KR102675407B1 - Manufacturing method of ion exchange resin with excellent extraction efficiency of platinum group metals - Google Patents

Abstract

The present invention relates to a method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals, and more specifically, to a raw material mixing step of mixing divinylbenzene with styrene monomer, and reacting the mixture prepared through the raw material mixing step with toluene. A polymerization step of polymerizing by mixing an initiator, a cleaning step of washing the polymer polymerized through the polymerization step with ethanol, a vacuum drying step of vacuum drying the polymer washed through the cleaning step, and a vacuum drying step of vacuum drying the polymer product washed through the cleaning step. It consists of a coating step in which the polymer is mixed with a platinum group extractant mixture and coated.
The ion exchange resin manufactured through the above process can extract platinum group metals with excellent extraction efficiency by binding to the surface of the ion exchange resin a platinum group extractant with low solubility in water and a long carbon chain compared to molecular weight.

Description

Method for manufacturing ion exchange resin with excellent extraction efficiency of platinum group metals {MANUFACTURING METHOD OF ION EXCHANGE RESIN WITH EXCELLENT EXTRACTION EFFICIENCY OF PLATINUM GROUP METALS}

The present invention relates to a method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals. More specifically, a platinum group extractant with low solubility in water and a long carbon chain compared to molecular weight is bound to the surface of the ion exchange resin to extract platinum group metals. It relates to a method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals that can be extracted with excellent extraction efficiency.

Platinum Group Metal (PGM) is a general term for six elements including ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). Platinum group metals (PGM) not only have excellent physical properties with a high melting point and large specific gravity, but are also not corroded by acids or alkalis and are chemically inert, so they are used as catalysts for automobile exhaust gas purification, petrochemical industry, electrode materials, and display industry-related materials. It is used for various purposes in various fields, and its demand has been rapidly increasing recently.

However, because reserves of these platinum group metals are limited, research has been actively conducted on processes and devices for recovering precious metals from waste materials such as automobile catalyst parts, oil refining parts, or electronic products, and the electronics industry has developed in Korea as well. , Due to the increase in production due to the development of the display industry and increased demand, and the resulting increase in scrap, there is a demand for technology to extract, separate, and purify platinum group metals more efficiently and economically from not only the main materials but also the waste materials generated in the process. It is emerging.

Conventionally, a method was used to remove the platinum group by contacting waste liquid containing the platinum group with a platinum group extractant, but there was a problem in that platinum group metals below a certain concentration were not extracted.

In order to solve the above problems, we attempted to develop a synthetic resin for extracting platinum group metals, including a method of attaching a functional group to an already synthesized resin structure to give it the ability to adsorb platinum group metals, and mixing a platinum group extractant during resin synthesis. A method was used in which the extractant becomes part of the resin structure and can adsorb the platinum group by synthesizing it. However, the method of attaching a functional group has an overly complicated process and low adsorption efficiency, and the method of mixing the platinum group extractant when synthesizing the resin was used. There was a problem in that the extraction efficiency was lowered due to the low adsorption capacity of platinum group metals.

Korean Patent Registration No. 10-1712763 (2017.02.27.) Korean Patent Registration No. 10-1922493 (2018.11.21.)

The purpose of the present invention is to develop an ion exchange resin with excellent extraction efficiency of platinum group metals, in which a platinum group extractant with low solubility in water and a long carbon chain compared to molecular weight is bound to the surface of the ion exchange resin to extract platinum group metals with excellent extraction efficiency. It provides a manufacturing method.

The object of the present invention is a raw material mixing step of mixing divinylbenzene with styrene monomer, a polymerization step of polymerizing the mixture prepared through the raw material mixing step by mixing toluene and a reaction initiator, and mixing the polymer polymerized through the polymerization step with ethanol. A cleaning step of cleaning, a vacuum drying step of vacuum drying the polymer washed through the cleaning step, and a coating step of mixing a platinum group extractant mixture and coating the polymer vacuum dried through the vacuum drying step. This is achieved by providing a method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals.

According to a preferred feature of the present invention, the raw material mixing step is performed by mixing 90 to 110 parts by weight of divinylbenzene with 100 parts by weight of styrene monomer.

According to a more preferred feature of the present invention, the polymerization step is performed by mixing 85 to 95 parts by weight of toluene and 0.1 to 0.2 parts by weight of a reaction initiator with 100 parts by weight of the mixture prepared through the raw material mixing step and heating at 250° C. at a temperature of 80 to 90° C. It is to be carried out for 10 to 15 hours at a speed of 350 rpm.

According to a more preferred feature of the present invention, the platinum group extractant mixture consists of 100 parts by weight of distilled water, 10 to 30 parts by weight of a platinum group extractant, and 0.5 to 1 part by weight of a dispersant, and the platinum group extractant is tributyl phosphate or di-n. -It shall be composed of octyl sulfate.

According to an even more preferred feature of the present invention, before the raw material mixing step, a washing step of sequentially washing the styrene monomer and the divinylbenzene using sodium hydroxide and distilled water with a mass concentration of 10% is further performed.

According to an even more preferred feature of the present invention, the vacuum drying step is performed at a temperature of 75 to 85 ° C. for 20 to 30 hours.

According to an even more preferred feature of the present invention, the coating step is performed by mixing 150 to 200 parts by weight of the platinum group extractant mixture with 100 parts by weight of the polymer vacuum dried through the vacuum drying step and drying the mixture at a temperature of 60 to 80° C. for 4 to 6 minutes. After stirring for a while, the process is performed by washing and drying.

The method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals according to the present invention is to extract platinum group metals with excellent extraction efficiency by combining a platinum group extractant with low solubility in water and a long carbon chain compared to molecular weight to the surface of the ion exchange resin. It shows an excellent effect in providing an ion exchange resin that can be used.

Figure 1 is a flowchart showing a method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals according to an embodiment of the present invention.
Figure 2 is a flowchart showing a method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals according to another embodiment of the present invention.
Figure 3 is a photograph taken using a scanning electron microscope (SEM) of the ion exchange resin prepared in Example 1 of the present invention.
Figure 4 is a graph showing the spectrum of ion exchange resins prepared through Comparative Examples 1 and 2 analyzed by FT-IR.
Figure 5 is a graph showing the spectrum of ion exchange resins prepared through Comparative Example 1 and Comparative Examples 3 to 4 analyzed by FT-IR.
Figure 6 is a graph showing the spectrum of the ion exchange resin and TBP (tributyl phosphate) prepared through Example 1 and Comparative Example 1 analyzed by FT-IR.
Figure 7 is a graph showing the spectrum of the ion exchange resin and DNOS (di-n-octyl sulfate) prepared through Example 2 and Comparative Example 1 analyzed by FT-IR.

Below, preferred embodiments of the present invention and the physical properties of each component are described in detail, but the purpose is to provide a detailed description so that a person skilled in the art can easily carry out the invention. This does not mean that the technical idea and scope of the present invention are limited.

The method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals according to the present invention includes a raw material mixing step (S101) of mixing divinylbenzene with styrene monomer, and reacting the mixture prepared through the raw material mixing step (S101) with toluene. A polymerization step (S103) of mixing and polymerizing an initiator, a cleaning step (S105) of washing the polymer polymerized through the polymerization step (S103) with ethanol, and vacuum drying the polymer product washed through the cleaning step (S105). It consists of a drying step (S107) and a coating step (S109) in which a platinum group extractant mixture is mixed and coated on the polymer vacuum dried through the vacuum drying step (S107).

The raw material mixing step (S101) is a step of mixing divinylbenzene with styrene monomer, and is preferably performed by mixing 90 to 110 parts by weight of divinylbenzene with 100 parts by weight of styrene monomer.

The styrene monomer and divinylbenzene are the main materials that make up the ion exchange resin. As described above, the ion exchange resin made from styrene monomer and divinylbenzene is close to transparent and has a gel structure, so it is called a gel-type ion exchange resin. do. In addition, an ion exchange resin with physical porosity can be manufactured using a special polymerization method, and such a resin is called a porous ion exchange resin. This resin is basically like a gel, but contains pores (macro) in the polymer gas. The difference is in the presence of pores.

At this time, before the raw material mixing step (S101), a washing step (S100) in which the styrene monomer and the divinylbenzene are sequentially washed using sodium hydroxide and distilled water with a mass concentration of 10% may be further performed.

Commercially available styrene monomer and divinylbenzene contain a polymerization inhibitor. To remove the polymerization inhibitor, it is preferable to wash them sequentially using sodium hydroxide and distilled water with a mass concentration of 10%, washing 2 to 4 times at a time. It is more desirable to proceed with the process.

The polymerization step (S103) is a step of polymerizing the mixture prepared through the raw material mixing step (S101) by mixing toluene and a reaction initiator. 85 parts by weight of toluene is added to 100 parts by weight of the mixture prepared through the raw material mixing step (S101). It consists of mixing 95 to 95 parts by weight of the reaction initiator and 0.1 to 0.2 parts by weight of the reaction initiator and performing suspension polymerization at a temperature of 80 to 90°C at a speed of 250 to 350 rpm for 10 to 15 hours under nitrogen substitution conditions.

At this time, the toluene serves to improve the recovery rate of platinum group metals by increasing the specific surface area by allowing pores to be formed in the ion exchange resin produced through the present invention.

In addition, the reaction initiator forms radicals to allow the polymerization reaction to proceed, and is preferably made of benzoyl peroxide (BPO).

The cleaning step (S105) is a step of cleaning the polymer polymerized through the polymerization step (S103) with ethanol. The polymer polymerized through the polymerization step (S105) is washed with ethanol 2 to 4 times to coat the surface of the polymer. It consists of a process of removing remaining unreacted monomers or solvent components.

The vacuum drying step (S107) is a step of vacuum drying the polymer cleaned through the cleaning step (S105). The polymer cleaned through the cleaning step (S105) is put into a vacuum dryer and dried at a temperature of 75 to 85 ° C. It consists of vacuum drying for 20 to 30 hours.

The coating step (S109) is a step of coating the polymer vacuum-dried through the vacuum drying step (S107) by mixing a platinum group extractant mixture, and 100 parts by weight of the polymer vacuum-dried through the vacuum drying step (S107) is applied. The process consists of mixing 150 to 200 parts by weight of the platinum group extractant mixture and stirring for 4 to 6 minutes at a temperature of 60 to 80° C., followed by washing and drying.

The platinum group extractant mixture consists of 100 parts by weight of distilled water, 10 to 30 parts by weight of a platinum group extractant, and 0.5 to 1 part by weight of a dispersant. After mixing the above components, the mixture is mixed at 450 to 450 parts by weight using a mixing device equipped with a stirrer and a heating mantle. It is preferably prepared by mixing at a speed of 550 rpm and a temperature of 75 to 85 ° C.

If the content of the platinum group extractant mixture is less than 150 parts by weight, the recovery rate of platinum group metals of the ion exchange resin may decrease, and if the content of the platinum group extractant mixture exceeds 200 parts by weight, the recovery rate of platinum group metals may actually decrease, according to the present invention. The mixing ratio of the styrene monomer, divinylbenzene, and platinum group extractant that constitutes the ion exchange resin prepared through is preferably 1:1:1 to 1.5 parts by weight.

At this time, the platinum group extractant is preferably made of tributyl phosphate or di-n-octyl sulfate, and the dispersant is preferably made of polyvinyl alcohol.

Hereinafter, the method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals according to the present invention and the physical properties of the ion exchange resin produced by the method will be described through examples.

<Preparation Example 1> Preparation of platinum group extractant mixture

Mix 500g of distilled water, 80g of tributyl phosphate, and 4.0g of dispersant (polyvinyl alcohol) and stir for 5 minutes at a temperature of 80°C and a speed of 500rpm using a mixing device equipped with a stirrer and heating mantle to obtain a platinum group extractant mixture. Manufactured.

<Preparation Example 2> Preparation of platinum group extractant mixture

A platinum group extractant mixture was prepared in the same manner as Preparation Example 1, except that di-n-octyl sulfate was used instead of tributyl phosphate.

<Example 1>

Styrene monomer and divinylbenzene were washed three times with an aqueous solution of sodium hydroxide having a mass concentration of 10%, and three times with purified water to remove the polymerization inhibitor.

Prepare a mixture by mixing 80 g of styrene monomer with the polymerization inhibitor removed and 80 g of divinylbenzene, 150 g of toluene and 0.2 g of polymerization initiator (benzoyl peroxide), and incubate for 12 hours at 300 rpm and 85°C under nitrogen substitution conditions. A polymer was prepared by suspension polymerization, and the polymer was washed three times with ethanol, placed in a vacuum dryer, and vacuum-dried at a temperature of 80° C. for 24 hours. 100 parts by weight of the polymer was mixed with the platinum group extract prepared in Preparation Example 1. An ion exchange resin with excellent extraction efficiency of platinum group metals was prepared by mixing 175 parts by weight of the mixture, stirring, washing, and drying at a temperature of 70°C for 5 minutes. (STM&DVB&TBP Copolymer)

<Example 2>

An ion exchange resin with excellent extraction efficiency of platinum group metals was prepared in the same manner as in Example 1, but using the platinum group extractant mixture prepared in Preparation Example 2. (STM&DVB&DNOS Copolymer)

<Comparative Example 1>

A mixture was prepared by mixing 80 g of styrene monomer from which the polymerization inhibitor was removed and 80 g of divinylbenzene, and mixing 150 g of toluene and 0.2 g of a polymerization initiator (benzoyl peroxide), followed by suspension polymerization for 12 hours at 300 rpm and a temperature of 85°C. The polymer was prepared and washed three times with ethanol, then placed in a vacuum dryer and vacuum dried at a temperature of 80°C for 24 hours to prepare a resin. (STM&DVB Copolmer)

<Comparative Example 2>

A mixture was prepared by mixing 80 g of styrene monomer from which the polymerization inhibitor was removed and 80 g of divinylbenzene, and mixing 150 g of toluene and 0.2 g of a polymerization initiator (benzoyl peroxide), followed by suspension polymerization for 12 hours at 300 rpm and a temperature of 85°C. A polymer was prepared, and the polymer was impregnated with tributyl phosphate, washed three times with ethanol, placed in a vacuum dryer, and vacuum dried at a temperature of 80°C for 24 hours to prepare a resin. (SD)

<Comparative Example 3>

A mixture was prepared by mixing 80 g of styrene monomer from which the polymerization inhibitor was removed and 80 g of divinylbenzene, and mixing 150 g of toluene and 0.2 g of a polymerization initiator (benzoyl peroxide), followed by suspension polymerization for 12 hours at 300 rpm and a temperature of 85°C. After preparing the polymer and washing it three times with ethanol, it was placed in a vacuum dryer and vacuum dried at 80°C for 24 hours to prepare a resin. The prepared resin was impregnated with phosphorus trichloride, mixed with ammonium chloride, and dried at 75°C. Phosphate-based functional group was introduced by stirring at high temperature for 5 hours, hydrolyzed with 2N-NaOH for 12 hours, and 1N-HCl and 1N-HNO ₃ solutions were oxidized and washed for 12 hours each to prepare an ion exchange resin. .(SDP)

<Comparative Example 4>

A mixture was prepared by mixing 80 g of styrene monomer from which the polymerization inhibitor was removed and 80 g of divinylbenzene, and mixing 150 g of toluene and 0.2 g of a polymerization initiator (benzoyl peroxide), followed by suspension polymerization for 12 hours at 300 rpm and a temperature of 85°C. After preparing the polymer and washing it three times with ethanol, it was placed in a vacuum dryer and vacuum dried at a temperature of 80°C for 24 hours to prepare a resin. The prepared resin was swelled in toluene for 1 hour, then chloromethylmethylether and ammonium chloride were added. After introducing a methyl group by stirring for 3 hours, it was impregnated with phosphorus trichloride, mixed with ammonium chloride, stirred at a temperature of 75°C for 5 hours to introduce a phosphoric acid-based functional group, and hydrolyzed with 2N-NaOH for 12 hours. Ion exchange resin was prepared by oxidizing and washing 1N-HCl and 1N-HNO ₃ solutions for 12 hours each (SDCMP).

The ion exchange resin prepared in Example 1 was photographed with a scanning electron microscope (SEM) and shown in Figure 3 below.

As shown in Figure 3 below, it can be seen that the ion exchange resin prepared through Example 1 of the present invention was formed into a sphere with a diameter of about 10㎛.

In addition, the spectrum of the ion exchange resin prepared through Comparative Examples 1 and 2 analyzed by FT-IR is shown in Figure 4 below.

As shown in Figure 4 below, there is no difference in spectrum between the ion exchange resins prepared in Comparative Examples 1 and 2, which shows that tributyl phosphate, a platinum group extractant, is not coated on the surface of the ion exchange resin through simple impregnation. You can.

In addition, the spectrum of the ion exchange resin prepared through Comparative Example 1 and Comparative Examples 3 to 4 analyzed by FT-IR is shown in Figure 5 below.

As shown in Figure 5 below, the characteristic peak for the P=O bond in the ion exchange resins prepared through Comparative Examples 3 and 4 appeared around 1,000 cm ^-1 . However, the characteristic peak of Comparative Example 4 (SDCMP) was found to be very low compared to Comparative Example 3 (SDP). This was believed to be because the introduction of the phosphate functional group became difficult as the methyl group was introduced or the functional group introduction reaction was not sufficiently carried out. do.

In addition, the spectrum of the ion exchange resin and TBP (tributyl phosphate) prepared through Example 1 and Comparative Example 1 analyzed by FT-IR is shown in Figure 6 below.

As shown in Figure 6 below, the characteristic peak for the P=O bond appeared around 1,000 cm ^-1 . It was confirmed that TBP was properly added to the extraction resin. When compared to the polymer without TBP coating, it was confirmed that the TBP-coated polymerized extraction resin showed the characteristic peak of TBP. In other words, it can be seen that when TBP is coated on the monomers STM and DVB, the resin is synthesized without changing the structure of TBP.

In addition, the spectrum of the ion exchange resin and DNOS (di-n-octyl sulfate) prepared through Example 2 and Comparative Example 1 analyzed by FT-IR is shown in Figure 7 below.

As shown in Figure 7 below, the characteristic peak for CH bonding appeared around 2,800 to 3,000 cm ^-1 . It was confirmed whether DNOS was properly added to the extraction resin. When compared to the polymer without DNOS coating, the extraction resin polymerized with DNOS coating showed characteristic peaks of DNOS. In other words, it can be seen that when DNOS is coated on the monomers STM, DVB, and polymer, the resin is synthesized without changing the structure of DNOS.

In addition, the same procedure as in Example 1 was carried out, but 100 g of raffinate waste liquid was added to a column filled with 25 g and 50 g, respectively, of ion exchange resin prepared at a ratio of 1:1:1 of styrene monomer, divinylbenzene, and tributyl phosphate. As a result of passing mL (based on HCl concentration of 2M), the platinum extraction efficiency of the extraction resin was found to be about 99%.

In addition, the same procedure as Example 1 was performed, but the extraction efficiency of platinum was measured while changing the ratios of styrene monomer, divinylbenzene, and tributyl phosphate as shown in Table 1 below.

{However, the extraction efficiency of platinum was measured with the concentration of platinum in the waste liquid being 46 mg/L.}

<Table 1>

As shown in Table 1, the best platinum extraction efficiency was achieved when the ratio of styrene monomer, divinylbenzene, and tributyl phosphate was 1:1:1.5.

In addition, to evaluate the performance of the ion exchange resin prepared in Example 2, the resin was filled in the column, the waste liquid was filtered at a constant flow rate, the passed filtrate was collected at each time period, and ICP analysis was performed. The results are shown in Table 2. It was.

{At this time, the concentration of palladium in the waste liquid was 45.2 mg/L, and 100 mL of raffinate waste liquid (based on Pd concentration of 45.2 mg/L and HCl concentration of 2 M) was passed through a column filled with 25 g and 50 g of ion exchange resin, respectively. method was used.}

<Table 2>

As shown in Table 2, when 50 g of the ion exchange resin prepared in Example 2 was filled, the extraction efficiency of palladium was confirmed to be about 99.95%.

Therefore, in the method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals according to the present invention, a platinum group extractant with low solubility in water and a long carbon chain compared to molecular weight is bound to the surface of the ion exchange resin to achieve excellent extraction efficiency of platinum group metals. It can be extracted.

S100 ; Washing step
S101 ; Raw material mixing stage
S103 ; polymerization step
S105 ; Cleaning step
S107 ; Vacuum drying step
S109 ; Coating step

Claims (7)

A raw material mixing step of mixing divinylbenzene with styrene monomer;
A polymerization step of polymerizing the mixture prepared through the raw material mixing step by mixing toluene and a reaction initiator;
A washing step of washing the polymer polymerized through the polymerization step with ethanol;
A vacuum drying step of vacuum drying the polymer cleaned through the cleaning step; and
A coating step of coating the polymer vacuum-dried through the vacuum drying step by mixing a platinum group extractant mixture,
The raw material mixing step is a method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals, characterized in that it is performed by mixing 90 to 110 parts by weight of divinylbenzene with 100 parts by weight of styrene monomer.
delete A raw material mixing step of mixing divinylbenzene with styrene monomer;
A polymerization step of polymerizing the mixture prepared through the raw material mixing step by mixing toluene and a reaction initiator;
A washing step of washing the polymer polymerized through the polymerization step with ethanol;
A vacuum drying step of vacuum drying the polymer cleaned through the cleaning step; and
A coating step of coating the polymer vacuum-dried through the vacuum drying step by mixing a platinum group extractant mixture,
In the polymerization step, 85 to 95 parts by weight of toluene and 0.1 to 0.2 parts by weight of the reaction initiator are mixed with 100 parts by weight of the mixture prepared through the raw material mixing step, and the mixture is heated at a temperature of 80 to 90 ° C. at a speed of 250 to 350 rpm for 10 to 15 hours. A method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals, characterized in that it is carried out during a process.
In claim 1 or 3,
The platinum group extractant mixture consists of 100 parts by weight of distilled water, 10 to 30 parts by weight of a platinum group extractant, and 0.5 to 1 part by weight of a dispersant,
A method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals, characterized in that the platinum group extractant consists of tributyl phosphate or di-n-octyl sulfate.
In claim 1 or 3,
Before the raw material mixing step, a washing step is further performed in which the styrene monomer and the divinylbenzene are sequentially washed using sodium hydroxide and distilled water with a mass concentration of 10%. Ion exchange with excellent extraction efficiency of platinum group metals Resin manufacturing method.
In claim 1 or 3,
A method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals, characterized in that the vacuum drying step is performed at a temperature of 75 to 85 ° C. for 20 to 30 hours.
A raw material mixing step of mixing divinylbenzene with styrene monomer;
A polymerization step of polymerizing the mixture prepared through the raw material mixing step by mixing toluene and a reaction initiator;
A washing step of washing the polymer polymerized through the polymerization step with ethanol;
A vacuum drying step of vacuum drying the polymer cleaned through the cleaning step; and
A coating step of coating the polymer vacuum-dried through the vacuum drying step by mixing a platinum group extractant mixture,
The coating step is a process of mixing 150 to 200 parts by weight of the platinum group extractant mixture with 100 parts by weight of the polymer vacuum dried through the vacuum drying step, stirring for 4 to 6 minutes at a temperature of 60 to 80 ° C., and then washing and drying. A method for producing an ion exchange resin with excellent extraction efficiency of platinum group metals, characterized in that it consists of.