64 ° C. When the sulfuric acid extraction treatment was completed, the pH was 0.7 and the temperature was 63 ° C.
Next, the slurry after the sulfuric acid extraction treatment is solid-liquid separated with a filter press to collect the squeezed solution, and 50 g of washing water is supplied to the cake-like insoluble matter and again squeezed with a filter press to collect the washing water. Then, it was mixed with the squeezed liquid to perform a solid-liquid separation process to obtain a nickel sulfate solution (U-16). Tables 4 and 5 show the compositions of the insoluble residue and the nickel sulfate solution, respectively.

As shown in FIG. 23, the recovered nickel sulfate solution was heated to evaporate 393 g of water and concentrated (U-17) to prepare a nickel sulfate concentrate. The resulting nickel sulfate concentrate is indirectly cooled to maintain the temperature at 0 ° C. to crystallize nickel sulfate crystals (U-18), and the nickel sulfate crystals are recovered by centrifugation and the remaining nickel sulfate solution. Was separated (U-19). Next, 46.6 g of 30% caustic soda and 200 g of water were added to the remaining nickel sulfate solution to adjust the pH to about 2, and the temperature was maintained at 60 ° C. and maintained for 10 minutes (U-20). The pH of the liquid at the start of pH adjustment was 2.0, the temperature was 76 ° C., the pH of the liquid after being held for 10 minutes was 1.9, and the temperature was 65 ° C.

Subsequently, 100.0 g of 30% calcium chloride is added to the liquid, the temperature is adjusted to 60 ° C., the pH is adjusted to about 2, and maintained for 20 minutes, and the sulfate radical and calcium chloride present in the liquid are reacted to form gypsum. (U-21). The pH of the liquid at the start of gypsum production was 2.0 and the temperature was 60 ° C. The pH of the liquid at the completion of gypsum production was 1.9 and the temperature was 58 ° C.
Next, the liquid is separated into solid and liquid with a filter press to collect the squeezed solution, and 100 g of washing water is supplied to the cake-like gypsum, and squeezed again with the filter press to collect the washing water and mix with the squeezed sulfuric acid A solid-liquid separation process was performed as a root removal liquid (U-22). The compositions of nickel sulfate crystals, residual nickel sulfate solution, gypsum, and sulfate radical removal solution are shown in Tables 4 and 5, respectively. Here, a part of the recovered sulfate radical removal solution is stored as a dilute solution of caustic soda used in the nickel fraction recovery step at the next processing. In the case of Example 3, the total nickel recovery rate was 61.4%.

Example 4
Copper, zinc, and nickel were separately collected in order from a multicomponent-containing nickel plating waste liquid sludge containing copper, zinc, and nickel (also simply referred to as plating sludge). FIG. 24 is a detailed process explanatory diagram of the recycling method for multicomponent-containing nickel plating waste liquid sludge, and FIGS. 25 to 28 show the operations of the recycling method for multicomponent-containing nickel plating waste liquid sludge.
As shown in FIG. 25, the plating sludge (5000.0 g, solid content 1825.0 g) is crushed (V-1), and 15% hydrochloric acid 9184.0 g is added so that the pH is 0.5. It was prepared and stirred for 60 minutes while heating so that the temperature of the slurry was 40 ° C., and the hydrochloric acid dissolution treatment was performed to dissolve the solid content to obtain a dissolution treatment liquid (V-2). The pH of the slurry at the start of the hydrochloric acid dissolution treatment was 0.5 and the temperature was 43 ° C. The pH of the dissolution treatment product at the end of hydrochloric acid extraction was 0.5 and the temperature was 42 ° C. Next, the dissolved processed product is separated into solid and liquid using a filter press and collected by squeezing, and 200 g of washing water is supplied to the cake-like insoluble residue and squeezed again by the filter press to collect the washing water and squeezed The solid-liquid separation process which made it a solution by mixing with (V-3) was performed. The compositions of the insoluble residue and the solution are shown in Table 6 and Table 7, respectively.

Subsequently, the remaining solution 1069.0 g and sulfate radical removal solution 436.5 g generated during the previous treatment were added to the collected solution 500.0 g and diluted to form a treatment diluted solution (V-4). Next, as shown in FIG. 26, while heating so that the temperature of the treatment diluted solution (1988. 1 g) is 60 ° C., 26.2 g of calcium carbonate is added so that the pH is about 5, and the mixture is stirred for 30 minutes. The copper neutralization process which changes a copper ion into copper hydroxide was performed (V-5). In addition, pH of the process dilution liquid at the time of a copper neutralization process start was 4.7, temperature was 57 degreeC, pH at the time of completion | finish of copper neutralization process was 5.4, and temperature was 62 degreeC. The composition of the treatment diluent is shown in Table 7.
Next, the processing diluted solution after completion of the copper neutralization treatment is separated into solid and liquid by a filter press to recover the squeezed solution, and 200 g of washing water is supplied to the cake-like copper hydroxide starch and squeezed again by the filter press. Then, the washing water was recovered and mixed with the squeezed liquid to perform a solid-liquid separation process to obtain a copper ion removing liquid (V-6). The compositions of the copper hydroxide starch and the copper ion removing solution are shown in Tables 6 and 7, respectively.

In addition, while heating the recovered copper ion removing liquid (2070.9 g) to 60 ° C., 31.6 g of 48% caustic soda is diluted with 534 g of residual liquid generated during the previous treatment and added to the makeup water. 42.2g was added, and it stirred for 60 minutes, and the zinc neutralization process which changes a zinc ion into zinc hydroxide was performed (V-7). The pH of the copper ion removing solution at the start of the zinc neutralization treatment was 6.8, the temperature was 43 ° C., the pH at the end of the zinc neutralization treatment was 6.2, and the temperature was 61 ° C.
Next, the solution after completion of the zinc neutralization treatment is separated into solid and liquid with a filter press to recover the squeezed solution, and 200 g of washing water is supplied to the cake-like zinc hydroxide starch and again squeezed with a filter press to be washed. Water was collected, mixed with the squeezed solution, and subjected to solid-liquid separation treatment to obtain a zinc ion removing solution. The compositions of the zinc hydroxide starch and zinc ion removing solution are shown in Tables 6 and 7, respectively.

As shown in FIG. 27, while heating the recovered zinc ion removal solution (2619.9 g) to 60 ° C., 65.2 g of 48% caustic soda was added and stirred for 60 minutes to convert nickel ions to nickel hydroxide. The nickel neutralization process which changes to (V-9) was performed. The pH of the zinc ion removing solution at the start of the nickel neutralization treatment was 11.4 and the temperature was 44 ° C. The pH of the solution when the nickel neutralization treatment was completed was 10.6 and the temperature was 61 ° C.
Next, the liquid after the nickel neutralization treatment is separated into solid and liquid with a filter press to recover the squeezed liquid, and 200 g of washing water is supplied to the cake-like nickel hydroxide starch and again squeezed with a filter press to wash the washing water. Were separated and mixed with the squeezed liquid to obtain a residual liquid (V-10). The compositions of nickel hydroxide starch and residual liquid are shown in Tables 6 and 7, respectively. A part of the recovered residual liquid is stored as a diluted liquid when preparing a processing diluted liquid from the dissolved liquid, or as a diluted liquid of caustic soda added during the zinc neutralization process, and the remaining part is processed as a waste liquid.

A slurry was prepared (repulped) by adding 150 g of water to the recovered nickel hydroxide starch (143.1 g, solid content 30.0 g) (V-11). Next, while heating so that the temperature of the nickel hydroxide starch slurry is 60 ° C., 60.6 g of 70% sulfuric acid is added so that the pH is about 0.7, and the mixture is stirred for 10 minutes. The sulfuric acid extraction process (V-12) which dissolves a starch in a sulfuric acid was performed. The pH of the slurry at the start of the sulfuric acid extraction treatment was 0.4 and the temperature was 58 ° C. The pH at the end of the sulfuric acid extraction treatment was 0.5 and the temperature was 60 ° C. Next, the slurry after the sulfuric acid extraction treatment is solid-liquid separated with a filter press to collect the squeezed solution, and 100 g of washing water is supplied to the cake-like insoluble residue and again squeezed with a filter press to collect the washing water. Then, it was mixed with the squeezed liquid and subjected to solid-liquid separation treatment to obtain a nickel sulfate solution (V-13). The compositions of insoluble residue and nickel sulfate solution are shown in Table 6 and Table 7, respectively.

As shown in FIG. 28, 391.5 g of the recovered nickel sulfate solution was heated to evaporate 259 g of water and concentrated (V-14) to prepare a nickel sulfate concentrate. The resulting nickel sulfate concentrate is indirectly cooled to maintain the temperature at 0 ° C. to crystallize the nickel sulfate crystals and then centrifuged to collect the nickel sulfate crystals and separate the remaining nickel sulfate solution. (V-15). Tables 6 and 7 show the compositions of the nickel sulfate crystals and the remaining nickel sulfate solution.
Next, 200 g of water was added to the residual nickel sulfate solution to dilute it (V-16), and 133.6 g of 30% calcium chloride was added while heating to a temperature of 60 ° C. By adding calcium chloride, the pH of the remaining nickel sulfate solution was 0.3 and the temperature was 58 ° C. Furthermore, 29.4 g of calcium carbonate was added and stirred for 30 minutes, and sulfate radical removal treatment was performed to react the sulfate radicals present in the residual nickel sulfate solution with calcium ions to produce gypsum (V-17). The solution immediately after the addition of calcium carbonate had a pH of 1.2 and a temperature of 68 ° C., and after stirring for 30 minutes, the pH was 1.1 and the temperature was 61 ° C.

The liquid after the sulfate radical removal treatment is separated into solid and liquid with a filter press to collect the squeezed liquid, and 100 g of washing water is supplied to the cake-like gypsum and squeezed again with the filter press to collect the washing water and Solid-liquid separation treatment was performed by mixing to make a sulfate radical removal solution (V-18). The compositions of the gypsum and sulfate radical removal solution are shown in Table 6 and Table 7, respectively. Here, a part of the recovered sulfate radical removal solution is stored for use as a diluent when preparing a treatment diluent from the solution, and the remainder is treated as a waste solution. In the case of Example 4, the total nickel recovery rate was 36.4%.

(Example 5)
The zinc hydroxide starch recovered in Example 4 (hereinafter referred to as the to-be-purified zinc hydroxide starch) is purified with zinc hydroxide, and the zinc content of the zinc hydroxide starch and the overall nickel recovery rate Improved. FIG. 29 and FIG. 30 show detailed explanatory views when refining zinc hydroxide.
As shown in FIG. 29, slurry preparation (repulping) was performed by adding 1000 g of water to a to-be-purified zinc hydroxide starch (527.8 g, solid content 99.2 g) (W-1). Next, 477.1 g of 15% hydrochloric acid was added so that the pH of the slurry was about 1, and the mixture was stirred for 30 minutes while heating to a temperature of 60 ° C. to dissolve the treated zinc hydroxide starch to prepare a slurry. Inorganic acid extraction treatment (hydrochloric acid dissolution treatment) was performed (W-2). The pH of the slurry at the start of the inorganic acid extraction treatment was 1.0, and the temperature was 61 ° C. Next, the dissolved processed product that has been subjected to the inorganic acid extraction treatment is solid-liquid separated with a filter press to collect the squeezed solution, and 100 g of washing water is supplied to the cake-like insoluble matter and is again squeezed with the filter press to obtain washing water. Was collected and mixed with the squeezed liquid to perform a solid-liquid separation process to obtain a zinc-containing liquid (W-3). Tables 8 and 9 show the compositions of the to-be-purified zinc hydroxide starch and the zinc-containing liquid, respectively.

Add 482.0 g of iron powder to 482.0 g of the recovered zinc-containing solution, add 85.0 g of 15% hydrochloric acid so that the pH is 4 or less, and maintain the temperature at 40 ° C. to oxidize the zinc-containing solution. Nickel produced by stirring for 180 minutes so that the reduction potential is about -470 mV, replacing nickel ions and iron in the zinc-containing liquid during stirring, and forming nickel-attached iron powder in which nickel is deposited on the surface of the iron powder A recovery cementation process (W-4) was performed. In addition, 2 ml of hydrochloric acid was added every 30 minutes from the start of stirring so that the pH would be 4 or less during stirring. When the nickel recovery cementation process was completed, the oxidation-reduction potential of the liquid was −592 mV, pH was 3.6, and temperature was 43 ° C. Then, the liquid after completion of the nickel recovery cementation process is separated into solid and liquid by a filter press to recover the squeezed liquid, and 100 g of washing water is supplied to the cake-like nickel-attached iron powder and again compressed by the filter press and washed. Water was collected and mixed with the squeezed liquid to perform a solid-liquid separation process to obtain a nickel ion-removed zinc-containing liquid (W-5). The compositions of the nickel-adhered iron powder and nickel ion-removed zinc-containing liquid are shown in Tables 8 and 9, respectively.

As shown in FIG. 30, the temperature of the recovered nickel ion-removed zinc-containing liquid (561.3 g) is heated to 40 ° C. and 42.3 g of hydrogen peroxide solution is added to adjust the redox potential to 600 mV or higher. Then, the mixture was stirred for 2 minutes, and an oxidation treatment was performed to change the ferrous ions in the nickel-containing zinc-containing liquid to ferric ions (W-6). The oxidation-reduction potential of the liquid after completion of the oxidation treatment was 569 mV, pH was 1.8, and temperature was 30 ° C.
Next, 29.8 g of calcium carbonate is added so that the pH is 4.5 or lower while heating the nickel ion-removed zinc-containing liquid that has undergone the oxidation treatment to 60 ° C., and the mixture is stirred for 15 minutes. Ferric iron neutralization treatment (W-7) was carried out to change the ferric ion to ferric hydroxide. When the ferric iron neutralization treatment was completed, the pH of the solution was 4.1 and the temperature was 60 ° C. Then, the liquid after the ferric iron neutralization treatment is separated into solid and liquid with a filter press to collect the squeezed liquid, and 200 g of washing water is supplied to the cake-like ferric hydroxide starch and pressed again with the filter press. Then, the washing water was recovered and mixed with the squeezed liquid to perform a solid-liquid separation process to obtain an iron ion-removed zinc-containing liquid (W-8). The compositions of the ferric hydroxide starch and the iron ion-removed zinc-containing liquid are shown in Table 8 and Table 9, respectively.

While heating so that the temperature of the recovered iron ion-removed zinc-containing liquid (555.5 g) is 60 ° C., 15.9 g of slaked lime is added to adjust the pH to the range of 8 to 12, and the mixture is stirred for 15 minutes. The zinc neutralization process which changes ion to zinc hydroxide was performed (W-9). When the zinc neutralization treatment was completed, the pH of the solution was 10.6 and the temperature was 64 ° C.
Next, the solution after completion of the zinc neutralization treatment is solid-liquid separated with a filter press to collect the squeezed solution (calcium chloride solution), and supply 200 g of washing water to the cake-like re-recovered zinc hydroxide starch and filter again. A solid-liquid separation process was performed by pressing with a press to collect washing water and mixing with the squeezed liquid to obtain a waste liquid (W-10). Tables 8 and 9 show the compositions of the re-recovered zinc hydroxide starch (starch having a high zinc hydroxide content) and the waste liquid, respectively. As shown in Table 8, 35% by weight of nickel is contained in the refined treated zinc hydroxide starch, whereas the nickel content in the re-recovered zinc hydroxide starch is 0.1% by weight. Thus, the content of zinc hydroxide in the re-recovered zinc hydroxide starch could be improved.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this embodiment, The change in the range which does not change the summary of invention is possible, Each above-mentioned embodiment is possible. The case where the recycling method of the multi-component-containing nickel plating waste liquid sludge according to the present invention is configured by combining some or all of the forms and modifications is also included in the scope of the present invention.
For example, in the first and third embodiments, the gypsum generation process and the solid-liquid separation process are performed in the inorganic acid extraction step, but these processes may be omitted. In the second embodiment, the filter aid mixing process, the gypsum generation process, and the solid-liquid separation process are performed. However, either one of the filter aid mixing process and the gypsum generation process may be omitted. All of the mixing process, the gypsum generation process, and the solid-liquid separation process can be omitted. Furthermore, in the first to third embodiments, the sulfate radical removing treatment step and the like can be omitted. Moreover, although hydrochloric acid was used as an inorganic acid in the inorganic acid extraction step, either sulfuric acid or nitric acid can be used.
Further, in the first and second embodiments, the multicomponent-containing nickel plating waste liquid sludge containing copper, chromium, zinc, iron, and nickel has been described. However, copper, iron and nickel, or copper, iron, nickel And zinc, or copper, chromium, iron and nickel, or chromium, iron and nickel, or multi-component nickel plating waste liquid sludge containing chromium, iron, nickel and zinc.
In addition, in the chromium ion removal process in the case of using a multicomponent-containing nickel plating waste liquid sludge containing chromium, iron, and nickel, a reducing agent is added to the solution obtained in the inorganic acid extraction step to add trivalent iron ions in the solution. Is reduced to divalent iron ions, an alkaline agent is added to adjust the pH, and chromium neutralization treatment is performed to change chromium ions in the solution to chromium hydroxide. Separated and used as a chromium ion removal solution.

It is process explanatory drawing of the recycling processing method of the multicomponent content nickel plating waste liquid sludge which concerns on the 1st Embodiment of this invention. It is explanatory drawing of the sulfate radical removal process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is explanatory drawing of the copper ion removal process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is explanatory drawing of the chromium ion removal process in the recycling processing method of the same multicomponent containing nickel plating waste liquid sludge. It is explanatory drawing of the iron ion removal process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is explanatory drawing of the zinc separation collection process in the recycling processing method of the same multicomponent containing nickel plating waste liquid sludge. It is explanatory drawing at the time of performing refinement | purification of the zinc hydroxide in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is explanatory drawing of the nickel fraction collection process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is explanatory drawing of the sulfuric acid extraction process and the nickel sulfate recovery process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is process explanatory drawing of the recycling processing method of the multicomponent content nickel plating waste liquid sludge which concerns on the 2nd Embodiment of this invention. It is explanatory drawing of the sulfate radical removal process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is process explanatory drawing of the recycling processing method of the multicomponent content nickel plating waste liquid sludge which concerns on the 3rd Embodiment of this invention. It is explanatory drawing of the copper ion removal process in the recycling processing method of the same multicomponent content nickel plating waste liquid sludge. It is process explanatory drawing of the recycling processing method of the multicomponent containing nickel plating waste liquid sludge in Example 1. FIG. FIG. 3 is a detailed explanatory diagram of a method for recycling a multicomponent-containing nickel plating waste liquid sludge in Example 1; FIG. 3 is a detailed explanatory diagram of a method for recycling a multicomponent-containing nickel plating waste liquid sludge in Example 1; FIG. 3 is a detailed explanatory diagram of a method for recycling a multicomponent-containing nickel plating waste liquid sludge in Example 1; It is explanatory drawing of the inorganic acid extraction process of the recycling processing method of the multicomponent containing nickel plating waste liquid sludge in Example 2. FIG. It is a detailed explanatory view of the recycling processing method of the multicomponent content nickel plating waste liquid sludge in Example 3. It is a detailed explanatory view of the recycling processing method of the multicomponent content nickel plating waste liquid sludge in Example 3. It is a detailed explanatory view of the recycling processing method of the multicomponent content nickel plating waste liquid sludge in Example 3. It is a detailed explanatory view of the recycling processing method of the multicomponent content nickel plating waste liquid sludge in Example 3. It is a detailed explanatory view of the recycling processing method of the multicomponent content nickel plating waste liquid sludge in Example 3. It is detailed explanatory drawing of the recycling processing method of the multicomponent containing nickel plating waste liquid sludge in Example 4. FIG. It is detailed explanatory drawing of the recycling processing method of the multicomponent containing nickel plating waste liquid sludge in Example 4. FIG. It is detailed explanatory drawing of the recycling processing method of the multicomponent containing nickel plating waste liquid sludge in Example 4. FIG. It is detailed explanatory drawing of the recycling processing method of the multicomponent containing nickel plating waste liquid sludge in Example 4. FIG. It is detailed explanatory drawing of the recycling processing method of the multicomponent containing nickel plating waste liquid sludge in Example 4. FIG. 6 is a detailed explanatory diagram of zinc hydroxide purification treatment in Example 5. FIG. 6 is a detailed explanatory diagram of zinc hydroxide purification treatment in Example 5. FIG.

Claims (23)

Inorganic acid extraction step of forming a dissolved treatment product by adding an inorganic acid to a multicomponent-containing nickel plating waste liquid sludge containing copper, iron, and nickel, and removing an insoluble matter from the dissolution treatment product to obtain a solution,
Add copper powder to the solution to adjust the oxidation-reduction potential, replace the copper ion in the solution with iron, separate the copper-attached iron powder with copper deposited on the surface, and use it as a copper ion removal solution A removal step;
An oxidizing agent is added to the copper ion removing solution, an oxidation treatment is performed to oxidize divalent iron ions in the copper ion removing solution to trivalent iron ions, an alkaline agent is added to adjust the pH, and the trivalent iron ions are adjusted. A ferric hydroxide neutralization treatment to convert ferric hydroxide into ferric hydroxide, and a ferric hydroxide starch produced as a separated treatment solution,
A nickel fractionation and recovery step of adjusting the pH by adding an alkaline agent to the treatment liquid, performing nickel neutralization treatment to change nickel ions in the treatment liquid to nickel hydroxide, and generating nickel hydroxide starch;
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
A method of recycling a multi-component nickel plating waste liquid sludge, comprising: a nickel sulfate recovery step of performing a cooling crystallization process on the nickel sulfate solution and recovering the crystallized nickel sulfate crystals. 2. The recycling method for multi-component nickel plating waste liquid sludge according to claim 1, wherein the alkaline agent used in either one or both of the ferric iron neutralization treatment and the nickel neutralization treatment is the previous nickel. It is diluted with a part of the residual liquid after recovering nickel hydroxide starch in the fractional recovery step, and the remaining part of the residual liquid is mixed with the multicomponent-containing nickel plating waste liquid sludge. Recycling method for multi-component nickel plating waste liquid sludge. An inorganic acid extraction step of forming a dissolved treatment product by adding an inorganic acid to a multicomponent-containing nickel plating waste liquid sludge containing chromium, iron, and nickel, and removing an insoluble matter from the dissolved treatment product to obtain a solution;
A reducing agent is added to the solution to reduce the trivalent iron ions in the solution to divalent iron ions, an alkaline agent is added to adjust the pH, and the chromium ions in the solution are hydroxylated. Chromium ion removal process that performs chromium neutralization treatment to change to chromium, separates the generated chromium hydroxide starch and makes a chromium ion removal solution,
An oxidizing agent is added to the chromium ion removing solution, an oxidation treatment is performed to oxidize divalent iron ions in the chromium ion removing solution to trivalent iron ions, an alkaline agent is added to adjust the pH, and the trivalent iron ions are adjusted. A ferric hydroxide neutralization treatment to convert ferric hydroxide into ferric hydroxide, and a ferric hydroxide starch produced as a separated treatment solution,
A nickel fractionation and recovery step of adjusting the pH by adding an alkaline agent to the treatment liquid, performing nickel neutralization treatment to change nickel ions in the treatment liquid to nickel hydroxide, and generating nickel hydroxide starch;
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
A method of recycling a multi-component nickel plating waste liquid sludge, comprising: a nickel sulfate recovery step of performing a cooling crystallization process on the nickel sulfate solution and recovering the crystallized nickel sulfate crystals. An inorganic acid extraction step of forming a dissolved processed product by adding an inorganic acid to a sludge sludge containing multicomponents containing copper, chromium, iron, and nickel to obtain a dissolved solution by removing an insoluble matter from the processed solution; ,
Add copper powder to the solution to adjust the oxidation-reduction potential, replace the copper ion in the solution with iron, separate the copper-attached iron powder with copper deposited on the surface, and use it as a copper ion removal solution A removal step;
An alkaline agent is added to the copper ion removing solution to adjust the pH, and a chromium neutralization treatment is performed to change chromium ions in the copper ion removing solution into chromium hydroxide. A chromium ion removal step as an ion removal solution;
An oxidizing agent is added to the chromium ion removing solution, an oxidation treatment is performed to oxidize divalent iron ions in the chromium ion removing solution to trivalent iron ions, an alkaline agent is added to adjust the pH, and the trivalent iron ions are adjusted. A ferric hydroxide neutralization treatment to convert ferric hydroxide into ferric hydroxide, and a ferric hydroxide starch produced as a separated treatment solution,
A nickel fractionation and recovery step of adjusting the pH by adding an alkaline agent to the treatment liquid, performing nickel neutralization treatment to change nickel ions in the treatment liquid to nickel hydroxide, and generating nickel hydroxide starch;
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
A method of recycling a multi-component nickel plating waste liquid sludge, comprising: a nickel sulfate recovery step of performing a cooling crystallization process on the nickel sulfate solution and recovering the crystallized nickel sulfate crystals. The recycling method of the multicomponent-containing nickel plating waste liquid sludge according to any one of claims 3 and 4, wherein any of the chromium neutralization treatment, the ferric iron neutralization treatment, and the nickel neutralization treatment is performed. The alkaline agent used in 1 or 2 or more is diluted with a part of the remaining liquid after recovering the nickel hydroxide starch in the previous nickel fraction recovery process, and the remaining part of the residual liquid is A method for recycling a multicomponent-containing nickel plating waste liquid sludge, wherein the multicomponent-containing nickel plating waste liquid sludge is mixed. In the recycling method of the multicomponent content nickel plating waste liquid sludge of any one of Claims 1-5, the residual nickel sulfate solution after collect | recovering the nickel sulfate crystal | crystallization crystallized in the last nickel sulfate recovery process The calcium source is added to the gypsum and the generated gypsum is separated to remove the sulfate radicals in the remaining nickel sulfate solution to form a sulfate radical removal solution, and part or all of the sulfate radical removal solution is mixed with the treatment solution A method for recycling a multi-component nickel-plated waste liquid sludge. In the recycling method of the multicomponent content nickel plating waste liquid sludge of any one of Claims 1-5, the residual nickel sulfate solution after collect | recovering the nickel sulfate crystal | crystallization crystallized in the last nickel sulfate recovery process is used. A method for recycling a multicomponent-containing nickel plating waste liquid sludge, wherein the multicomponent-containing nickel plating waste liquid sludge is mixed. The recycling method of the multicomponent-containing nickel plating waste liquid sludge according to claim 1, wherein when the multicomponent-containing nickel plating waste liquid sludge further contains zinc, it is used in the nickel fractional recovery step in the nickel fractional recovery step. The alkali neutralization agent is added to the treatment liquid to adjust the pH, and the zinc neutralization treatment is performed to generate and separate zinc hydroxide starch from the zinc ions in the treatment liquid, and then the nickel neutralization treatment is performed. Recycling method of nickel component waste liquid sludge containing multiple components. The recycling method of the multi-component-containing nickel plating waste liquid sludge according to claim 8, wherein the alkali agent used in the ferric iron neutralization treatment, the nickel neutralization treatment, and the zinc fraction collection treatment is It is diluted with a part of the residual liquid after recovering the nickel hydroxide starch in the nickel fraction recovery step, and the remaining part of the residual liquid is mixed with the multicomponent-containing nickel plating waste liquid sludge. Recycling method for multi-component nickel plating waste liquid sludge. In the recycling method of the multi-component-containing nickel plating waste liquid sludge according to any one of claims 3 and 4, in the case where the multi-component-containing nickel plating waste liquid sludge further contains zinc, Then, an alkaline agent is added to the treatment liquid used in the nickel separation and recovery step to adjust the pH, and after performing a zinc separation and recovery treatment that generates and separates zinc hydroxide starch from zinc ions in the treatment liquid. A method for recycling a multicomponent nickel-plated waste liquid sludge, wherein the nickel neutralization treatment is performed. The recycling method of the multicomponent-containing nickel plating waste liquid sludge according to claim 10, wherein any one of the chromium neutralization treatment, the ferric iron neutralization treatment, the nickel neutralization treatment, and the zinc fraction collection treatment Alternatively, the alkali agent used in two or more is diluted with a part of the remaining liquid after the nickel hydroxide starch is recovered in the previous nickel fraction recovery step, and the remaining part of the residual liquid is A method for recycling a multi-component nickel plating waste liquid sludge, which is mixed with the component-containing nickel plating waste liquid sludge. The residual nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step in the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to any one of claims 8 to 11 The gypsum produced by adding a calcium source is separated to remove sulfate radicals in the residual nickel sulfate solution to form a sulfate radical removal solution, and a part or all of the sulfate radical removal solution is zinc from the treatment solution. A recycling method for multi-component nickel plating waste liquid sludge, which is mixed with a nickel ion-containing liquid after removing ions. The residual nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step in the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to any one of claims 8 to 11 Is mixed with the multicomponent-containing nickel plating waste liquid sludge. A method for recycling the multicomponent-containing nickel plating waste liquid sludge. The recycling method of the multi-component nickel plating waste liquid sludge according to any one of claims 8 to 13, wherein the zinc hydroxide starch is treated with an inorganic acid with respect to the separated zinc hydroxide starch. Inorganic acid extraction treatment to prepare a zinc-containing solution by dissolving in,
A nickel ion-removed zinc-containing liquid in which iron powder is added to the zinc-containing liquid to adjust the oxidation-reduction potential to replace nickel ions and iron in the zinc-containing liquid and nickel is deposited on the surface. Nickel ion separation treatment to be formed;
An oxidizing agent is added to the nickel ion-removed zinc-containing liquid to oxidize divalent iron ions in the nickel-ion-removed zinc-containing liquid to trivalent iron ions, and then the pH is adjusted to generate hydroxyl from the trivalent iron ions. An iron ion separation process for separating ferric starch to form an iron ion-removed zinc-containing liquid;
Water for recovering starch having a high zinc hydroxide content by adjusting the pH by adding an alkaline agent to the iron ion-removed zinc-containing solution and changing zinc ions in the iron ion-removed zinc-containing solution to zinc hydroxide A method of recycling a multi-component nickel plating waste liquid sludge characterized by performing a zinc oxide re-recovery treatment. An inorganic acid extraction step for forming a dissolved treatment product by adding an inorganic acid to a multicomponent-containing nickel plating waste liquid sludge containing copper, zinc, and nickel, removing an insoluble matter from the dissolved treatment product, and collecting the solution.
An alkaline agent is added to the solution to adjust the pH, and a copper neutralization treatment is performed in which the copper ions in the solution are changed to copper hydroxide, and the resulting copper hydroxide starch is separated into a copper ion removing solution. A copper ion removal step;
Zinc ions obtained by adjusting the pH by adding an alkaline agent to the copper ion removing liquid, and performing zinc neutralization treatment to change the zinc ions in the copper ion removing liquid to zinc hydroxide, and separating the generated zinc hydroxide starch A zinc ion removal step for forming a removal solution;
Nickel separation and recovery step of adjusting the pH by adding an alkaline agent to the zinc ion removing liquid, performing nickel neutralization treatment to change nickel ions in the zinc ion removing liquid into nickel hydroxide, and generating nickel hydroxide starch When,
A sulfuric acid extraction step of adding sulfuric acid to the recovered nickel hydroxide starch to form a nickel sulfate solution;
A method of recycling a multi-component nickel plating waste liquid sludge, comprising: a nickel sulfate recovery step of performing a cooling crystallization process on the nickel sulfate solution and recovering the crystallized nickel sulfate crystals. 16. The recycling method for multi-component nickel plating waste liquid sludge according to claim 15, wherein the alkali used in any one or more of the copper neutralization treatment, the zinc neutralization treatment, and the nickel neutralization treatment. The agent is diluted with a part of the residual liquid after the nickel hydroxide starch is recovered in the previous nickel fraction recovery step, and the remaining part of the residual liquid is mixed with the multi-component nickel plating waste liquid sludge. A method for recycling a multi-component nickel plating waste liquid sludge, characterized in that: The recycling method of the multi-component nickel plating waste liquid sludge according to any one of claims 15 and 16, wherein the zinc hydroxide starch is converted into an inorganic acid with respect to the separated zinc hydroxide starch. An inorganic acid extraction treatment to prepare a zinc-containing solution by dissolving;
A nickel ion-removed zinc-containing liquid in which iron powder is added to the zinc-containing liquid to adjust the oxidation-reduction potential to replace nickel ions and iron in the zinc-containing liquid and nickel is deposited on the surface. Nickel ion separation treatment to be formed;
An oxidizing agent is added to the nickel ion-removed zinc-containing liquid to oxidize divalent iron ions in the nickel-ion-removed zinc-containing liquid to trivalent iron ions, and then the pH is adjusted to generate hydroxyl from the trivalent iron ions. An iron ion separation process for separating ferric starch to form an iron ion-removed zinc-containing liquid;
Water for recovering starch having a high zinc hydroxide content by adjusting the pH by adding an alkaline agent to the iron ion-removed zinc-containing solution and changing zinc ions in the iron ion-removed zinc-containing solution to zinc hydroxide A method of recycling a multi-component nickel plating waste liquid sludge characterized by performing a zinc oxide re-recovery treatment. In the recycling method of the multicomponent nickel plating waste liquid sludge of Claim 17, the alkaline agent used by the said zinc hydroxide re-recovery process collect | recovered nickel hydroxide starch in the last nickel fraction collection process. A method for recycling a multicomponent-containing nickel plating waste liquid sludge, wherein a part of the remaining liquid is diluted. The residual nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step in the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to any one of claims 15 to 18 The gypsum produced by adding a calcium source is separated to remove sulfate radicals in the residual nickel sulfate solution to form a sulfate radical removal solution, and a part of the sulfate radical removal solution is used as the solution, the copper ion A recycling method for multicomponent-containing nickel plating waste liquid sludge, wherein the removal liquid and any one or more of the zinc ion removal liquid are mixed. The residual nickel sulfate solution after recovering the nickel sulfate crystals crystallized in the previous nickel sulfate recovery step in the recycling method of the multicomponent-containing nickel plating waste liquid sludge according to any one of claims 15 to 18 Is mixed with the multicomponent-containing nickel plating waste liquid sludge. A method for recycling the multicomponent-containing nickel plating waste liquid sludge. The recycling method of the multicomponent-containing nickel plating waste liquid sludge according to any one of claims 1 to 20, wherein in the inorganic acid extraction step, a calcium source is added to the dissolved processed product, A method of recycling a multi-component nickel plating waste liquid sludge comprising reacting with a sulfate group to produce gypsum and removing the gypsum together with the insoluble matter. 21. The recycling method for multi-component nickel plating waste liquid sludge according to any one of claims 1 to 20, wherein in the inorganic acid extraction step, the insoluble matter is removed from the dissolved product, and then calcium is removed. A method for recycling a multicomponent nickel-plated waste liquid sludge, wherein a source is added to react with sulfate radicals to form gypsum, and the gypsum is removed to obtain the solution. The recycling method of the multicomponent-containing nickel plating waste liquid sludge according to any one of claims 1 to 22, wherein the inorganic acid is hydrochloric acid. Processing method.

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