KR101619344B1 - Refining method of waste tin plating solution using ion exchange resin - Google Patents
Refining method of waste tin plating solution using ion exchange resin Download PDFInfo
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- KR101619344B1 KR101619344B1 KR1020150189374A KR20150189374A KR101619344B1 KR 101619344 B1 KR101619344 B1 KR 101619344B1 KR 1020150189374 A KR1020150189374 A KR 1020150189374A KR 20150189374 A KR20150189374 A KR 20150189374A KR 101619344 B1 KR101619344 B1 KR 101619344B1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
Abstract
Description
The present invention relates to a method for purifying a tin plating waste solution which can greatly increase purity of a tin solution by removing a large amount of metal and organic impurities from a solution recovered from a tin plating waste solution using an ion exchange resin.
Tin is a metal used as an essential material for LED TVs, alloy materials, plating materials, and electric and electronic products, and demand is steadily increasing as it becomes a core material for next generation. However, the annotation resources are burdened only in some countries such as Southeast Asia, and they are smelted only in these countries, which causes the price increase due to unstable supply and demand. Therefore, recently, a technique of recovering and reusing tin from waste metal resources such as scrap and sludge has attracted much attention, and some of them have been commercialized. Techniques for recovering tin from wastes containing tin have been disclosed such as melting, dry reduction, solvent extraction and wet reduction. However, these methods are mostly recovered from waste solder, scrap and sludge, which are relatively high in tin content. However, the technology for recovering tin from a waste solution (<
The tin-containing waste solution is mainly generated in the plating process and contains a large amount of organic substances, so that it is very difficult to develop suitable treatment techniques because the precipitation or compound formation by the general chemical treatment method is not smooth.
On the other hand, the ion exchange resin can remove impurities such as anions and cations according to the functional groups of the resin by recovering and removing the metal from the solution in which the metal is recovered.
As a prior art related to this, there is a method of recovering the fluorine component contained in the wastewater generated in the etching process disclosed in Korean Patent Laid-Open Publication No. 2015-0138461 (published on Dec. 10, 2015).
Accordingly, it is an object of the present invention to provide a method for adsorbing tin and metal impurities from a tin plating waste solution using an ion exchange resin, and extracting the tin and metal impurities from the waste solution to recover a high purity tin solution.
The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.
In order to solve the above problems, the present invention provides a method of preparing a tin plating waste liquid containing impurities and organic substances and adjusting the pH of the tin plating waste solution to 2.5 to 3.0 (Step 1-1); Circulating the pH-adjusted tin plating waste solution into an ion-exchange resin layer filled with an iminodiacetic acid ion-exchange resin to adsorb tin and impurities in the tin plating waste solution (Step 1-2 ); (Step 1-3) of adding water to the ion exchange resin layer to wash the water; (
The present invention also provides a tin plating waste solution containing impurities and organic substances and adjusting the pH of the tin plating waste solution to 1.5 to 2.5 (Step 2-1); The pH-adjusted tin plating waste solution was circulated through an ion-exchange resin layer filled with di- (2-ethylhexyl) phosphoric acid-based ion exchange resin to form a tin- A step of adsorbing tin (step 2-2); (Step 2-3) of adding water to the ion exchange resin layer to wash the water; Adding an acid washing liquid to the ion exchange resin layer, and extracting the tin adsorbed on the ion exchange resin as a solution to recover a second purification solution (Step 2-4). A method for purifying a waste liquid is provided.
According to another aspect of the present invention, there is provided a process for preparing a tin plating waste solution comprising impurities and organic substances and adjusting the pH of the tin plating waste solution to 2.5 to 3.0 (first step); Circulating the pH-adjusted tin plating waste solution to an ion-exchange resin layer filled with an iminodiacetic acid ion-exchange resin to adsorb tin and impurities in the tin plating waste solution (second step); Washing the ion exchange resin layer by adding distilled water thereto (third step); Adding an acid washing solution to the ion exchange resin layer, extracting tin and metal impurities adsorbed on the ion exchange resin as a solution to recover the first purification solution (fourth step); Adjusting the pH of the first purification solution to 1.5 to 2.5 (fifth step); The pH-controlled first purification solution is circulated through an ion-exchange resin layer filled with di- (2-ethylhexyl) phosphoric acid-based ion exchange resin to form the first purification Adsorbing tin in the solution (sixth step); Washing the water by adding distilled water to the di- (2-ethylhexyl) phosphonic acid-based ion exchange resin layer (step 7); (Step 8) of adding an acid washing liquid to the di- (2-ethylhexyl) phosphonic acid based ion exchange resin layer to extract the adsorbed tin into a solution to recover a second purified solution A method for purifying a tin plating waste solution using a resin is provided.
According to the present invention, a tin plating waste solution containing a high concentration of organic matter and metal impurities, which is not easy to purify, is selectively adsorbed to an ion-exchange resin to recover a high purity tin solution in which the content of tin is increased and organic matters and metal impurities are purified can do.
The refined tin solution can be used again as the primary rate gold solution, and the tin metal recovery efficiency can be greatly increased when the tin solution is acid treated to recover the tin metal.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the structure of an ion exchange resin layer in a method for purifying a tin plating waste liquid using an ion exchange resin according to an embodiment of the present invention. FIG.
FIG. 2 is a process flow chart showing a procedure of a method for purifying a tin plating waste solution using an ion exchange resin according to an embodiment of the present invention.
FIG. 3 is a process flow chart showing a procedure of a method for purifying a tin plating waste solution using an ion exchange resin according to another embodiment of the present invention.
4 is a process flow chart showing a procedure of a method for purifying a tin plating waste solution using an ion exchange resin according to another embodiment of the present invention.
5 is a graph showing the recovery rate of tin according to the amount of di- (2-ethylhexyl) phosphonic acid ion exchange resin according to an embodiment of the present invention.
6 is a graph showing the concentration of metal impurities according to the amount of di- (2-ethylhexyl) phosphonic acid ion exchange resin according to an embodiment of the present invention.
7 is a photograph showing a bench scale ion exchange system apparatus according to another embodiment of the present invention.
8 is a graph showing tin recovery of di- (2-ethylhexyl) phosphonic acid ion exchange resin according to another embodiment of the present invention.
9 is a graph showing the recovery rate of tin according to the amount of iminodiacetic acid-based ion exchange resin according to another embodiment of the present invention.
10 is a graph showing the concentration of metal impurities according to the amount of iminodiacetic acid-based ion exchange resin according to another embodiment of the present invention.
11 is a graph showing tin recovery of an iminodiacetic acid type ion exchange resin according to another embodiment of the present invention.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.
The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.
In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.
FIG. 2 is a process flow chart of a method for purifying a tin plating waste solution using an ion exchange resin according to an embodiment of the present invention.
Referring to the drawings, a method for purifying a tin plating waste solution using an ion exchange resin according to the present invention comprises: preparing a tin plating waste solution containing metal impurities and an organic substance and adjusting the pH of the tin plating waste solution to 2.5 to 3.0 Step 1-1); Circulating the pH-adjusted tin plating waste solution into an ion-exchange resin layer filled with an iminodiacetic acid ion-exchange resin to adsorb tin and impurities in the tin plating waste solution (Step 1-2 ); (Step 1-3) of adding water to the ion exchange resin layer to wash the water; (Step 1-4) of adding an acid washing solution to the ion exchange resin layer and extracting the tin and metal impurities adsorbed on the ion exchange resin as a solution to recover the first purification solution.
The ion exchange resin can remove anions and cation impurities depending on the functional groups of the resin, and can selectively remove metal impurities according to the pH control. The ion exchange resin is capable of adsorbing metal ions without being influenced by organic matter, and has the advantage that tin adsorption is possible even in a tin plating waste liquid containing an organic matter of 40,000 ppm.
The tin plating waste liquid is preferably a waste liquid discharged from a plating process of a circuit board (PCB) or a lead frame because a tin recovery efficiency is very high when a waste liquid having a tin amount of 2 wt% or less is used, But is not limited to the content.
Therefore, the tin plating waste liquid may contain tin at a concentration of 1,000 to 25,000 ppm.
If the concentration of tin in the tin plating waste solution exceeds 25,000 ppm, additional ion exchange resin may be required, so that the tin recovery efficiency can be increased in the case of using a tin plating waste liquid containing tin within the above range.
The tin plating waste solution may be at least one selected from the group consisting of Fe, Zn, Na, Ca, Mg, Cu, Si, Ni, Potassium (K), and the like.
The organic material may be contained in the tin plating waste solution in an amount of 5 to 50% by weight.
When the content of the organic substance is more than 5 wt%, it is difficult to treat by a general chemical method, and the organic compound may be produced or the purity of the product may be reduced even after the treatment.
The pH of the tin plating waste solution can be adjusted to 2.5 to 3.0 (S01).
When the tin plating waste solution is circulated in an ion exchange resin layer filled with an iminodiacetic acid ion exchange resin in the pH range, the ion exchange resin adsorbs not only tin but also metal impurities (S02).
Here, in order to adjust the pH, any one selected from the group consisting of sodium oxide, ammonia water, hydrochloric acid and sulfuric acid, or one or more selected from the group consisting of hydrochloric acid and sulfuric acid may be mixed.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing the structure of an ion-exchange resin layer in a method for purifying a tin plating waste solution using an ion-exchange resin layer according to an embodiment of the present invention. FIG.
1, a
The
Here, the ion exchange resin layer may be filled with 400 to 1000 ml of the ion exchange resin per 1000 ml of the tin plating waste solution.
If the volume of the ion exchange resin with respect to the tin plating waste liquid is within the above range, the adsorption amount of tin and metal impurities may be increased. If the amount is outside the above range, the amount of tin adsorption may be decreased or the amount of metal impurities may be increased, The content of metal impurities may increase.
The ion exchange resin filled in the ion exchange resin layer may be an iminodiacetic acid ion exchange resin.
The iminodiacetic acid type ion exchange resin has an advantage over the di- (2-ethylhexyl) phosphoric acid type ion exchange resin in fill factor. However, in addition to the tin, the metal impurity Also, the purity of the tin of the solution recovered by adsorption may be lowered.
Therefore, in another embodiment of the present invention, the purity of the purified solution containing tin recovered by selectively using the ion exchange resin can be controlled, and the metal impurities in the tin plating waste solution can be regenerated first through the iminodiacetic acid ion exchange resin The tin solution containing tin can be recovered in high purity by increasing the purity of the tin recovered through the di- (2-ethylhexyl) phosphonic acid-based ion exchange resin.
On the other hand, in the step 1-2, the pH-adjusted tin plating waste solution is circulated to an ion-exchange resin layer filled with an iminodiacetic acid ion-exchange resin to adsorb tin and metal impurities in the tin- (S02).
At this time, it is preferable to circulate the pH-adjusted tin plating waste solution at a rate of 2.5-3 BV (bed volume) to the ion exchange resin layer for 3 hours to 5 hours to adsorb tin and metal impurities to the ion exchange resin Do.
When the passage time of the ion-exchange resin layer is less than 2.5 BV, the process time is prolonged and the productivity is reduced. When the passing time is more than 3 BV, the adsorption rate of the ion-exchange resin and tin may be reduced.
In the step 1-3, distilled water may be injected into the ion exchange resin layer to wash water (S03).
The purification solution containing high purity tin can be recovered by removing impurities and organic substances remaining in the ion exchange resin layer during the washing process.
In the washing step, 1000 to 2000 ml of distilled water may be added to the ion-exchange resin layer, and the plate may be washed with 10 to 20 BV for 30 to 60 minutes.
If the amount of distilled water is less than 1000 ml, the water washing effect may be reduced. If the feeding rate is less than 10 BV, the process time may increase and the efficiency may be decreased. The recovery of tin may be lowered due to the loss of adsorbed tin. Also, if the circulation time is less than 30 minutes, the washing efficiency may decrease, and if the circulation time exceeds 60 minutes, the process time may increase.
In step 1-4, the acid washing solution is added to the ion exchange resin layer, and the tin and the impurity metal adsorbed on the ion exchange resin are extracted as a solution to recover the first purification solution (S04).
In the step of introducing the pickling solution, tin and metal impurities adhered to the ion exchange resin can be extracted as a solution by circulating for 3 to 5 hours at a rate of 3 to 20 BV using 10 to 20 wt% sulfuric acid.
If the concentration of sulfuric acid in the pickling solution is lower than 10 wt%, the recovery rate of tin may be decreased, and if it exceeds 20 wt%, the process cost may increase.
In addition, if the rate of the acid scrubbing liquid is less than 3 BV, the process time is increased and the efficiency is decreased. If the acid scrubbing liquid is more than 20 BV, the ion exchange resin may be lost.
If the circulation time is less than 3 hours, the recovery rate of the tin may be decreased, and if the circulation time is more than 5 hours, the process time may increase.
In another embodiment of the present invention, the present invention provides a method for purifying a tin plating waste solution using an ion exchange resin, which is a bench scale level process rather than a laboratory scale process scale.
In the step of adsorbing tin and metal impurities in the tin plating waste solution in the step 1-2, 20 liters of the tin plating waste solution having a pH of 3.0 in the bench scale process is added to the ion exchange resin layer At a rate of 5 to 20 BV for 3 to 5 hours.
In the case of scaling up beyond the above range, the adsorption amount of tin is so small that the efficiency of the process is decreased or the adsorption amount of the metal impurity is too large, so that the purity of the purified solution extracted into the solution may be lowered.
In the step of washing the water by adding distilled water to the ion-exchange resin layer, it may be washed three to four times in total in the bench scale process, and in the case of washing with water less than three times, The purity of the solution is lowered, and if it is washed more than 4 times, the efficiency of the process may be lowered.
In the step of extracting the tin and the impurity metal adsorbed on the ion exchange resin, 20 L of 10 to 20 wt% sulfuric acid is circulated for 3 to 5 hours at a rate of 3 to 20 BV in the bench scale process, The tin attached to the resin can be extracted with a solution.
If less than 10% by weight of sulfuric acid is used outside the above range, recovery of tin from the ion exchange resin is difficult, and if it exceeds 20% by weight, the process cost may increase.
Further, in the step of putting the acid washing liquid in the ion exchange resin layer, in the case of the bench scale process, the acid washing liquid may be a mixed acid of hydrochloric acid and sulfuric acid.
When the mixed acid of sulfuric acid and hydrochloric acid is not used, there is a problem that a precipitate such as sulfate is formed in the ion exchange resin layer.
A method for purifying a tin plating waste solution using an ion exchange resin according to another embodiment of the present invention includes preparing a tin plating waste solution containing metal impurities and an organic substance and adjusting the pH of the tin plating waste solution to 1.5 to 2.5 -Stage 1); The pH-adjusted tin plating waste solution was circulated through an ion-exchange resin layer filled with di- (2-ethylhexyl) phosphoric acid-based ion exchange resin to form a tin- A step of adsorbing tin (step 2-2); (Step 2-3) of adding water to the ion exchange resin layer to wash the water; (Step 2-4) of adding an acid washing liquid to the ion exchange resin layer and extracting the tin adsorbed on the ion exchange resin as a solution to recover the second purification solution.
The pH of the tin plating waste solution can be adjusted to 1.5 to 2.5 (S05).
The tin plating waste solution may be circulated through the ion exchange resin layer filled with the di- (2-ethylhexyl) phosphonic acid ion exchange resin in the pH range (S06).
When the pH of the tin plating waste liquid is out of the above range, tin is not adsorbed to the ion exchange resin, resulting in a problem that the adsorption rate is very low.
The di- (2-ethylhexyl) phosphonic acid-based ion exchange resin layer may be filled with 600 to 1200 ml per 1,000 ml of the tin plating waste solution.
When the ion-exchange resin layer is filled in the tin plating waste solution out of the above-mentioned range, the adsorption rate of tin is low and the efficiency of the process can be greatly reduced.
The step of adsorbing the tin in the tin plating waste liquid in the step 2-2 may be performed in the pH adjusted tin plating waste solution at a rate of 2.5 to 3 BV (bed volume) for 3 to 5 hours So that the tin can be adsorbed to the ion exchange resin (S06).
If the concentration is out of the above range, the efficiency of the process becomes too low or the tin is not adsorbed sufficiently, so that a high purity purification solution can not be obtained when recovered into the purification solution.
In the step 2-3, 1000 to 2000 ml of distilled water may be added to the ion exchange resin layer, and the solution may be washed with 10 to 20 BV for 30 to 60 minutes. If the solution is washed out of the above range, It is impossible to obtain a high-purity purification solution containing impurities.
If the amount of distilled water is less than 1000 ml, the water washing effect may be reduced. If the feeding rate is less than 10 BV, the process time may increase and the efficiency may be decreased. The recovery of tin may be lowered due to the loss of adsorbed tin.
In addition, if the circulation time is less than 30 minutes, the washing efficiency may decrease, and if the circulation time exceeds 60 minutes, the process time may increase.
In the step 2-4, the acid washing liquid is circulated for 3 to 5 hours at a rate of 3 to 20 BV using 20 to 60 vol% hydrochloric acid to extract the tin attached to the ion exchange resin into a solution, The solution can be recovered (S08).
If less than 20 vol% hydrochloric acid is used outside the above range, recovery of tin from the ion exchange resin is difficult, and if hydrochloric acid exceeding 60 vol% is used, the process cost may increase.
In another aspect of the present invention, there is provided a process for producing a tin (II) salt using an ion exchange resin at a bench scale process level rather than a laboratory scale using a di- (2-ethylhexyl) A method for purifying a plating waste solution is provided.
In the bench scale process, 20 L of the tin plating waste solution having a pH of 1.5 is adsorbed to the ion exchange resin layer of 12 to 24 L in an amount of 5 to 20 BV Lt; / RTI > for 3 to 5 hours.
In the case of scaling up beyond the above range, the adsorption amount of tin is so small that the efficiency of the process is decreased or the adsorption amount of the metal impurity is too large, so that the purity of the purified solution extracted into the solution may be lowered.
When the tin adsorbed on the ion exchange resin is recovered as a solution and recovered in step 2-4, 20 L of 40 to 60% by volume hydrochloric acid is recovered for 3 to 5 hours at a rate of 3 to 20 BV in the bench scale process The tin attached to the ion exchange resin can be circulated and extracted into the solution.
If less than 40 vol.% Hydrochloric acid is used outside of the above range, recovery of tin from the ion exchange resin is difficult. If it exceeds 60 vol.%, The process cost may increase.
Meanwhile, in the step of injecting acid washing liquid into the ion exchange resin layer and extracting tin as a solution, a storage part capable of storing the remaining waste liquid remaining in the ion exchange resin layer in a bench scale process is provided, And a step of processing the data.
According to another embodiment of the present invention, the present invention provides a method of preparing a tin plating waste solution comprising a metal impurity and an organic substance and adjusting the pH of the tin plating waste solution to 2.5 to 3.0 (first step); Circulating the pH-adjusted tin plating waste solution to an ion-exchange resin layer filled with an iminodiacetic acid ion-exchange resin to adsorb tin and metal impurities in the tin plating waste solution (second step) ; Washing the ion exchange resin layer by adding distilled water thereto (third step); Adding an acid washing solution to the ion exchange resin layer, extracting tin and metal impurities adsorbed on the ion exchange resin as a solution to recover the first purification solution (fourth step); Adjusting the pH of the first purification solution to 1.5 to 2.5 (fifth step); The pH-controlled first purification solution is circulated through an ion-exchange resin layer filled with di- (2-ethylhexyl) phosphoric acid-based ion exchange resin to form the first purification Adsorbing tin in the solution (sixth step); Washing the water by adding distilled water to the di- (2-ethylhexyl) phosphonic acid-based ion exchange resin layer (step 7); (Step 8) of adding an acid washing liquid to the di- (2-ethylhexyl) phosphonic acid based ion exchange resin layer to extract the adsorbed tin into a solution to recover a second purified solution A method for purifying a tin plating waste solution using a resin is provided.
When the tin plating waste solution is ion-exchanged in order with the ion exchange resin in this order to obtain a purified solution containing tin, metal impurities are removed and the purity of tin is very high.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention.
< Example 1> Using ion exchange resin Tin plating waste liquid refine
The tin plating waste solution was obtained by obtaining an organic acid tin waste solution containing a large amount of organic additive. The tin plating waste solution was found to contain about 10 to 25 g / l of tin, a high concentration of organic substances of 40,000 ppm or more, and a small amount of impurities such as copper, nickel and lead. Iron, zinc, magnesium, copper, nickel and lead were optionally prepared and used to confirm the metal impurity removal effect.
The ion exchange resin used was an iminodiacetic acid system and a di- (2-ethylhexyl) phosphonic acid system.
The recovery rate of tin and the removal rate of impurities due to the change in the volume of the ion exchange resin layer and the pH of the solution were measured. The composition of the solution was measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES, PerkinElmer, Optima-7300 DV), and the total organic carbon (TOC, Shimadzu, TOC-L CPH ).
< Experimental Example 1> Tin recovery of di- (2-ethylhexyl) phosphonic acid ion exchange resin
The recoveries of tin (Sn) and the amount of metal impurity increase were measured according to the amount of ion exchange resin when tin was recovered using di- (2-ethylhexyl) phosphonic acid ion exchange resin.
When tin is adsorbed by using di- (2-ethylhexyl) phosphonic acid ion exchange resin, the recovery rate of tin is increased as the amount of ion exchange resin is increased, but the adsorption rate of metal impurities is also increased. Experiments were conducted to measure the amount of resin.
1000 ml of tin plating solution was adjusted to pH 1.5, and the tin was adsorbed by circulating at a rate of 2.5 BV to 600, 800, 1000 and 1200 ml of di- (2-ethylhexyl) phosphonic acid ion exchange resin. After adsorption of tin, 1000 ml of distilled water was used to circulate the ion exchange resin at a rate of 10 BV for 30 minutes to wash the ion exchange resin. The washed ion exchange resin was recovered by extracting the adsorbed tin as a solution by circulating the ion exchange resin for 3 hours at a rate of 3 BV using 60 vol% hydrochloric acid (HCl). The extracted tin solution was analyzed for tin content and impurity removal using ICP.
FIG. 5 is a graph showing the recovery rate of tin according to the amount of di- (2-ethylhexyl) phosphonic acid ion exchange resin according to an embodiment of the present invention, and FIG. 6 is a graph showing the recovery rate of tin according to an embodiment of the present invention. (2-ethylhexyl) phosphonic acid-based ion exchange resin.
As a result, the recovery of tin was increased to 50, 65, 77, and 87% as the amount of ion exchange resin increased to 600, 800, 1000, and 1200 ml in the di- (2-ethylhexyl) phosphonic acid ion exchange resin. 1, 2, and 7 ppm of copper, 3, 8, 15, and 74 ppm of lead, and 5, 15, 45, and 85 ppm of iron, , Respectively.
The di- (2-ethylhexyl) phosphonic acid ion exchange resin adsorbs tin first at pH 1.5 and adsorbs iron (Fe), lead (Pb), copper (Cu), and nickel Respectively. The purity of recovered tin solution increased with decreasing amount of ion exchange resin, but the purity of recovered tin solution decreased with increasing amount of ion exchange resin. That is, it was confirmed that the purity of the purified solution containing the recovered tin can be adjusted by controlling the amount of the di- (2-ethylhexyl) phosphonic acid ion exchange resin. From the results, it was confirmed that the di- (2-ethylhexyl) ) In 1000 ml of a phosphoric acid-based ion exchange resin, a tin refining solution having a tin recovery of 77%, impurities of iron 45,
< Experimental Example 2> Scale-up of di- (2-ethylhexyl) phosphonic acid based ion exchange resin
A bench scale level experiment was conducted to confirm whether or not 20 liters of tin plating waste solution can be treated with di- (2-ethylhexyl) phosphonic acid ion exchange resin.
7 is a photograph showing a bench scale ion exchange system apparatus according to another embodiment of the present invention.
This experiment was carried out to understand the problems of recovery of tin using ion exchange resin when the scale was increased and to design a pilot scale scale tin recovery system.
First, 20 L of the tin plating solution was adjusted to pH 1.5, and the tin was adsorbed by circulating for 3 hours at a rate of 5 BV to 20 L of the di- (2-ethylhexyl) phosphonic acid ion exchange resin. After the adsorption of tin, the ion exchange resin was washed with 20 L of distilled water for 30 minutes at an ion exchange resin at a rate of 10 BV. Washing was conducted three times in total to remove the residual plating solution and organic matter. The washed ion exchange resin was recovered by extracting the adsorbed tin into a solution by circulating the ion exchange resin for 3 hours at a rate of 3 BV using 20 L of 60% by volume of HCl.
The extracted tin solution was analyzed for recovery of tin by ICP. The test was repeated 5 times and the tin recovery and ion exchange resin reliability tests were conducted.
8 is a graph showing tin recovery of di- (2-ethylhexyl) phosphonic acid ion exchange resin according to another embodiment of the present invention.
Referring to FIG. 8, the initial tin recovery rate of the di- (2-ethylhexyl) phosphonic acid ion exchange resin was as low as 62%, but as the recovery was repeated, 77, 82, 83, The recovery rate was 78%, which was similar to the lab scale ion exchange resin test.
Experimental results of the bench scale show that the initial ion exchange resin should be activated during the pickling process when the tin is recovered using the ion exchange resin.
In addition, since the capacity of the ion exchange resin is high, the remaining amount of residual liquid remaining in the ion exchange resin layer after the recovery of tin from the tin plating waste liquid is as high as about 1 L. In order to remove this residual liquid, Apparatus, and the like, and a storage unit capable of storing the remaining waste liquid remaining in the ion exchange resin layer was newly provided to treat the remaining waste liquid.
Based on the experimental results, it was confirmed that a pilot scale ion exchange resin device can be designed.
< Experimental Example 3> Iminodiacetic acid system Tin recovery of ion exchange resin
When the tin was recovered using iminoacetic acid ion exchange resin, recovery of tin (Sn) and increase of impurities were measured according to the amount of ion exchange resin. This experiment failed to remove iron (Fe) and lead (Pb) when tin was recovered using di- (2-ethylhexyl) phosphonic acid ion exchange resin, so that iminodiacetic acid ion exchange resin Was used to confirm the removal of iron and lead and to determine the optimum amount of ion exchange resin.
In the experimental procedure, 1000 ml of tin plating solution was adjusted to pH 2.5, and the tin was adsorbed by circulating the iminodiacetic acid type ion exchange resin to 400, 600, 800, and 1000 ml at a rate of 2.5 BV. After adsorption of tin, 1000 ml of distilled water was used to circulate the ion exchange resin at a rate of 10 BV for 30 minutes to wash the ion exchange resin. The washed ion exchange resin was recovered by extracting the adsorbed tin into a solution by circulating the ion exchange resin for 3 hours at a rate of 3 BV using 20 wt% sulfuric acid (H 2 SO 4 ). The extracted tin solution was analyzed for tin content and impurity removal using ICP.
FIG. 9 is a graph showing the recovery rate of tin according to the amount of iminodiacetic acid-based ion exchange resin according to another embodiment of the present invention, and FIG. 10 is a graph showing the recovery rate of tin by the amount of iminodiacetic acid ion exchange FIG. 3 is a graph showing the concentration of metal impurities according to the amount of resin. FIG.
As shown in the figure, the recovery of tin (Sn) increased to 66, 84, 96 and 99% as the amount of iminodiacetic acid ion exchange resin was increased to 400, 600, 800 and 1000 ml, 1, 3, 8 and 17 ppm of copper (Cu), 0, 1 and 2 ppm of lead (Pb), 1, 4, 10 and 20 ppm of impurities Fe, 20, 21, 51 and 120 ppm of Ni, , 1 and 2 ppm, respectively.
As a result of the above experiment, it was confirmed that the iminodiacetic acid type ion exchange resin adsorbed tin first at pH 2.5 and adsorbed in the order of nickel (Ni), iron (Fe), copper (Cu) and lead (Pb). The purity of the recovered tin solution increased as the amount of the ion exchange resin decreased, but the purity of the recovered tin solution decreased as the amount of the ion exchange resin increased. As a result, the amount of lead (Pb) and iron (Fe), which are metal impurities that have not been completely removed from the di- (2-ethylhexyl) phosphonic acid ion exchange resin, In the case of using a nodiacetic acid-based ion exchange resin, it was confirmed that all the lead was removable and the iron was also partially removed.
According to the experimental results, the process can be selectively changed according to the impurity concentration of the tin plating waste solution. In the case where a large amount of impurities of lead and iron are contained, iron and lead are removed through the iminodiacetic acid type ion exchange resin Thereafter, when the tin was recovered using the di- (2-ethylhexyl) phosphonic acid-based ion exchange resin, a high-purity tin solution could be recovered.
< Experimental Example 4> Iminodiacetic acid system Ion exchange resin Scale-up
A bench scale level process experiment was conducted to verify that 20 liters of tin plating waste can be treated using iminoacetic acid based ion exchange resin. The above experiment was intended to identify the problem of recovery of tin using ion exchange resin when the tin plating waste liquid increased at a scale similar to that of the previous experiment, and to design a pilot scale scale tin recovery system.
In the experimental method, 20 liters of tin plating solution was adjusted to pH 3.0, and tin was adsorbed to 16 liters of iminodiacetic acid type ion exchange resin for 3 hours at a rate of 5 BV. After the adsorption of tin, the ion exchange resin was washed with 20 L of distilled water for 30 minutes at an ion exchange resin at a rate of 10 BV. Washing was conducted three times in total to remove the residual plating solution and organic matter. The washed ion exchange resin was recovered by extracting the adsorbed tin as a solution by circulating the ion exchange resin for 3 hours at a rate of 3 BV using 20 vol% H 2 SO 4 20 L.
The extracted tin solution was analyzed for recovery of tin by ICP. Also, by repeating this experiment five times, tin recovery, ion exchange resin recovery and reliability test were performed.
11 is a graph showing tin recovery of an iminodiacetic acid type ion exchange resin according to another embodiment of the present invention.
Referring to the drawings, the iminodiacetic acid ion exchange resin had an initial tin recovery of 91%, and tin recovery rates of 2, 3, 4, and 5 times showed tin recovery rates of 93, 89, 93, and 91% . The average recovery of iminodiacetic acid-based ion exchange resin was 91.4%, which was lower than the tin recovery rate of 96% on the laboratory scale (Lab scale).
As a result of bench scale experiments, it was confirmed that when the tin was recovered using iminoacetic acid-based ion exchange resin, the recovery rate of the tin was lower than that of the laboratory scale. As a result, It was found that most of the tin was recovered with a tin content of 0.1% or less. However, after extraction with the solution, the tin was not recovered as tin but remained in the ion exchange resin or precipitate such as sulfate was formed, Respectively.
Therefore, extraction with a solution of sulfuric acid and hydrochloric acid was used to obtain a similar recovery rate on a laboratory scale.
According to the method for purifying a tin plating waste solution using the ion exchange resin according to the present invention, tin is extracted from a waste tin plating solution containing low-purity tin, which has not been recovered in the past, as a solution to obtain an extract having a greatly increased tin content In addition, since the metal impurities such as lead and iron can be selectively removed according to the tin plating waste solution, the efficiency of the purification process can be greatly increased, and the bench scale level process for the pilot design can be performed. Further, the purity can be reused as a plating solution based on the tin-containing extract having a controlled purity, and highly purified tin can be recovered by acid treatment, thereby greatly increasing the efficiency of the tin separation process.
Although a concrete embodiment of the method for purifying tin plating waste liquid using the ion exchange resin according to the present invention has been described so far, it is obvious that various modifications can be made within the scope of the present invention.
Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.
It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.
Claims (20)
Circulating the pH-adjusted tin plating waste solution into an ion-exchange resin layer filled with an iminodiacetic acid ion-exchange resin to adsorb tin, lead and iron in the tin plating waste solution (first- 2);
(Step 1-3) of adding water to the ion exchange resin layer to wash the water;
Adding an acid washing solution to the ion exchange resin layer, extracting tin, lead and iron adsorbed on the ion exchange resin with a solution to recover a first purification solution (Step 1-4)
Wherein the ion-exchange resin layer comprises
1000 ml of the tin plating waste solution is filled with 400 to 1000 ml of an ion exchange resin,
And circulating the ion-exchange resin layer to adsorb tin, lead and iron in the tin plating waste liquid,
And the tin plating waste solution having the pH adjusted therein is circulated with the ion exchange resin layer at a rate of 2.5 to 3 BV (Bed volume) for 3 hours to 5 hours to adsorb tin and lead and iron to the ion exchange resin A method for purifying a tin plating waste solution using an ion exchange resin.
The tin plating waste liquid may contain,
Tin in a concentration of 1,000 to 25,000 ppm,
(Fe), zinc (Zn), sodium (Na), calcium (Ca), magnesium (Mg), copper (Cu), silicon (Si), nickel (Ni) Wherein the at least one metal impurity is selected from the group consisting of metal impurities and organic substances.
Wherein 1000 to 2000 ml of distilled water is added to the ion-exchange resin layer, and the water is washed with 10 to 20 BV for 30 to 60 minutes.
In the step of applying the pickling liquid,
Characterized in that tin and metal impurities adhering to the ion exchange resin are circulated for 3 to 5 hours at a rate of 3 to 20 BV using 10 to 20 wt% sulfuric acid to thereby extract the tin and metal impurities adhering to the ion exchange resin as a solution. ≪ / RTI >
In the step of adsorbing tin and metal impurities in the tin plating waste liquid,
In the case of a bench scale process, 20 L of the tin plating waste solution having a pH of 3.0 is circulated in an ion exchange resin layer of 16 to 17 L at a speed of 5 to 20 BV for 3 to 5 hours. Method for purifying tin - plating waste liquid using resin.
In the step of putting the distilled water into the ion-exchange resin layer and washing with water,
And in the case of a bench scale process, the water is washed three to four times in total.
In the step of extracting the tin and the impurity metal adsorbed on the ion exchange resin into a solution,
In a bench scale process, 20 L of 10 to 20 wt% sulfuric acid is circulated for 3 to 5 hours at a rate of 3 to 20 BV to extract the tin attached to the ion exchange resin as a solution. A method for purifying a tin plating waste solution.
In the step of injecting the pickling liquid into the ion exchange resin layer,
And in the case of a bench scale process, the pickling solution is a mixture of hydrochloric acid and sulfuric acid.
Circulating the pH-adjusted tin plating waste solution to an ion-exchange resin layer filled with an iminodiacetic acid ion-exchange resin to adsorb tin, lead and iron in the tin plating waste solution (second step );
Washing the ion exchange resin layer by adding distilled water thereto (third step);
Adding an acid washing liquid to the ion exchange resin layer, extracting tin, lead and iron adsorbed on the ion exchange resin with a solution to recover the first purification solution (fourth step);
Adjusting the pH of the first purification solution to 1.5 to 2.5 (fifth step);
The pH-controlled first purification solution is circulated through an ion-exchange resin layer filled with di- (2-ethylhexyl) phosphoric acid-based ion exchange resin to form the first purification Adsorbing tin in the solution (sixth step);
Washing the water by adding distilled water to the di- (2-ethylhexyl) phosphonic acid-based ion exchange resin layer (step 7);
(Step 8) of adding an acid washing liquid to the di- (2-ethylhexyl) phosphonic acid ion exchange resin layer to extract the adsorbed tin as a solution to recover a second purification solution,
Wherein the ion-exchange resin layer comprises
1000 ml of the tin plating waste solution is filled with 400 to 1000 ml of an ion exchange resin,
And circulating the ion-exchange resin layer to adsorb tin, lead and iron in the tin plating waste liquid,
The tin plating waste solution having the pH adjusted therein is circulated to the ion exchange resin layer at a rate of 2.5-3 BV (bed volume) for 3 hours to 5 hours to adsorb tin and lead and iron to the ion exchange resin,
The ion-exchange resin layer filled with the above-mentioned di- (2-ethylhexyl) phosphoric acid-based ion exchange resin,
Filled with 600 to 1200 ml per 1,000 ml of the tin plating waste solution,
In the step of adsorbing tin in the tin plating waste liquid,
Wherein the tin plating waste solution having the pH adjusted is circulated to the ion exchange resin layer at a rate of 2.5-3 BV (bed volume) for 3 hours to 5 hours to adsorb tin to the ion exchange resin. A method for purifying a tin plating waste solution using the method.
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| KR101467356B1 (en) * | 2014-04-22 | 2014-12-11 | 인천화학 주식회사 | Recovering Method of high concentration nickel from waste electroless nickel plating |
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| KR101467356B1 (en) * | 2014-04-22 | 2014-12-11 | 인천화학 주식회사 | Recovering Method of high concentration nickel from waste electroless nickel plating |
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