JP2879688B2 - Process for producing a solution containing zinc-containing material containing Al - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a dissolving solution obtained by dissolving zinc or a zinc-containing substance such as plated dross or solder generated in a zinc-based plating plant in a basic ammonium carbonate solution. And a method for producing the same.

[Conventional technology]

In recent years, at steelworks, in order to achieve advanced utilization of steel sheets,
As zinc or a zinc-based plated steel sheet, it is increasingly used as a steel sheet for automobiles and a steel sheet for home appliances. In such a plating step, a relatively large amount of plating dross is generated, but conventionally, there is almost no use of the plating dross, and it is sold at a low price to a specialized zinc supplier. To increase the purity.

The above-mentioned Zn-Al plating dross particularly contains, for example, about 0.1 to 10% of Al. Therefore, the Al content should be removed and reused in the zinc or zinc-based plating step. It is desirable to use zinc oxide as a magnetic material.

On the other hand, the present applicant disclosed in Japanese Patent Application Laid-Open No. 59-88319 or the like that a zinc-containing substance containing Fe and Pb was dissolved in a basic ammonium carbonate solution, and then a step of removing impurities (particularly, removing Fe and Pb) was performed. The solution was led to a crystallization step, and it was proposed to recover zinc as basic zinc carbonate by a crystallization operation, and it was confirmed that the method was a practically superior method (hereinafter referred to as a prior method).

[Problems to be solved by the invention]

As described above, the Zn-Al plating dross contains a relatively large amount of Al, and if this is not removed, the Zn
When used for plating, there are problems such as impairing the plating properties or deteriorating the magnetic properties.

Therefore, removal of Al is an important issue, and if a zinc carbonate solution having a low content of Al can be obtained when a zinc-containing substance is dissolved in a basic ammonium carbonate solution, a carbonate according to the above-mentioned prior method can be obtained. Can be recovered as zinc.

However, the subject zinc-containing material in the above publication was not a raw material whose Al content was a problem, so that care was not required for its removal. However, it has been found that when the Al content is large, as in the case of the above-mentioned Zn-Al plated dross, even if the prior method is applied as it is, it is impossible to obtain a zinc carbonate crystal with very little Al.

Therefore, various Al removal methods were tried, but failed completely.

Therefore, an object of the present invention is to obtain a zinc solution having a low Al content.

[Means for solving the problem]

The above object is to dissolve a zinc-containing material containing Al in a basic ammonium carbonate solution, and to dissolve NH ₃ : CO ₃
The problem can be solved by setting the concentration weight ratio to 1: 0.8 to 1: 1.8.

[Action]

The present inventors have found that, even for a zinc-containing substance containing Al, it is excellent to be dissolved by a basic ammonium carbonate solution, and in the solution production step, the Al content is reduced, and the solution having a low Al content is reduced. It has been found that, after that, zinc can be recovered as high-purity zinc carbonate by applying the prior method as it is. If necessary, zinc oxide can be further calcined to obtain zinc oxide.

On the other hand, the present inventor disclosed in the above publications that when dissolving a zinc-containing substance with a basic ammonium carbonate solution, the respective concentrations of NH ₄ OH and (NH ₄ ) ₂ CO ₃ were 5 to 40.
% Was preferred, but at the time of the proposal, it was not intended to dissolve zinc-containing substances having a high Al content, which is the object of the present invention. Although not required, in dissolving a zinc-containing material having a high Al content, in order to surely reduce the Al content, it may not be possible to obtain a desired solution in the above rough concentration range. There was found. In particular, NH ₃ : CO
_The concentration-to-weight ratio was found to be important.

However, according to the present invention, it has been found that when the NH ₃ : CO ₃ concentration weight ratio is 1: 0.8 to 1 to 1.8, the Al content can be surely reduced.

[Specific configuration of the invention]

 Hereinafter, the present invention will be described in more detail.

As the zinc-containing material containing Al targeted in the present invention (hereinafter sometimes abbreviated as zinc-containing material), as described above,
This includes Zn-Al plating dross discharged from the plating process and waste solder from a solder manufacturing plant. Although there is no limitation on the Al content in the zinc-containing material to be subjected, 1000 pp
It should be noted that even if the content is not less than m, the concentration of Al in the zinc carbonate solution can be reduced to 10 mg /, particularly 5 mg / or less.

The zinc content is dissolved in the basic ammonium carbonate solution. This basic ammonium carbonate solution can be obtained by contacting aqueous ammonia with carbon dioxide gas. In any case, when dissolving the zinc-containing material containing Al, it is essential that the NH ₃ : CO ₃ concentration weight ratio be 1: 0.8 to 1: 1.8. A more preferred range of the concentration-weight ratio is 1: 1 to 1: 1.5.

The reason why this range is preferable was found by the following experiment.

That is, Zn-Al plated dross discarded from a hot-dip galvanizing plant of an ironworks containing about 10% by weight of Al (hereinafter, all percentages are all by weight) and about 89% of zinc as a zinc-containing material of the present invention, This was dissolved in a zinc solution having various CO ₃ : NH ₃ concentrations and weight ratios, and the concentrations of Zn and Al in the solution after the dissolution were examined. The results shown in Table 1 and FIG. 1 were obtained. .

According to this result, when the NH ₃ : CO ₃ concentration weight ratio of the present invention is within the above range, a Zn solution having a large Zn dissolution amount and a low Al concentration can be obtained, and the NH ₃ : CO ₃ concentration can be obtained. When the weight ratio exceeds the line of 1: 1.8 in FIG. 1, the amount of dissolution decreases although the Al concentration is relatively low, while NH ₃ :
It is understood that when the weight ratio of the CO ₃ concentration is less than 1: 0.8, the Al concentration increases. If the dissolution amount of Zn is small, it takes time and an excessive dissolution apparatus to dissolve the zinc-containing material, and economic operation cannot be performed. If the amount of Al dissolved is large, of course, when zinc carbonate is subsequently crystallized, only crystals having a high Al content can be obtained.

The solution obtained as described above can be used for recovery of zinc carbonate according to the prior art.

According to the present invention, the Al concentration in the zinc carbonate solution is 5 mg /
If it is less than the above, the Al content in zinc carbonate finally obtained by crystallization will be 30 mg / kg or less, and extremely high quality zinc carbonate crystals can be obtained. Note that if the Al concentration in the zinc carbonate solution is 1 mg / or less,
The Al content will be 10 mg / kg or less.

Hereinafter, specific examples of the method of the present invention and other related matters are described in the second section.
This will be described with reference to the drawings.

First, in the dissolving solution adjusting device 1, water, carbon dioxide gas
CO ₂ and NH ₄ OH, and the
Prepare a basic ammonium carbonate solution with a NH ₃ : CO ₃ concentration weight ratio. This basic ammonium carbonate solution whose concentration has been adjusted is temporarily stored in the solution tank 2 and guided to the required first solution tank 3.
A first settling / separation tank 4, a second settling tank 5, a second settling / separation tank 6, a first partial crystallization tank 7, and a second partial crystallization tank 8 are disposed in the subsequent stage of the first dissolving tank 3. ing.

Into the first dissolution tank 3 and the second dissolution tank 5, a target zinc-containing material 9 is charged by charging means 10 and 11, respectively.
The dissolution is achieved. The dissolution can be performed, for example, by circulating the dissolving solution by the illustrated circulation pumps 12A and 12B.

The clarified liquid in the first dissolving tank 3 is led to the first sedimentation separation tank 4, where a Zn-containing slurry containing a large amount of undissolved Zn and containing aluminum hydroxide at a high concentration is pumped into the first dissolving tank 3. I will send it back. The clarified liquid in the first settling / separation tank 4 is supplied to the second dissolution tank 5, and a new zinc-containing substance is supplied to the second dissolution tank 5 to dissolve the same. The clarified liquid in the second dissolving tank 5 is led to the second sedimentation / separation tank 6, where a Zn-containing slurry having a high Zn content and containing aluminum hydroxide in a high concentration is provided in the second and fifth dissolving tanks 5 and 1 in the preceding stage. Return to 3. The clarified liquid in the second settling / separation tank 6 is sequentially supplied to the first and second partial crystallization tanks 7 and 8.

In the present invention, in the first dissolving tank 3 and the second dissolving tank 5, the zinc solution is adjusted so that the NH ₃ : CO ₃ concentration weight ratio is within the above range. In particular,
For example, mainly in the dissolving solution adjusting device 1, NH ₃ : CO ₃
The concentration weight ratio is adjusted.

On the other hand, if the Si content in the finally obtained zinc carbonate crystal has a problem in obstructing the plating properties, the illustrated Si removing means is added as necessary.

That is, iron hydroxide such as magnetite is added to the zinc carbonate solution. In reducing the content of Si, the present inventors, in JP-B-63-50414,
It was previously proposed to add an iron sulfate solution. However, it has been found that, although relatively effective, it is still not sufficient for the solution containing the zinc-containing substance of the present invention, and that the addition of iron hydroxide is more preferable.

Therefore, as shown in FIG. 2, the iron sulfate solution from the iron sulfate FeSO ₄ solution tank 20 and the hydrogen peroxide from the hydrogen peroxide tank 21 are supplied to the oxidation tank 22 and the neutralizing agent is supplied to the oxidation tank 22. For example, ammonia water or basic ammonium carbonate solution is added for neutralization, and iron hydroxide (eg, Fe ₃ O ₄ .nH ₂
O), the clarified liquid is discharged from the iron hydroxide supply tank 23 to the outside of the system, and the iron hydroxide slurry is supplied to the second dissolution tank 5, the second sedimentation separation tank 6, the first partial crystallization tank 7, and Second partial crystallization tank 8
And the soluble silica SiO ₂ is adsorbed on iron hydroxide, and is discharged out of the system as solids by solid-liquid separators 42 and 53 described below. Further, in this embodiment, the reason why the magnetite slurry is added to the zinc carbonate solution in the form of iron hydroxide instead of the form of iron sulfate is because magnetite slurry is more excellent in sedimentation and filterability than iron sulfate slurry, This is because the effect is large and the content of Si remaining in the zinc carbonate solution can be further reduced.

 In this regard, the following experiment was conducted.

That is, as shown in FIG. 3, about 89% of Zn and about 10% of Al
100 g of Zn-Al-plated dross is dissolved in a basic ammonium liquid (solvent) at a liquid temperature of 40 ° C., and then filtered to obtain a filtrate (NH ₃ : 136 g /, Zn: 123 g /, Fe: 286 mg /, Si: 1.5 mg
/) Got.

For 100 ml of the filtrate, (1) air oxidation, (2) FeSO ₄ addition + air oxidation, (3) FeSO ₄ addition + H ₂
O ₂ oxidation, (4) magnetite slurry (Fe ₃ O ₄ .nH ₂ O
(5 g) was added, and (5) the solution after the addition of 10 ml of the magnetite slurry was filtered, the concentration in the filtrate was examined, and a solvent (basic ammonium carbonate solution) was added to the cake slurry. Then, when the concentration of the cake and the filtrate at the time of filtration was examined,
The results shown in the figure were obtained.

From these results, the method of adding the magnetite slurry shown in the step (5) was particularly effective in determining the Si concentration in the zinc carbonate solution.
It can be reduced to 0.35 mg /, which proves to be an excellent method.

In addition, magnetite (Fe ₃ O ₄
· NH ₂ O) as a 5 to 20 g /, preferably added 1 to 4 g / magnetite as Fe. Also, oxidation rate for FeSO ₄ for obtaining the magnetite is preferably 50-80%.

When it is necessary to significantly reduce the Al content in the zinc carbonate solution or in the zinc carbonate crystal finally obtained, it is effective to perform partial crystallization.

For example, as shown in FIG. 2, the zinc carbonate solution from the first and second partial crystallization tanks 7 and 8 is led to the condenser 30 by heating or evaporating under reduced pressure of each tank, and ammonium is evaporated and removed. A portion is crystallized, and a portion of the crystallized product is guided to a subsequent dissolution / metal zinc addition step by a route 41 on the solution side of a solid-liquid separator 40, for example, a centrifuge, and with the evaporation of ammonia, Al dissolved in zinc carbonate solution
At the same time as aluminum hydroxide, which is returned to the partial crystallization tanks 7 and 8, and the zinc carbonate slurry containing aluminum hydroxide from the second partial crystallization tank 8 is supplied to the solid-liquid separation device 40, Remove solids. Thereby, the Al content in the zinc carbonate solution discharged from the solid-liquid separation device 40 is extremely reduced.

Incidentally, it was dissolved Mekkidorosu As in the previous experiments, zinc carbonate solution (Zn: 100g /, Al: 5mg /, NH 3: 104g /
) Was obtained, and a partial crystallization rate of 15 wt% was obtained. Subsequently, the concentration of the filtrate after removing the insoluble residue and the partially crystallized portion by filtration was determined to be Zn: 8.
8 g /, Al: 1 mg / or less, NH _3: 73 g /, and the decrease of the Al concentration by partial crystallization were remarkably observed.

Incidentally, the partial crystallization rate of the total crystallized product, 5-30
% Is preferred. If it exceeds 30, the equipment cost will increase, and the partial crystallization of less than 5% cannot be stably performed.

The solid-side slurry from the solid-liquid separation device 40 contains aluminum hydroxide at a high concentration. Also, when the aluminum hydroxide slurry once precipitated is brought into contact with a basic ammonium carbonate solution or a zinc carbonate solution, zinc is eluted but aluminum is not eluted. Therefore, in order to recover zinc, the solid-side slurry from the solid-liquid separator 40 is once stored in the storage tank 42, and then returned to the first dissolution tank 3 to be reused as a zinc carbonate solution. Is preferred.

By the way, the solid-side slurry from the solid-liquid separator 40 is returned to the first dissolving tank 3, and as described above,
A Zn-containing slurry having a large undissolved Zn content from the first sedimentation tank 4 and containing aluminum hydroxide at a high concentration is supplied to the first dissolution tank 3, and a Zn-containing slurry from the second sedimentation separation tank 6 is provided. It is returned to the first dissolving tank 3 together with the second dissolving tank 5. The main purpose of this return is to recover Zn, and to further reduce the Al concentration in the zinc carbonate solution.

The reason why Al can be effectively removed by this return is considered to be as follows.

That is, in the first dissolution tank 3 and the second dissolution tank 5, when the target zinc-containing substance is dissolved in the basic ammonium carbonate solution, Al in the zinc-containing substance becomes aluminate, and Al
In the part where the ions are supersaturated,
The seeds of Al (OH) ₃ are brought into contact with each other to eliminate the supersaturated state, and at the same time, Al (OH) ₃ crystals are grown, whereby the Al content in the resulting zinc carbonate solution is reduced. It is thought that.

This fact can be sufficiently inferred from the experimental results shown in FIG. The experiment was carried out using the same Zn-plated dross as that obtained in FIG. 1 and dissolved in a solvent (basic ammonium carbonate solution), and then insoluble matter was removed by filtration.
The insoluble material was dissolved in a solvent together with the plating dross in three steps, and the Al concentration in the filtrate was investigated. Further, the final insoluble material was simply dissolved in a solvent, and the filtrate obtained by filtration was also examined for the Al concentration.

Therefore, when the filtrate A and the filtrate C are compared, the Al concentration in the filtrate C is reduced to 1/5 or less, and it is understood that the returning of the slurry is effective for reducing the Al concentration, and the filtrate D From the result of the Al concentration in the aluminum hydroxide, it was found that Al in the aluminum hydroxide slurry did not redissolve in the basic ammonium carbonate solution.

The return of the aluminum hydroxide results in the growth of Al (OH) ₃ crystals as described above. Thereby, the sedimentation property and the filtration property are improved. In fact, the insolubles S1 and S3 in the experimental process of FIG. 4 were washed with a basic ammonium carbonate solution to remove Zn, and then washed with water.
The composition of the sample dried at 105 ° C was
Inspection by X-ray analysis, and electron microscopy
The crystals of (OH) ₃ were visually observed.

 Table 2 shows the resulting sample compositions.

The Al (OH) ₃ crystal was observed under an electron microscope to show that the insoluble S1 sample had a thickness of about 0.2 mm.
μm, about 1-2 μm long needle-like crystals,
The sample of the insoluble matter S3 is a needle-like crystal having a thickness of about 0.2 to 0.3 μm and a length of about 2 to 3 μm, and the Al (OH) ₃ crystal obtained by the returning operation is growing. It turns out.

On the other hand, the amount of aluminum hydroxide slurry to be returned is
Since an amount sufficient to grow Al (OH) ₃ crystals is sufficient, a surplus is generated. Therefore, as shown in FIG.
42 and / or a part of the aluminum hydroxide slurry from the first sedimentation separation tank 4 is temporarily stored in storage tanks 50 and 51, and is washed from the filtrate tank 52 by a solid-liquid separator 53 such as a filter press during filtration. While the solid-liquid separation is performed and the cake is discarded, the filtrate can be returned to the above-mentioned adjusting device 1 and added to the basic ammonium carbonate solution. This makes it possible to recover Zn.

By the way, the zinc carbonate solution from the solid-liquid separation device 40 is supplied to the ion replacement tanks 60 to 62 to remove impurities such as Fe and Pb. At that time, as in the prior method, the addition of metallic zinc 64 is performed in two stages, and in the embodiment, an ion exchange tank is used.
The zinc carbonate solution from the sedimentation / separation tank 63 is led to a crystallization step (not shown) according to the prior art, and zinc carbonate crystals are generated. Thereafter, the zinc oxide obtained by firing is used as a raw material for plating, a pigment or a magnetic material.
65 is a metal zinc supply device. Further, the settled slurry in each tank is supplied to the preceding stage, and countercurrent ion replacement is performed. The slurry in the ion exchange tank 60 is returned to the second dissolution tank 5.

Further, a solid-liquid separator such as a filter may be provided between the ion replacement step and the crystallization step, and the slurry by the solid-liquid separation is returned to the first dissolution tank 3 and the like as shown in FIG. it can.

In the above embodiment, the number of bases of the dissolution tank, the sedimentation separation tank or the partial crystallization tank can be appropriately selected. For example, the zinc-zinc-containing substance may be dissolved at one time. Further, as the solid-liquid separation device, an appropriate means such as a sedimentation separation tank, a centrifugal separator, and a filter can be used.

〔The invention's effect〕

As described above, according to the present invention, a zinc carbonate solution having an extremely low Al concentration can be obtained.

[Brief description of the drawings]

FIG. 1 is a graph of the concentration of Zn and Al dissolved according to the change in the NH ₃ : CO ₃ concentration weight ratio, FIG. 2 is a flow sheet showing an example of a method for producing a zinc carbonate solution, and FIGS. It is explanatory drawing of a different experiment process. DESCRIPTION OF SYMBOLS 1 ... Basic ammonium carbonate liquid adjusting device, 2 ... Dissolution tank, 3, 5 ... Dissolution tank, 4, 6 ... Sedimentation separation tank, 7, 8 ... Partial crystallization tank, 20 ... Iron sulfate Tank 21 Hydrogen peroxide tank 22 Oxidation (neutralization) tank 30 Condenser 40 Solid-liquid separator (centrifuge) 53 Solid-liquid separator (filter) , 60-62 ... Ion replacement tank, 64 ... Metal zinc.

Claims (1)

(57) [Claims] (1) dissolving a zinc-containing material containing Al in a basic ammonium carbonate solution, and at the time of dissolving, adjusting the NH ₃ : CO ₃ concentration ratio by weight to 1: 0.8 to 1: 1.8. A method for producing a solution containing a zinc-containing material containing Al.