KR101737944B1 - A method of recovering indium or tin from indium or tin-containing solution or mixture with adsorption and further desorption procedure - Google Patents

Abstract

The present invention relates to a method for recovering indium or tin from an indium and / or tin-containing solution or mixture by using an adsorption / desorption process, and the method for recovering indium or tin according to the present invention is a method for recovering indium or tin from seawater containing indium, Industrial wastewater generated in electronic manufacturing processes such as industrial water, wastewater, cooling water, and display panels, electronic wastes such as solutions extracted from electronic wastes such as display panels or display panels, especially ITO etchant waste or waste ITO sludge The indium and / or tin can be recovered through the adsorption / desorption process with very high selectivity and efficiency.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering indium or tin from an indium or a tin-containing solution or mixture,

The present invention relates to a method for the recovery of indium or tin using an adsorption / desorption process from an indium or tin-containing solution or mixture.

Recent developments in industry and civilization have attracted much attention in securing resources. The government has designated manganese, molybdenum, lithium, magnesium, titanium, cobalt, chromium, rare earth, indium and tungsten as strategically rare metals in order to secure rare metal resources that are the main raw materials for the new growth engine industry.

Of these rare metals, indium (In) is a metal resource that is importantly used in LCDs, hybrid vehicles, and the like. The global display market is exploding with the desire of consumers to replace cathode ray tube (CRT) TV with liquid crystal display (LCD) and flat TVs of LED or FLAT PANEL TV. Accordingly, the demand for indium (In), which is an important basic material of these products, is also increasing.

Indium (In) is a rare metal and does not naturally produce a metal or a compound at all. It is usually contained in a small amount in sulfide minerals such as zinc and copper, and is concentrated in refining residues of zinc, slag and the like. Is the main source of indium.

Considering the situation of Korea lacking natural resources, it is considered that 10 major strategic metals (manganese, molybdenum, lithium, magnesium, titanium, cobalt, chromium, rare earth, indium, tungsten) including lithium and uranium from seawater as high value- Development of scarce metal recovery technology from ground and recycled resources including recovery technology development is very important.

As a conventional technique for recovering such a valuable metal, Korean Patent Laid-Open Publication No. 2014-0109053 discloses selective adsorption of indium using a cation exchange resin, but does not disclose selective desorption technology thereof. Korean Patent No. 10-1155359 discloses a technique for selectively recovering indium through an electrochemical method, but it has a disadvantage that a special apparatus is required. Korean Patent No. 101308972 discloses a technique of using a phosphorus-substituted sawdust as an adsorbent. However, this technique is limited not only to the adsorption of indium but also to the adsorption amount of 2.0 mg / g, But it is not enough to apply it. Furthermore, International Patent Application No. PCT / KR2013 / 000437 discloses a method including recovering valuable metals according to the characteristics of wastewater as an adsorption process, but discloses a technique for recovering metals by desorption after adsorption not.

It is an object of the present invention to provide a method for selectively recovering indium or tin using an adsorption / desorption process from an indium or tin-containing solution or mixture.

In a first aspect of the present invention, there is provided a method for producing a metal-phosphorus-based metal oxide nanoparticle by adding an adsorbent containing at least one selected from metal-phosphate or non-metal-phosphate molecular sieves represented by the following formula (1) to a solution or mixture containing indium, Tin, or both, to an adsorbent to obtain an adsorbent to which indium, tin or both are adsorbed (step 1); And a step (step 2) of desorbing the tin by desorbing indium or stirring in an alkali solution by stirring the adsorbent in which the indium, tin or both are adsorbed in an acid solution, to thereby recover the indium or tin.

[Chemical Formula 1]

M _a (PO) _b X _c

Wherein M is at least one element selected from the group consisting of Ni, Ti, Vd, Cr, Mn, Fe, Co, Zn, At least one phosphate ion consisting of HPO ₄ or PO ₄ and X is at least one metal selected from the group consisting of NH 2, of _3, H ₂ 0, a hydroxy group (-OH), a halogen group, a nitro group (-NO ₃₎ and seulpon acid group and (-SO ₃ H) one or more ionic or capable of coordination compound is selected from, a real number from 0.01 to 20 , b is a number from 1 to 60, and c is a real number from 0 to 100).

In a second aspect of the present invention, there is provided a method for producing indium or tin using ITO etching waste liquid or waste ITO sludge, comprising the steps of: adding a metal-phosphate or nonmetal-phosphate molecular sieve represented by the following formula 1 to an ITO etching waste liquid or waste ITO sludge Adding an adsorbent comprising one or more selected materials to adsorb indium, tin or both on the adsorbent to obtain an adsorbent on which indium, tin or both are adsorbed (step a); And a step (b) of desorbing the tin by desorbing indium or stirring the adsorbent in which the indium, tin or both are adsorbed in an acid solution or stirring in an alkali solution.

[Chemical Formula 1]

M _a (PO) _b X _c

Wherein M is at least one element selected from the group consisting of Ni, Ti, Vd, Cr, Mn, Fe, Co, Zn, At least one phosphate ion consisting of HPO ₄ or PO ₄ and X is at least one metal selected from the group consisting of NH 2, of _3, H ₂ 0, a hydroxy group (-OH), a halogen group, a nitro group (-NO ₃₎ and seulpon acid group and (-SO ₃ H) one or more ionic or capable of coordination compound is selected from, a real number from 0.01 to 20 , b is a number from 1 to 60, and c is a real number from 0 to 100).

Hereinafter, the present invention will be described in detail.

Conventional indium or tin recovery technology is an adsorption technique using an adsorbent, which is difficult to selectively desorb indium or tin from an adsorbent on which indium or tin has been adsorbed, or requires a post-treatment process of a multi-step process, The process is complicated and the reuse of the adsorbent is difficult. In the present invention, a porous molecular sieve such as a metal-phosphate or a non-metal-phosphate molecular sieve represented by the general formula (1) is used as an adsorbent of indium or tin, and indium, tin or both are adsorbed to the adsorbent and then stirred in an acid solution or an alkali solution It is found that indium or tin can be selectively desorbed from the adsorbent without a separate pretreatment process and that the adsorbent after desorption can be reused because of its structural stability. The present invention is based on this.

The method for recovering indium or tin according to the present invention comprises the steps of adding an adsorbent containing at least one selected from metal-phosphate or non-metal-phosphate molecular sieves represented by formula (1) to a solution or mixture containing indium, Adsorbing indium, tin or both on an adsorbent to obtain an adsorbent on which indium, tin or both are adsorbed (step 1); And a step (step 2) of desorbing the tin by desorbing indium or stirring in an alkali solution by stirring the adsorbent on which the indium, tin or both are adsorbed in an acid solution.

Step 1 is a step of obtaining an adsorbent to which indium, tin or both are adsorbed by adsorbing indium, tin or both on the adsorbent by adding an adsorbent to a solution or mixture containing indium, tin or both.

As used herein, the term "solution or mixture comprising indium, tin or both" refers to solutions, dispersions, mixtures, etc., comprising indium, tin or both and includes, for example, indium, tin or both Liquid wastes such as industrial wastewater generated in the manufacturing process of electronic products such as industrial wastewater, wastewater, cooling water, and display panel, and solutions extracted from electronic wastes such as display panels, in particular, ITO (indium tin oxide) And may also be a material in the form of a mixture of electronic waste such as display panels, especially waste ITO (indium tin oxide) sludge, but is not limited thereto.

The solution or mixture comprising indium, tin or both may be a transition metal, a typical metal and a lanthanum metal, especially aluminum, calcium, iron, nickel, manganese, molybdenum, lithium, magnesium, titanium , Cobalt, chromium, rare earth, tungsten, and the like.

Since the detection limit of indium in a solution or a mixture containing indium, tin or both, which can be used in the method for recovering indium or tin according to the present invention, is several ppb or so, a solution or mixture containing indium, tin or both Containing at least several ppb of indium can be used.

The metal-phosphate or non-metal-phosphate molecular sieve used as an adsorbent for adsorbing indium, tin or both in the present invention means a metal or a non-metal and a phosphorus compound consisting of a metal-phosphate or a non-metal-phosphate bond represented by the above formula can do.

In the present invention, by using the metal-phosphate or non-metal-phosphate molecular sieve as the adsorbent of indium, tin or both, it is possible to induce the indium ion and / or tin ion to be more efficiently adsorbed by strong bonding with the phosphate structure.

In the present invention, the metal-phosphate or non-metal-phosphate molecular sieve as the adsorbent of indium and / or tin is used in an amount of 0.1 wt% or more, preferably 0.5 wt% or more, Can be adsorbed in an amount of not less than 1% by weight, particularly preferably not more than 10% by weight, and the tin content is not less than 0.1% by weight, preferably not less than 0.2% by weight, more preferably not less than 0.3% by weight, It can be adsorbed in an amount of 1% by weight.

In the present invention, preferred examples of the metal-phosphate molecular sieve include porous nickel-phosphate molecular sieve or porous silicoaluminophosphate molecular sieve. The porous nickel-phosphate molecular sieve, for example _{VSB-1 (Ni 18 (HPO} 4) 14 (OH) 3 F 9 (H 3 O / NH 4) 4 · 12H 2 O) and the _{VSB-5 (Ni 20 [(} OH ) and the like, such as VSB-based material _{12 (H 2 O) 6]} [(HPO 4) 8 (PO 4) 4] · 12H 2 O). Examples of the porous silicoaluminophosphate molecular sieve include SAPO-34, SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-20, SAPO-35, SAPO-37, SAPO- , SAPO-44, SAPO-31 and SAPO-41.

The VSB materials may also include metals other than nickel, such as titanium, vanadium, chromium, manganese, iron, cobalt, zinc, silicon, , Magnesium (Mg), lanthanum (La), and cerium (Ce), and the materials disclosed in Korean Patent No. 0680889 may be mentioned.

In one embodiment of the present invention, VSB-5 (Ni ₂₀ [(OH) ₁₂ (H ₂ O) ₆ ] [(HPO ₄ ) ₈ (PO ₄ )] used as an adsorbent of indium and / ₄ ] · 12H ₂ O) is a nickel and phosphorus nanoporous material (24-membered ring structure) composed of 24 oxygen pores and has a pore size of about 6.4 Å, VSB-5 disclosed in Japanese Patent No. 0525209 can be mentioned.

One method for synthesizing VSB-5 is a method of synthesizing vanadium and phosphorus compounds by adding a base of diamines ranging from 1,2-ethylenediamine to 1,8-octanediamine [J. Am. Chem. Soc., Vol. 125, pp. 1309 1312, 2003; Angew. Chem. Int. Ed. vol. 40, pp. 2831-2834, 2001). As the base component of the diamines, 1,3-diaminopropane (DAP) is mainly used. The composition of VSB-5 molecular sieve is approximately 1.0 Ni: 2.1 P: 5.0 DAP: 140 H2O in a molar ratio, and this mixture can be hydrothermally reacted at 180 ° C for 56 days to obtain VSB-5 molecular sieve. However, since diamines used as bases are expensive, they have to be heat-treated to remove amines after synthesis, and some pore structures are collapsed or clogged during heat treatment to reduce the surface area of VSB-5 molecular sieve, Problems that can be reported are being reported.

An example of another synthesis method of VSB-5 is disclosed in Korean Patent No. 0525209, wherein a VSB-5 molecular sieve composition containing a nickel compound and a phosphorus compound as raw materials and a base as a pH controlling material 5, which is capable of exhibiting redox characteristics, optical properties, and electric and electronic properties, unlike the conventional VSB-5 molecular sieve composition. In particular, the VSB- And can be applied to organic amines such as monoamines which can be obtained from VSB-5 molecular sieve, which can be applied to the present invention, and the heat treatment process can be omitted in the case of using an inorganic base, A manufacturing method has been reported.

In a preferred embodiment of the present invention, the porous nickel-phosphate molecular sieve prepared according to the above-described preparation method can be used as an adsorbent for adsorbing indium and / or tin, and porous nickel-phosphate Molecular sieves can also be used.

When the porous nickel-phosphate molecular sieve is used as an adsorbent of indium in the method for recovering indium according to the present invention, indium is preferably extracted from a solution or mixture containing indium by 80% or more, , More preferably not less than 90%, particularly preferably not less than 99%.

In the case of using the porous nickel-phosphate molecular sieve as the adsorbent of tin in the method for recovering tin according to the present invention, tin is preferably extracted from the solution or mixture containing tin by 80% or more, , More preferably not less than 90%, particularly preferably not less than 99%.

According to one preferred embodiment of the invention, the porous nickel-phosphate molecular sieve as an adsorbent of indium is present in an amount of at least 1% by weight, preferably at least 5% by weight, more preferably at least 10% by weight, % Or more, particularly preferably 20 wt% or more. In the present invention, some porous nickel-phosphate molecular sieves can adsorb substantially all indium from a solution containing indium to a level of ppb or less, which is the detection limit.

According to one preferred embodiment of the invention, the porous nickel-phosphate molecular sieve as a sorbent of tin is present in an amount of not less than 1% by weight, preferably not less than 5% by weight, more preferably not less than 10% by weight, Or more, particularly preferably 20 wt% or more. In the present invention, some porous nickel-phosphate molecular sieves can adsorb substantially all of the tin from a solution containing tin to levels below the detection limit, specifically ppb units.

In the present invention, a metal-phosphate or non-metal-phosphate molecular sieve is added to a solution or a mixture containing indium, tin or both, as described above, in an amount of 0.1 to 150 g per liter of a solution or mixture containing indium, tin or both, To 100 g, and more preferably 1 to 80 g. However, the amount is not particularly limited and may be adjusted depending on the adsorption temperature, stirring speed, adsorption time, and the like. Specifically, as the amount of the metal-phosphate or non-metal-phosphate molecular sieve used and / or the stirring speed is increased, the adsorption time of indium and tin can be shortened, so that the amount of the molecular sieve and the stirring speed can be adjusted as necessary.

Step 2 is a step of desorbing tin from the adsorbent by desorbing indium from the adsorbent or stirring in an alkali solution by stirring the adsorbent on which indium, tin or both are adsorbed in an acid solution.

In the present invention, when the adsorbent in which indium, tin or both are adsorbed in the step 2 is stirred in an acid solution, it is confirmed that indium is selectively desorbed. Therefore, the indium can be selectively recovered by stirring the adsorbent in which indium, tin or both are adsorbed in the step 2 in an acid solution.

In addition, in the present invention, it was confirmed that when the adsorbent adsorbed with indium, tin or both was stirred in an alkali solution in step 2, tin was selectively desorbed. Therefore, the tin can be selectively recovered by stirring the adsorbent in which indium, tin or both are adsorbed in the step 2 in an alkali solution.

In the present invention, the stirring treatment in the acid solution or the alkaline solution in the step 2 is carried out irrespective of the order so that the indium and the tin are sequentially recovered, so that indium and tin can be obtained individually as a result.

In a preferred embodiment, step 2 is performed by desorbing the indium, tin or both adsorbed adsorbent in an acid solution to desorb the indium, stirring the solution in an alkali solution to desorb the tin, thereby recovering the indium first, Can be recovered.

In a preferred embodiment, step 2 is performed by desorbing the tin by stirring the adsorbent in which the indium, tin or both are adsorbed in an alkali solution, and stirring the solution in an acid solution to desorb the indium, thereby recovering the tin first, Can be recovered.

As used herein, the term "acid solution" may refer to a material in the form of a solution in acid form. For example, the acid solution can be to include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid or mixtures thereof as the acid, may be to include water, C _{1 -6} alcohol or a mixed solvent thereof as a solvent.

In the present invention, the desorption rate of indium may vary depending on the pH of an acid solution used for desorption. In order to increase the desorption rate, the acid solution preferably has a pH of 1 to 3. Specifically, in one embodiment of the present invention, indium desorption occurs at a pH of 1.6 to 2.8, but indium desorption does not occur at a pH of 5 or higher (Table 3).

In the present invention, the acid solution can selectively desorb indium from the adsorbent, effectively recovering indium from a solution or mixture containing metals other than indium (Table 4).

The term "alkali solution" as used in the present invention may mean a substance in the form of a solution in an alkaline solution. For example, the alkali solution is sodium hydroxide as the alkali (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) _2), ammonia water (NH ₄ OH), magnesium hydroxide (Mg (OH) ₂₎ or mixtures thereof be one that includes, and may be one comprising water, C _{1 -6} alcohol or a mixed solvent thereof as a solvent.

In the present invention, the desorption rate of the tin may vary depending on the pH of the alkali solution used for desorption. In order to increase the desorption rate, the alkali solution preferably has a pH of 10 to 12. Specifically, it was confirmed that selective desorption of tin occurs at pH 12 in one embodiment of the present invention (FIG. 4).

In the present invention, it is preferable that stirring of step 2 is performed for a sufficient time to allow the indium and / or tin to be desorbed. Preferably, the stirring time may be from 30 minutes to 12 hours.

In the present invention, it may further include drying the adsorbent on which indium and / or tin has been adsorbed before the step 2. Through this drying step, the indium and / or tin desorption in the subsequent step 2 can be performed more efficiently.

In accordance with the present invention, indium and / or tin are adsorbed from a solution or mixture comprising indium, tin or both using metal-phosphate or non-metal-phosphate molecular sieves, and then stirred in an acid solution to selectively desorb indium, The process of recovering tin by selectively withdrawing tin by recovery and / or stirring in an alkaline solution can be carried out according to a process known to a person skilled in the art without limitation, such as continuous, batch or the like.

The method for producing indium or tin using ITO etching waste liquid or waste ITO sludge according to the present invention is characterized in that the ITO etching waste liquid or waste ITO sludge is impregnated with any one selected from metal-phosphate or nonmetal- Adding an adsorbent comprising the above material to adsorb indium, tin or both on the adsorbent to obtain an adsorbent on which indium, tin or both are adsorbed (step a); And a step (b) of desorbing the tin by desorbing indium or stirring in an alkali solution by stirring the adsorbent in which the indium, tin or both are adsorbed in an acid solution.

[Chemical Formula 1]

M _a (PO) _b X _c

Wherein M is at least one element selected from the group consisting of Ni, Ti, Vd, Cr, Mn, Fe, Co, Zn, At least one phosphate ion consisting of HPO ₄ or PO ₄ and X is at least one metal selected from the group consisting of NH 2, of _3, H ₂ 0, a hydroxy group (-OH), a halogen group, a nitro group (-NO ₃₎ and seulpon acid group and (-SO ₃ H) one or more ionic or capable of coordination compound is selected from, a real number from 0.01 to 20 , b is a number from 1 to 60, and c is a real number from 0 to 100).

ITO transparent electrodes are used in many electronic products. Accordingly, indium and / or tin, which can be industrially reused, can be produced by recovering indium and / or tin from an etching solution or a discarded ITO transparent electrode when manufacturing an ITO transparent electrode.

In the method for producing indium or tin using ITO etching waste solution or waste ITO sludge according to the present invention, steps a and b may be performed in the same manner as step 1 and step 2 of the method for recovering indium or tin, respectively.

INDUSTRIAL APPLICABILITY According to the indium or tin recovery method of the present invention, industrial wastewater generated in an electronic manufacturing process such as water, wastewater, cooling water, and display panel including indium, tin or both is extracted from electronic waste such as display panels Indium and / or tin from an electronic waste such as a solution or a display panel, especially an ITO etching waste solution or a waste ITO sludge, can be recovered through an adsorption / desorption process with very high selectivity and efficiency.

1 is a graph showing the amount of desorbed indium and tin according to pH by stirring VSB-5 adsorbed on indium and other metal ions on an indium-etching waste liquid according to an embodiment of the present invention, to be.
FIG. 2 is a graph showing VSB-5 adsorbed on indium and other metal ions on an indium-etching waste liquid according to an embodiment of the present invention by stirring in an aqueous solution of pH 2 and showing desorption amount with time.
(B) VSB-5 adsorbing indium and other metal ions on the indium-etched waste liquid, and (c) adsorbing metal on the adsorbed VSB-5 adsorbent. In accordance with an embodiment of the present invention, VSB-5 was desorbed and dried after stirring in an aqueous solution of pH 2, (d) stirred for 4 hours in a pH 2 aqueous solution, and then stirred for 4 hours in a pH 7 aqueous solution to further remove the salt. to be.
FIG. 4 is a graph showing VSB-5 adsorbed on indium and other metal ions on an indium-etching waste liquid according to an embodiment of the present invention and agitating VSB-5 in an aqueous solution of pH 12 and showing desorption amount with time.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the examples.

Manufacturing example  1: Porous nickel- Phosphate  Manufacture of molecular sieves

The porous nickel-phosphate molecular sieve is composed of nickel, phosphorus, oxygen and metal components and the manufacturing method is as follows. First, 3.42 g of nickel chloride hexahydrate (NiCl ₂ 6H ₂ O) was dissolved in 24.7 g of distilled water. 1.01 g of 85% phosphoric acid was added dropwise to the mixed solution, and 2.55 g of ammonia water was added to obtain a reaction product having a composition of 1 Ni: 0.63 P: 3.0 NH ₃ : 100.0 H ₂ O and a pH of 7.7. 30 g of the reaction product obtained above was sealed in a Teflon reactor and sealed. The resultant was kept in a microwave reactor at 180 ° C for 1 hour to crystallize and then cooled at 25 ° C to obtain VSB-5 molecular sieve after solid-liquid separation. The VSB-5 molecular sieve thus obtained had a BET surface area of 400 m ² / g and the same structure as that described in Korean Patent No. 0525209 as a result of XRD diffraction analysis.

Manufacturing example  2: Porous nickel- Phosphate  Manufacture of molecular sieves

First, 3.30 g of nickel chloride hexahydrate (NiCl ₂ 6H ₂ O) was dissolved in 23.86 g of distilled water. 1.6 g of 85% phosphoric acid was added dropwise to the mixed solution, and 1.28 g of ammonium fluoride was added to obtain a reaction product having a composition of 1.00 Ni: 1.00 P: 2.5 NH ₄ F: 100 H ₂ O in terms of molar ratio. 30 g of the reaction product obtained above was sealed in a Teflon reactor and sealed. The resultant was kept in a microwave reactor at 180 ° C for 1 hour to crystallize and then cooled at 25 ° C to obtain VSB-1 molecular sieve after solid-liquid separation. The XRD diffraction analysis of the VSB-1 molecular sieve obtained above was the same as that described in Korean Patent No. 0525209.

Manufacturing example  3: Porosity Silica alumino Phosphate -34 ( SAPO -34) Manufacturing

To 5.34 g of phosphoric acid (85%) was added 28.08 ml of water. Thereafter, 9.57 g of tetraethylammonium hydroxide (TEAOH) was added. 3.15 g of aluminum isopropoxide (98%) was slowly added dropwise to the solution while stirring and the mixture was stirred for 30 minutes at room temperature. 1.17 g of the silica precursor Ludox-AS40 was gradually dropped while stirring. Since the physical properties vary depending on the degree of dispersion of the gel, it was sufficiently stirred. At this time, SAPO-34 molecular sieve was prepared by using the molar ratio of the reaction gel to 1.0 Al ₂ O ₃ : 0.89 P ₂ O ₆ : 0.3 SiO ₂ : 2.0 TEAOH: 60 H ₂ O. The gel-state solution was placed in an autoclave and heated at 180 占 폚 for 48 hours with stirring. The SAPO-34 molecular sieve prepared above was separated by centrifugation to recover the unreacted material and to obtain SAPO-34 molecular sieve of crystalline part, and was recovered by washing with water several times. The SAPO-34 molecular sieve thus prepared was dried at 110 ° C to obtain a powder. To remove the casting product, SAPO-34 molecular sieve was prepared by heating at 600 ° C for 10 hours while blowing air.

Example  1: Nickel- Phosphate  Evaluation of indium and tin adsorption capacity from indium wastewater solution using molecular sieve

The porous crystalline nickel-phosphate molecular sieve prepared in Preparation Example 1, specifically 0.1 g of VSB-5 molecular sieve, was added to 100 ml of an indium waste water solution and stirred for 10 hours or longer to adsorb indium and tin to the molecular sieve And the solution was collected. The solution was subjected to elemental analysis, and after the adsorption was terminated, the adsorption performance of the valuable metal was tested as follows by analyzing the element adsorbed on the crystalline porous nickel-phosphate molecular sieve by filtration. In this case, the indium wastewater solution is an ITO etching waste solution formed during etching in the process of sputtering ITO thin film, which is a transparent electrode, on a glass surface in a LCD manufacturing process and forming a pattern by photolithography, Recovery, RIST Research Papers 2007, Vol. 21, No. 4, 352-355) were used.

When VSB-5 is used, the concentration of 96.8 mg / L indium element contained in the indium wastewater solution, more precisely, 9.68 mg / 10 ml of indium contained in 10 ml of the solution can be adsorbed after stirring for 10 hours, When adsorbed, VSB-5 adsorbed at 79 mg / lg when converted to VSB-5 / g. The above procedure was carried out using VSB-1 and SAPO-34 as adsorbents, respectively, and the results are shown in Table 2 below.

The tin adsorption amount was evaluated by the same procedure as above, and the results are shown in Table 2 below.

Specific surface area (m < 2 > / g) Indium adsorption amount (mg / g) Tin adsorption amount (mg / g) VSB-5 430 78.9 7.8 VSB-1 145 25.2 6.6 SAPO-34 750 16.8 4.0

VSB-5 was adsorbed at 78.9 mg / g for 10 hours adsorption, 25.2 mg / g for VSB-1 adsorbed, and 16.8 mg / g adsorbed for SAPO-34 adsorbed on the adsorbent as shown in Table 2 Respectively.

Example  2: VSB Evaluation of indium desorption capacity in indium wastewater solution using

In order to evaluate the desorption characteristics for recovering indium in the porous nickel-phosphate molecular sieve adsorbed with indium, tin and metal ions using VSB-5 as an adsorbent in Example 1, the following experiment was conducted. First, 0.1 g of the porous nickel-phosphate molecular sieve adsorbed metal ions was stirred in a 1 M hydrochloric acid solution in an aqueous solution whose pH of the aqueous solution was adjusted as shown in Table 2, followed by filtration and drying, followed by desorption The dose was evaluated. The results are shown in Table 3 below.

From Table 3, it can be seen that 75% of the adsorbed amount of indium adsorbed at pH 2 is desorbed. As the acid strength decreases at pH 2.2, the desorption rate drops below 40%. On the other hand, the desorption rate of tin was less than 1% at pH 2. Therefore, in the prior art, indium and tin could not be selectively separated through the adsorption and desorption processes. However, in the present invention, indium without tin can be selectively recovered through the adsorption and desorption processes.

Example  3: Porous metal under acidic conditions - Phosphate  Molecular sieve VSB -5, VSB Comparative evaluation of indium and tin desorption using SAPO-34

The desorption amounts of indium and tin of VSB-5, VSB-1 and SAPO-34 were compared and evaluated in the same manner as in Example 2 above. The results are shown in Table 4 below. The measurement results of the change in desorption amount according to the pH change and stirring time in the case of using VSB-5 are shown in Fig. 1 and Fig. 2, respectively.

absorbent pH metal Adsorption amount (mg / g) Removal rate (%) VSB-1 2.2 In 14.8 59.2 Sn 0.3 4.7 2.4 In 13.6 54.4 Sn 0.0 0.0 VSB-5 2 In 59.0 74.8 Sn 0.0 0.0 2.2 In 32.8 42.0 Sn 0.0 0.0 SAPO-34 2 In 8.6 51.4 Sn 0.0 0.0 2.2 In 7.0 41.4 Sn 0.0 0.0

It can be seen from Table 4 that although desorption rates differ depending on pH, it is common that only desorption of indium is selectively performed under acidic conditions. 1 and 2, there is a difference in the desorption rate depending on the pH, but when the stirring time is 1 hour to 4 hours, there is no significant change in the desorption rate depending on the agitation time.

Example  4: Porous metal- Phosphate  Evaluation of structural stability of molecular sieve

VSB-5 obtained in Preparation Example 1, VSB-5 adsorbed on indium, tin and other metal ions obtained in Example 1, VSB-5 adsorbed on indium by stirring for 4 hours in a pH 2 aqueous solution, and pH 2 The solution was agitated for 4 hours in aqueous solution and then agitated for 4 hours in pH 7 aqueous solution. VSB-5, from which the salt was further removed, was subjected to X-ray diffraction analysis to observe the change of structure.

The results are shown in Fig. VSB-5 adsorbed indium, tin and other metal ions, (c) VSB-5 adsorbed indium by stirring for 4 hours in a pH 2 aqueous solution, (b) VSB- d) is the result of VSB-5 with stirring for 4 hours in pH 2 aqueous solution followed by stirring for 4 hours in pH 7 aqueous solution to further remove the salt.

In FIG. 3 (b), VSB-5 adsorbed on the metal was observed to have a reduced intensity of X-ray diffraction peaks due to the diffraction interference phenomenon of metal ions and other salts. (c), the intensity of the peak was recovered as the desorbed indium was removed. Further, in (d), as the salt was removed due to the further purification, the peak recovered to be equivalent to (a).

3, it can be seen that the porous metal-phosphate molecular sieve is restored to its original structure even after the intake / desorption by using the absorption / desorption process of the present invention, and thus has structural stability.

Example  5: Under the alkaline conditions, the porous metal- Phosphate  Comparative evaluation of indium and tin desorption using molecular sieve

In order to evaluate the desorption characteristics of tin in the porous nickel-phosphate molecular sieve adsorbed with indium, tin and metal ions using VSB-5 as an adsorbent in Example 1, the following experiment was conducted. First, 0.1 g of the porous nickel-phosphate molecular sieve adsorbed metal ions was stirred in an aqueous solution of 1 M NaOH solution in which the pH of the aqueous solution was adjusted to 12 for each hour, filtered and dried to obtain a filtrate The desorption capacity was evaluated by elemental analysis. The results are shown in Fig.

It can be seen from FIG. 4 that tin is selectively desorbed in comparison with indium under alkaline conditions. Further, it can be seen from FIG. 4 that the desorption amount of tin increases with time under an alkaline condition.

Claims (15)

Tin and indium in an adsorbent to adsorb tin and indium on an adsorbent by adding an adsorbent containing at least one selected from metal-phosphate or non-metal-phosphate molecular sieve represented by the following formula (1) Obtaining the adsorbed adsorbent (step 1);
Stirring the adsorbent on which the tin and indium adsorbed in the acid solution to desorb the indium (step 2-1); And
(Step 2-2) of desorbing the tin by stirring in an alkali solution,
Steps 2-1 and 2-2 are performed in any order,
A method for recovering indium and tin, characterized in that both indium and tin are recovered individually.
[Chemical Formula 1]
M _a (PO) _b X _c
Wherein M is at least one element selected from the group consisting of Ni, Ti, Vd, Cr, Mn, Fe, Co, Zn, At least one phosphate ion consisting of HPO ₄ or PO ₄ and X is at least one metal selected from the group consisting of NH 2, of _3, H ₂ 0, a hydroxy group (-OH), a halogen group, a nitro group (-NO ₃₎ and seulpon acid group and (-SO ₃ H) one or more ionic or capable of coordination compound is selected from, a real number from 0.01 to 20 , b is a number from 1 to 60, and c is a real number from 0 to 100).
The method according to claim 1, wherein the solution or mixture comprising tin and indium is selected from the group consisting of tin and indium, industrial wastewater generated from seawater industrial water, wastewater, cooling water, electronic product manufacturing processes, A method of recovering indium and tin characterized by being an electronic waste.
The method for recovering indium and tin according to claim 2, wherein the solution or mixture containing tin and indium is an indium tin oxide (ITO) etchant waste or a waste ITO (indium tin oxide) sludge.
The method of claim 1, wherein the solution or mixture comprising tin and indium further comprises at least one metal selected from the group consisting of transition metals, typical metals and lanthanide metals.
5. The method of claim 4, wherein the solution or mixture comprising tin and indium is selected from the group consisting of aluminum, calcium, iron, nickel, manganese, molybdenum, lithium, magnesium, titanium, cobalt, chromium, rare earth, and tungsten Or more of the metal.
The method of claim 1, wherein the metal-phosphate molecular sieve is a porous nickel phosphate molecular sieve or a porous silicoaluminophosphate molecular chain of indium and tin.
7. The method of claim 6, wherein the metal-phosphate molecular sieve is selected from the group consisting of VSB-1, VSB-5, SAPO-34, SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO- -37, SAPO-40, SAPO-42, SAPO-44, SAPO-31, SAPO-41 or mixtures thereof.
delete The method of claim 1, wherein the acid solution comprises hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid or a mixture thereof as an acid.
The method for recovering indium and tin according to claim 1, wherein the acid solution and the alkali solution each independently contain water, C _1-6 alcohol or a mixed solvent thereof as a solvent.
The method for recovering indium and tin according to claim 1, wherein the acid solution has a pH of 1 to 3.
The method of claim 1, wherein the alkali solution is sodium hydroxide as the alkali (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) _2), ammonia water (NH ₄ OH), magnesium hydroxide (Mg (OH) ₂₎ ≪ / RTI > or a mixture thereof.
The method for recovering indium and tin according to claim 1, wherein the alkali solution has a pH of 10 to 12.
The method according to claim 1, wherein each stirring time in steps 2-1 and 2-2 is 30 minutes to 12 hours.
A method for producing indium and tin using ITO etching waste liquid or waste ITO sludge,
An adsorbent containing at least one selected from metal-phosphate or non-metal-phosphate molecular sieve represented by the following formula (1) is added to the ITO etching waste liquid or waste ITO sludge to adsorb tin and indium on the adsorbent to adsorb tin and indium (Step a);
Stirring the adsorbent in which the tin and indium adsorbed in an acid solution to desorb the indium (step b-1); And
Desorbing the tin by stirring in an alkali solution (step b-2)
The steps b-1 and b-2 are performed in any order,
A method for producing indium and tin, characterized in that both indium and tin are recovered individually.
[Chemical Formula 1]
M _a (PO) _b X _c
Wherein M is at least one element selected from the group consisting of Ni, Ti, Vd, Cr, Mn, Fe, Co, Zn, At least one phosphate ion consisting of HPO ₄ or PO ₄ and X is at least one metal selected from the group consisting of NH 2, of _3, H ₂ 0, a hydroxy group (-OH), a halogen group, a nitro group (-NO ₃₎ and seulpon acid group and (-SO ₃ H) one or more ionic or capable of coordination compound is selected from, a real number from 0.01 to 20 , b is a number from 1 to 60, and c is a real number from 0 to 100).

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