KR101467349B1 - Recovering Method of high concentration Tin from waste containing tin - Google Patents

Abstract

The present invention relates to a method for recovering a high concentration of tin from tin-containing waste water and, more specifically, to a method for recovering a high concentration of tin, comprising: removing impurities from tin-containing waste water; manufacturing an ion-exchange resin, in which tin is absorbed, by removing an organic substance or the like by using an ion-exchange resin method; obtaining a tin compound solution by processing the same with an acid solution; regenerating the ion-exchange resin; and repeatedly performing the same process by using the regenerated ion-exchange resin and the tin compound solution. The present invention has an effect of reducing process costs in comparison with the existing tin recovery method; and reducing production costs and manufacturing a high concentration of nickel as the high costs of a concentration process such as an evaporation method can be skipped by the existing solution concentration method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering tin from a tin-

The present invention relates to a method for concentrating and recovering tin at a high concentration from a tin-containing waste liquid generated at an industrial site using an ion exchange resin process.

Tin is a strategic metal that is expected to grow as an essential material for LED TVs, electrical and electronic products, and is emerging as a core material to replace indium in next-generation displays.

These annotations are becoming a cause of price increase due to unstable supply and demand due to resource amendment. Recently, Korea, which is a resource shortage country due to depletion of resources and rising raw material prices, needs technology to recover and recycle tin waste generated at industrial sites .

There have been various studies on recovering tin by using tin-containing waste resources. However, most of them are recovered in waste shoulder, scrap and sludge with high tin content. Tin recovery using tin- There is no technology in Korea.

These tin-containing wastes are mainly generated in PCB / lead frame plating processes, barrel plating and plating solution processes, and these wastes have a tin content of about 20 to 200 g / l. These waste liquids are not recovered due to the undeveloped treatment technology and are discarded, resulting in environmental problems.

As a method for recycling the tin-containing waste liquid as described above, in Japan, tin is adsorbed using a strong acidic ion exchange resin, tin is removed from the ion exchange resin using an acid, tin is recovered, Or recovering tin by reducing the tin hydroxide has been studied.

However, in the case of the above method, it is difficult to completely separate the Sn ion and the Fe ion, so that the Fe content of the recovered tin is so high that it is difficult to use it as a tin hydroxide form, there is a problem.

In addition, techniques for recovering a specific metal from a metal-containing waste liquid using an ion exchange resin have been developed and studied (Korean Registration No. 10-1053416, Korean Registration No. 10-0201544). However, Research is lacking.

DISCLOSURE Technical Problem Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for concentrating and recovering tin at a high concentration using an ion exchange resin after controlling pH from a tin containing waste liquid.

In order to accomplish the above object, the present invention relates to a method for recovering tin from a tin-containing waste liquid at a high concentration, comprising: a first step of preparing a tin-containing waste liquid; A second step of removing impurities by a chemical precipitation method of the tin-containing waste liquid; A third step of removing impurities and organic substances from the tin-containing waste liquid from which the impurities have been removed by using an ion exchange resin and adsorbing tin in the ion exchange resin; A fourth step of washing the ion-exchange resin adsorbed on the tin; A fifth step of treating the washed ion exchange resin with an acid solution to prepare a tin compound solution and regenerating the ion exchange resin; And a sixth step of re-performing the first through fifth steps using the regenerated ion exchange resin. In the fifth step of the sixth step, the tin compound solution is reused as an acid tax solution The tin can be recovered at a high concentration.

As described above, the present invention can recover a high-purity tin solution from a waste solution containing tin at a low concentration. As a result, the process cost can be reduced as compared with the conventional tin recovery process In addition, since a high-concentration concentration process such as the evaporation method can be omitted by the existing solution concentration method, the production cost can be greatly reduced.

FIG. 1 is a flow chart schematically showing the recovery of tin from a tin-containing waste liquid using an ion exchange resin according to an embodiment of the present invention.

Hereinafter, the tin recovery method using the ion exchange resin from the tin-containing waste liquid of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is not limited thereto, Lt; / RTI >

FIG. 1 is a flow chart schematically illustrating the recovery of tin from a tin-containing waste liquid according to an embodiment of the present invention using an ion exchange resin. As shown in FIG. 1, the present invention comprises a first step (S01) of preparing a tin-containing waste liquid as a raw material; A second step (S02) of removing impurities by a chemical precipitation method by adjusting pH of the tin-containing waste liquid; A third step (S03) of removing the impurities from the tin-containing waste liquid by using an ion exchange resin to remove impurities and organic substances, and adsorbing tin in the ion exchange resin; A fourth step (S04) of washing the ion exchange resin to which the tin is adsorbed; A fifth step (S05) of treating the washed ion-exchange resin with an acidic solution to prepare a tin compound solution and regenerating the ion-exchange resin; And a sixth step (S06) of re-executing the first to fifth steps using the regenerated ion exchange resin. The fifth step of the sixth step is characterized in that the tin compound solution is reused as an acidic solution.

First, as in the first step S01, the concentration of the tin-containing waste solution should be 0.4 wt% to 2.5 wt%, preferably 0.4 wt% to 2.0 wt% in constituting the raw material such as the tin-containing waste liquid. If the tin concentration is more than 2.5% by weight, the scale of the ion exchange resin may increase and the process scale and the freight cost may become large. If the tin concentration is less than 0.4% by weight, There is a problem that the cost of the waste liquid to be treated is increased.

The tin-containing waste solution may contain at least one selected from the group consisting of Fe, Al, Ca, Mn, Mg, Cu, Si, Ni, (P), and potassium (K), and may further include at least one selected from the group consisting of chromium (Cr), zinc (Zn), cobalt (Co) have.

Preferably, the iron has a concentration of 1,000 ppm or less, aluminum has a concentration of 10 ppm or less, calcium has a concentration of 300 ppm or less, manganese has a concentration of 50 ppm or less, magnesium has a concentration of 30 ppm or less , Copper at a concentration of 50 ppm or less, silicon at a concentration of 100 ppm or less, nickel at a concentration of 50 ppm or less, lead at a concentration of 50 ppm or less, and potassium at a concentration of 100 ppm or less. More preferably, the above-mentioned tin-containing waste liquid contains magnesium in a concentration of 400 to 900 ppm, aluminum in a concentration of 0.5 to 10 ppm, calcium in a concentration of 20 to 150 ppm, manganese in a concentration of 1 to 20 ppm, 25 ppm, 1 to 30 ppm of copper, 1 to 30 ppm of silicon, 1 to 20 ppm of nickel, 1 to 20 ppm of lead and 1 to 50 ppm of potassium can do.

Next, in the second step (SO2), a step of removing impurities and organic substances from the tin-containing waste solution by chemical precipitation is firstly carried out by adding a pH adjusting agent to adjust the pH of the solution to 1.0 to 3.0, 2.0 in order to increase the tin adsorption efficiency of the ion exchange resin and adsorb only tin excluding impurities. In addition, filtration is performed after adjusting the pH to remove impurities such as floating matters and organic matters in the waste solution containing tin.

At this time, when the pH of the tin-containing waste solution is more than 2, it may not be possible to recover high-purity tin by adsorbing not only tin but also impurities to the ion-exchange resin when passing through the ion-exchange resin. The pH adjuster for adjusting the pH of the tin-containing waste liquid may be a conventional pH adjuster used in the art, and preferably one or a mixture of two or more selected from sodium hydroxide, ammonia water, hydrochloric acid and sulfuric acid can be used . When sulfuric acid is used as a pH regulator, lead (Pb) in the tin-containing waste solution can be precipitated with sulfuric acid and precipitated with PbSO ₄ .

The step of removing the primary impurities by the chemical precipitation method is preferably performed at 20 ° C to 40 ° C, more preferably at 20 ° C to 35 ° C, and at 20 ° C to 60 ° C, , There may be a problem that the reactivity is decreased. When the temperature exceeds 60 ° C, there is a problem that the economical efficiency is lowered.

Next, in the third step (SO3), the impurities are removed and the pH-adjusted tin-containing waste liquid is passed through the ion exchange resin to remove impurities and organic substances, and the tin is adsorbed to the ion exchange resin. The ion exchange resin used in this case may be a general ion exchange resin used in the industry, but preferably a di-2- (ethyl hexyl) phosphoric acid series is used good. During the adsorption process, the cationic impurities present in the tin-containing waste solution are separated, so only tin is adsorbed on the ion-exchange resin, and the cationic impurities are passed through the waste liquid. It is preferable that the passing speed of passing through the ion exchange resin is 1 BV to 5 BV, preferably 1 BV to 3 BV. At this time, if the passing speed is less than 1 BV, there is a problem that the process time is excessively long and the productivity is inferior. If the passing speed exceeds 5 BV, the adsorption rate of tin in the ion exchange resin may decrease. It is good to do.

The concentration of the solution of 1% tin content is reduced by 40 times in order to obtain the 40% crystals. Therefore, the present invention takes a great deal of processing cost by introducing impurity removal and concentration process through the ion exchange resin, Can be saved.

Next, in the fourth step (SO4), distilled water is passed through the ion exchange resin adsorbed with the tin, that is, the water is washed to remove residual impurities and organic substances present in the ion exchange resin column. Through this washing process, residual impurities and organic substances are removed, so that high-purity tin (or tin solution) can be obtained. The passage speed at which the distilled water passes through the ion exchange resin is preferably 2 BV to 10 BV, preferably 2 BV to 8 BV. At this time, if the passing speed is less than 2 BV, the washing process time becomes too long If the passing speed exceeds 10 BV, the passing speed of the distilled water is too fast, so that the tin adsorbed in the ion exchange resin may also be washed. Therefore, it is preferable to flush with the passing speed.

Next, in the fifth step SO5, an acidic solution (acidic solution) of 10 wt% to 40 wt% is passed through the ion-exchange resin adsorbed on the tin to regenerate the ion-exchange resin, The tin is recovered as a tin compound solution by recovering the tin as an acidic solution such as acidic solution. In the case of the acidic solution, it is preferable to use one or two selected from the group consisting of an aqueous hydrochloric acid solution having a concentration of 10 wt% to 40 wt% and an aqueous sulfuric acid solution having a concentration of 10 wt% to 40 wt% The tin compound of the tin compound solution is present as tin chloride and / or tin sulfate. The pH of the acid solution is preferably 0.5 or less. If the pH exceeds 0.5, the recovery of tin may be lowered and the regenerating ability of the ion exchange resin may be lowered.

The passing speed of passing the acid washing liquid through the ion exchange resin is 1 BV to 10 BV, preferably 2 BV to 5 BV. At this time, if the passing speed is less than 1 BV, the process execution time becomes too long, If the passing speed exceeds 10 BV, the passing rate of the acid washing liquid may be too fast to reduce the amount of tin recovered in the tin compound solution, so that it is preferable to pass the acid washing liquid at the passing speed.

The sixth step S06 is a step of increasing the concentration of the tin compound in the tin compound solution by reusing the tin compound solution as an acid solution, The content of the tin compound in the solution can be increased by reusing the recovered tin compound solution as the acidic solution used in the fifth step (S05) after re-executing the fourth step (SO4). Preferably, the pH of the reusable tin compound solution should be reused in a range of 0.5 or less. When the pH is high, the recovered tin solution can be reused by adding an additional acidic solution.

The sixth step may be repeatedly performed according to the concentration of the tin compound to be used by repeating at least one time, so that the tin compound can be concentrated at a higher concentration. The concentration of the tin compound in the tin compound solution subjected to the sixth step is 2.0 wt% or more, preferably 2.5 wt% or more, more preferably 2.5 wt% to 5 wt%, and other metal materials, non- Other impurities may not be present.

In order to obtain a high concentration tin compound solution from a waste solution, there has been a problem in that the production cost is greatly increased since the decompression concentration process must be performed. For example, in order to obtain a tin compound solution of 2.0 wt.% To 5.0 wt.%, It is necessary to carry out a vacuum concentration step from 8 to 20 times. However, by introducing an ion exchange resin process and a recycling process, the present invention can provide a high concentration tin compound solution with high productivity and economy.

INDUSTRIAL APPLICABILITY As described above, the present invention provides a tin recovery method and a concentration method using an ion exchange resin from a tin-containing waste liquid. The tin-containing waste liquid is adjusted in pH to make conditions for recovering only tin by the ion exchange resin. After the tin is adsorbed, the tin is recovered from the ion-exchange resin through the pickling process and the ion-exchange resin is recycled. By recycling the recovered tin compound solution as an acid solution, it is possible to recover the high-purity tin solution by increasing the content of tin or tin compound in the solution, so that the process cost can be reduced as compared with the existing tin recovery process The effect can be obtained.

In addition, the tin compound solution recovered by the method proposed by the present invention contains a tin compound at a high concentration, and the tin compound solution itself can be used as a raw material of the product, or a common depressurization and concentration method used in the art It may be further concentrated and used as a raw material of the product.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Example]

Example 1

The tin-containing waste solution (pH 0.8) having the composition shown in the following Table 1-a was collected, and 10 L of the tin-containing waste solution was added to a reactor having a capacity of 10 L. Then, the solution was added with 5 M NaOH while stirring with a stirrer, The pH of the waste solution was adjusted to 1.5, and stirred and reacted for about 1 hour. After completion of the reaction, the resulting initial suspension and impurities were removed by filtration.

The tin-containing waste solution having the impurities removed and the pH adjusted therein was passed through 5 liters of an ion exchange resin of di- (2-ethylhexyl) phosphoric acid series. Next, the tin-containing waste solution passed through the ion exchange resin was circulated to the ion exchange resin for about 3 hours for complete tin recovery. At this time, the ion exchange resin passage speed of the tin-containing waste solution was made to be about 2 BV (10 L / h). After 3 hours, the components of the passed waste solution were analyzed by inductively coupled plasma atomic emission spectroscopy (ICP-OES), and the results are shown in Table 2-a , And the amount of tin was checked by comparing the tin content of the waste liquid. It was confirmed that tin was recovered to about 97.5% by comparing the content of tin in Table 1-a and Table 2-a, and it was confirmed that a small amount of iron (Fe) and magnesium (Mg) I could.

Next, 10 liters of distilled water was passed through the ion exchange resin adsorbed on tin as described above to wash the tin-containing waste liquid present in the ion exchange resin column. At this time, the flow rate of the ion exchange resin in the distilled water was about 5 BV (25 L / h).

Next, 20% by weight of H ₂ SO ₄ solution as an acidic solution of 10 L was passed through the ion exchange resin adsorbed on the washed tin to prepare a tin compound solution recovered from the adsorbed tin on the ion exchange resin, The resin was regenerated. At this time, the ion exchange resin passing speed of the 20 wt% H ₂ SO ₄ solution was 2 BV (10 L / h), and the acid solution was circulated for about 3 hours for the complete recovery of tin. The components of the tin compound solution thus passed are shown in Table 3-a. As shown in Table 3-a, it was confirmed that most of the tin (Sn) adsorbed on the ion exchange resin was recovered, and it was confirmed that there were no impurities other than iron (Fe) and calcium (Ca) The tin content of the recovered tin-containing solution was 0.9 wt% of the total weight of the tin-containing solution, and the tin concentration was practically difficult to commercially use.

Next, using the regenerated ion exchange resin, the above steps were repeated in the same manner and repeated three times. At this time, the content of tin in place of the 20 wt% H ₂ SO ₄ solution 0.9 wt% of the recovered tin compound solution was reused as an acid solution to prepare a tin compound solution in which the tin component was concentrated. At this time, about 5 wt% of H ₂ SO ₄ was added to the recovered tin compound solution to be reused and reused, and the pH of the tin compound solution to be reused as an acid solution was 0.1 to 0.2.

The components of the concentrated tin compound solution are shown in Table 4-a. As can be seen from Table 1-a and Table 4-a, the tin concentration increased from 9265 ppm to 25,548 ppm by 2.75 times, which is about 2.5% by weight of the total weight of the concentrated tin-containing solution, Concentration.

Example 2

A concentrated tin compound solution was prepared in the same manner as in Example 1, and a tin-containing waste solution (pH 0.8) having the composition shown in the following Table 1-b was collected and used. The components of the ion- b, and the components of the tin compound solution are shown in Table 3-b, respectively. The tin concentration in the final concentrated tin compound solution is shown in Table 4-b.

Example 3

A concentrated tin compound solution was prepared in the same manner as in Example 1, and a tin-containing waste solution (pH 0.8) having the composition shown in the following Table 1-c was collected and used. The components of the ion- c, and the components of the tin compound solution are shown in Table 3-c, respectively. The tin concentration in the final concentrated tin compound solution is shown in Table 4-c.

Example 4

A concentrated tin compound solution was prepared in the same manner as in Example 1, and a tin-containing waste solution (pH 0.8) having the composition shown in the following Table 1-d was collected and used. The components of the ion- d, and the components of the tin compound solution are shown in Table 3-d, respectively. The tin concentration in the final concentrated tin compound solution is shown in Table 4-d.

However, an ion exchange resin having a high tin content in the initial tin-containing waste liquid and having a capacity two times larger than that of the ion exchange resin of Example 1 was used.

ingredient unit a b c d Sn ppm 9265 4117 7840 27190 Fe 868 13 5871 2 Co trace trace trace trace Al One trace 5 trace Ca 58 70 18 7 Mn 4 trace 6 trace Mg 12 10 One trace Cu 4 6 8526 3 Si 10 trace trace trace Cr trace trace 8 trace Ni 4 trace 4 30240 Pb 4 1531 5381 trace K 10 12 3 8 P trace trace trace trace

ingredient unit a b c d Sn ppm 230 183 221 350 Fe 825 11 5320 2 Co trace trace Trace Trace Al One trace 4 Trace Ca 55 65 17 7 Mn 4 trace 5 Trace Mg 11 9 One Trace Cu 4 6 8421 3 Si 10 trace Trace Trace Cr trace trace 7 Trace Ni 4 trace 4 29851 Pb 4 1425 5013 Trace K 10 12 3 8 P trace Trace Trace trace

ingredient unit a b c d Sn ppm 8950 3995 7541 26520 Fe 25 One 159 trace Co trace trace trace trace Al trace trace trace trace Ca One One trace trace Mn trace trace trace trace Mg trace trace trace trace Cu trace trace 21 trace Si trace trace trace trace Cr trace trace trace trace Ni trace trace trace 125 Pb trace 54 126 trace K trace trace trace trace P trace trace trace trace

ingredient unit a b c d Sn ppm 25548 23095 28522 49232 Fe 56 4 482 trace Co trace trace trace trace Al trace trace trace trace Ca One One trace trace Mn trace trace trace trace Mg trace trace trace trace Cu trace trace 61 trace Si trace trace trace trace Cr trace trace trace trace Ni trace trace trace 220 Pb trace 198 360 trace K trace trace trace trace P trace trace trace trace

As can be seen from the results of Tables 1 to 4, the pH of the tin-containing waste solution containing impurities as shown in Table 1 was adjusted so that the ion exchange resin could recover only tin, After the tin is adsorbed, the tin is recovered from the ion-exchange resin through the pickling process, the ion-exchange resin is regenerated, and the recovered tin compound solution is reused as an acid solution to increase the tin content in the solution to produce a high purity tin solution .

Claims (10)

A first step of preparing a tin-containing waste liquid containing impurities and organic matter including tin, metal, and non-metal;
A second step of adjusting the pH of the tin-containing waste liquid to 1 to 2 to remove impurities by a chemical precipitation method;
A third step of removing impurities and organic substances from the tin-containing waste liquid from which the impurities have been removed by using an ion exchange resin and adsorbing tin in the ion exchange resin;
A fourth step of washing the ion-exchange resin adsorbed on the tin;
A fifth step of treating the washed ion exchange resin with an acid solution having a pH of 0.5 or less to prepare a tin compound solution and regenerating the ion exchange resin;
And a sixth step of performing the first through fifth steps again using the regenerated ion exchange resin,
In the fifth step of the sixth step, the tin compound solution is reused as an acid solution,
The tin compound solution to be reused as the acidic solution in the sixth step has a pH of 0.5 or less,
And the sixth step is repeatedly performed 2 to 8 times.
The method according to claim 1, wherein the tin-containing waste liquid in the first step contains tin at a concentration of 2,000 to 35,000 ppm,
(Fe), aluminum (Al), calcium (Ca), manganese (Mn), magnesium (Mg), copper (Cu), silicon (Si), nickel (Ni) And the phosphorus (P) is further contained in the tin-containing waste liquid.
delete The method of claim 1, wherein the ion exchange resin is di (2-ethylhexyl) phosphoric acid ion-exchange resin. Way.
The method according to claim 1, wherein the acid solution in the fifth step comprises at least one selected from the group consisting of an aqueous hydrochloric acid solution having a concentration of 10% by weight to 40% by weight and an aqueous sulfuric acid solution having a concentration ranging from 10%
Wherein the tin compound of the tin compound solution contains at least one selected from tin chloride and tin sulfate.
delete delete delete The method according to claim 1, wherein the tin compound solution produced by the sixth step has a Fe content of 60 ppm or less, a Ca content of 2 ppm or less, a Sn content of 20,000 ppm or more, And recovering tin from the tin-containing waste liquid.
The method of claim 1, wherein the tin compound solution after step 6 comprises tin in an amount of 2.5 wt% or more.

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