KR101268441B1 - Recovering method of platinum from platinum scrap leaching solution using synthetic extraction resins - Google Patents

Abstract

PURPOSE: A recovering method of platinum from platinum scrap leachate using synthetic extraction resins is provided to separate iron(Fe) and aluminum(Al) by using a first synthetic extraction resin synthesized by using D2EHPA (di-(2-ethylhexyl)phosphoric acid) and also to separate only platinum(Pt) from rhodium(Rh) by using a second synthetic extraction resin synthesized by using TBP(Thyroxine Binding Protein). CONSTITUTION: A recovering method of platinum from platinum scrap leachate using synthetic extraction resins comprises the following steps. A first synthetic extraction resin and a second synthetic extraction resin are produced by being synthesized by a suspension polymerization method. The first synthesis extraction resin is injected in the platinum scrap leachate. The Aluminum(Al) and iron(Fe) of platinum scrap leachate are absorbed in the first synthesis extraction resin by stirring and reacting the first synthesis extraction resin and platinum scrap leachate at the temperature of 35 to 55°C, and the first synthesis extraction resin, in which the Aluminum and iron are absorbed, is removed. The second synthesis extraction resin is added to the platinum scrap leachate in which the first synthesis extraction resin is removed, and the platinum of platinum scrap leachate is absorbed in the second synthesis extraction resin. The second synthesis extraction resin, in which the platinum is absorbed, is removed, and the platinum is recovered by detaching the platinum from the second synthesis extraction resin by using detaching solution.

Description

Platinum recovery method from platinum scrap leaching solution using synthetic extract resin {RECOVERING METHOD OF PLATINUM FROM PLATINUM SCRAP LEACHING SOLUTION USING SYNTHETIC EXTRACTION RESINS}

The present invention relates to a method for recovering platinum from a platinum scrap leachate, and more particularly, by effectively extracting platinum from a platinum scrap leachate using a synthetic extraction resin prepared using a suspension polymerization method, thereby ensuring excellent extraction performance. The present invention relates to a method for recovering platinum from platinum scrap leaching liquor using a synthetic extract resin.

Platinum group metals have excellent electrical, chemical and physical properties, which are important not only in the traditional jewelry industry but also as materials for the electronics industry, and their demand is increasing. It is widely used in aviation materials, petrochemicals and automobile catalysts because of its stable chemical properties at high temperatures, and is widely used in industrial and commercial industries such as the electrical and medical industry where corrosion resistance is required.

In addition, as the demand increases, industrial wastes such as waste electronic equipment scrap, petrochemical waste catalysts and automobile waste catalysts are rapidly increasing. These wastes include copper as well as expensive precious metals such as gold, silver, platinum, palladium, and rhodium. It is a secondary resource because it contains various valuable metals. At this time, when recovering the platinum group metal with high recovery rate by using the waste catalyst discarded without treatment, it can be used as a core technology in realizing high value-adding of materials and developing technologies in high-tech industries, and it is possible to use high purity rare metals as well as catalysts. Can be used as a platinum group material.

Much research has been conducted on the separation of platinum by conventional solvent extraction, and it is classified as an extractant by ion exchange and ion solvation depending on the extractant used. The extractant by ion exchange includes amines, the extractant by ion solvation, and ethers, and ketones and phosphates. Solvent extraction of platinum by the extractant TBP was excellent.

However, the separation by the solvent extraction method is inconvenient due to the change of the concentration of the separation solution by the solvent itself and the inconvenience of the purification of the solvent, and the ion exchange method uses a lean solution, which is used for commercial scale separation and purification processes. There are economic constraints.

On the other hand, when the extraction resin is synthesized using a conventional extraction agent and then used in the separation process, it has many advantages such as low loss of the extraction agent, rapid separation according to the mobile phenomenon, and production of high purity products. Due to the easy extraction of gold.

Related prior arts are Korean Patent Laid-Open Publication No. 10-2012-0086861 (published Aug. 6, 2012), which describes the recovery of platinum using a hydrochloric acid-based leaching solution from a three-way catalyst.

An object of the present invention is the first synthetic extract resin synthesized using D2EHPA (di-2-ethylhexylphosphoric acid) by suspension polymerization method, and iron (Fe) and aluminum (Al) are first separated, and rhodium (Rh) and platinum ( Platinum from platinum scrap leachate using a synthetic extract resin that can maximize platinum recovery by separating only platinum (Pt) from Pt) using a second synthetic extract resin synthesized using TBP (tri-butyl-phosphate) It is to provide a recovery method.

Platinum recovery method from the platinum scrap leachate using a synthetic extraction resin according to an embodiment of the present invention for achieving the above object is (a) a first synthesis by synthesizing the first extraction resin and the second extraction resin by the suspension polymerization method respectively; Preparing an extract resin and a second synthetic extract resin; (b) mixing the first synthetic extract resin with a platinum scrap leach solution; (c) reacting the mixed solution of the first synthetic extract resin and the platinum scrap leach solution at 35 to 55 ° C. while stirring to adsorb aluminum (Al) and iron (Fe) to the first synthetic extract resin, and then the aluminum ( Collecting the first synthetic extract resin to which Al) and iron (Fe) are adsorbed; (d) adsorbing platinum (Pt) to the second synthetic extract resin by adding a second synthetic extract resin to the mixed solution in which the first synthetic extract resin is collected; And (e) recovering platinum (Pt) by desorbing platinum (Pt) from the second synthetic extract resin using a desorption solution after collecting the second synthetic extract resin to which the platinum (Pt) is adsorbed; Characterized in that it comprises a.

The present invention primarily extracts iron (Fe) and aluminum (Al) in order to separate the platinum (Pt) in the platinum scrap leachate (Pt, Rh, Fe, Al) as part of valuable metal recovery The first extraction resin was synthesized using D2EHPA (di-2-ethylhexylphosphoric acid). In addition, a separation experiment was performed using a second extraction resin synthesized using TBP (tri-butyl-phosphate) as an extractant to separate platinum (Pt) from rhodium (Rh) and platinum (Pt). At this time, TBP showed excellent performance in selectively separating only platinum (Pt) among rhodium (Rh) and platinum (Pt), which are platinum group metals, but when used primarily in platinum scrap leachate, not only platinum (Pt) but also platinum scrap It was confirmed that 20 to 40% extraction of iron (Fe) and aluminum (Al) in the leach solution.

Therefore, in the present invention, firstly, iron (Fe) and aluminum (Al) are separated with the first synthetic extract resin synthesized using D2EHPA, and only platinum (Pt) among rhodium (Rh) and platinum (Pt) is used by using TBP. By separating using the synthesized second synthetic extract resin, it was proved that there is an effect that can maximize the platinum recovery.

In the present invention, the acidity effect for desorption of platinum (Pt) extracted by the TBP extraction resin and the effect of the temperature and the amount of the addition of the extraction resin when the suspension polymerization method was used during the synthesis of the resin were investigated. .

1 is a process flowchart showing a method for recovering platinum from platinum scrap leachate using a synthetic extract resin according to an embodiment of the present invention.
FIG. 2 is a process flowchart illustrating a method of manufacturing the first synthetic extract resin of FIG. 1.
Figure 3 is a microstructure photograph showing the first synthetic extract resin powder prepared using D2EHPA.
Figure 4 is a microstructure photograph showing a second synthetic extract resin powder prepared using TBP.
FIG. 5 shows the results of measuring the first and second synthetic extract resin powders prepared using D2EHPA and TBP using infrared spectroscopy, respectively.
FIG. 6 is a graph showing the extraction performance of Fe and Al in the platinum scrap leach simulant using the extracted resin synthesized using D2EHPA into the platinum scrap leach simulating solution.
FIG. 7 is a graph showing the extraction performance of Pt in the platinum scrap leach simulating solution after adding the extraction resin synthesized using TBP into the platinum scrap leach simulating solution from which Fe and Al are removed.
8 and 9 are graphs showing the extraction efficiency by temperature for the extraction resin synthesized using D2EHPA.
10 and 11 are graphs showing the extraction efficiency for each temperature of the extraction resin synthesized using TBP.
Figure 12 shows the extraction rate according to the addition amount of each of the extraction resin synthesized using D2EHPA and TBP.
13 is a view showing the recovery of Pt adsorbed on TBP resin according to the desorption solution.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as being 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. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

Hereinafter, a method for recovering platinum from platinum scrap leachate using a synthetic extract resin according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 is a process flowchart showing a method for recovering platinum from platinum scrap leachate using a synthetic extract resin according to an embodiment of the present invention.

Referring to Figure 1, the platinum recovery method from the platinum scrap leaching solution using the synthetic extract resin according to the embodiment of the present invention shown in the first and second synthetic extract resin manufacturing step (S110), the first synthetic extract resin / platinum Scrap leachate mixing step (S120), adsorbing the aluminum and iron in the platinum scrap leach solution to the first synthetic extract resin (S130), adsorbing platinum in the platinum scrap leach solution to the second synthetic extract resin (S140) and the second Desorbing the platinum from the synthetic extract resin (S150).

Preparation of the first and second synthetic extract resin

In the first and second synthetic extract resin manufacturing step (S110), the first extract resin and the second extract resin are synthesized by suspension polymerization, respectively, to prepare the first synthetic extract resin and the second synthetic extract resin.

Such first and second synthetic extract resins may be prepared by suspension polymerization. When using this suspension polymerization method, a high purity polymer can be obtained, and the operation method is convenient. In addition, the suspension polymerization method is advantageous for synthesizing the polymer support, in particular polystyrene, poly-methacrylate, poly-vinyl chloride, polyacrylonitrile It is advantageous to produce a vinyl copolymer such as).

2 is a flowchart illustrating a method of manufacturing the first synthetic extract resin of FIG. 1, which will be described in more detail with reference to the drawing.

Referring to FIG. 2, the step of preparing the first synthetic extract resin includes mixing and stirring the first extract resin raw material (S111), adding a swelling agent, pore former and stabilizer (S112), and adding a reaction initiator (S113). do. In addition, the first synthetic extract resin manufacturing step may further include a first synthetic extract resin pressure filtering / drying step (S114) and the first synthetic extract resin powder grinding step (S115).

In the first extraction resin raw material mixing and stirring step (S111), distilled water, a monomer, a crosslinking agent, and D2EHPA (di-2-ethylhexylphosphoric acid), which is a first extractant, are added to a reaction tank, and then heated and stirred at a first temperature. As a monomer, styrene monomer may be used as an example, and as an example, a divinyl benzene may be used as a crosslinking agent.

At this time, the stirring is preferably carried out at a speed of 300 ~ 400rpm. If the stirring speed is less than 300rpm, the extracted resins are entangled with each other to produce large particles because the speed is too slow. On the contrary, when the stirring speed exceeds 400rpm, the effect of improving the speed is insignificant, which is not economical.

In the swelling agent, the pore former and the stabilizer addition step (S112), the pore former and the stabilizer are added to the reaction tank while being maintained at the second temperature lower than the first temperature. Toluene may be used as the swelling agent, and n-heptane may be used as the pore forming agent, and polyvinyl alcohol may be used as the stabilizer. At this time, the first temperature may be 80 ~ 100 ℃, the second temperature may be 75 ~ 85 ℃.

In the reaction initiator addition step (S113), BOP (benzoyl peroxide), which is a reaction initiator, is added to the reaction tank in 1 to 5 times and synthesized. At this time, the synthesis is preferably carried out for 10 to 14 hours. In this step, when the synthesis time is less than 10 hours, it may be difficult to secure a uniform particle shape and particle size due to insufficient synthesis. On the contrary, if the synthesis time exceeds 14 hours, it may act as a factor that raises the cost only without any further effect, which is not economical.

At this time, the inventors of the present invention confirmed through experiments that even if the reaction initiator is divided into 1 to 5 times at intervals of 1 hour, the particle shape and particle size of the synthesized extract resin is evenly distributed. In particular, when the reaction initiator was divided into three times at 1 hour intervals, the particle shape was close to a spherical shape, and the particle size was found to be most evenly distributed.

In the first synthetic extract resin pressure filtering / drying step (S114), the synthesized first extract resin is filtered under pressure and then dried. At this time, the drying is preferably carried out for 20 to 30 hours at 20 to 40 ℃. If the drying temperature is less than 20 ℃, or if the drying time is less than 20 hours, there is a problem that the crystallinity deteriorates due to insufficient drying. On the contrary, when the drying temperature exceeds 40 ° C or the drying time exceeds 30 hours, it may act as a cause of an increase in manufacturing cost and time, and thus it is not economical.

In the first synthetic extract resin powder crushing step (S115), the dried first synthetic extract resin powder is pulverized and screened to a particle size of 75 to 100 μm. As such, the first synthetic extract resin powder selected to a particle size of 75 ~ 100㎛ is preferably stored in a sealed state.

Meanwhile, the process of preparing the first synthetic extract resin and the process of preparing the second synthetic extract resin may be substantially the same. However, the first synthetic extract resin uses D2EHPA (di-2-ethylhexylphosphoric acid) as the first extractant, and the second synthetic extract resin uses TBP (tri-butyl-phosphate) as the second extractant. There are only differences in use, and since they are substantially the same, a detailed description thereof will be omitted.

First Synthetic Extraction Resin / Platinum Scrap Leachate Mixing

In the first synthetic extract resin / platinum scrap leach liquid mixing step (S120), the first synthetic extract resin is added to the platinum scrap leach liquid. At this time, the platinum scrap leaching solution may be a solution containing Pt, Al, Fe, Rh.

In this step, the first synthetic extract resin is preferably added to 3 ~ 5g per 100ml of the platinum scrap leaching solution. At this time, it was confirmed through experiments that the first synthetic extraction resin exhibits the maximum extraction efficiency when added in the above range.

Adsorption of aluminum and iron in platinum scrap leachate to the first synthetic extraction resin

In the step (S130) of adsorbing aluminum and iron in the platinum scrap leach solution to the first synthetic extract resin, the first synthetic extract resin and the platinum scrap leach solution are reacted at 35 to 55 ° C. while stirring, and the platinum scrap leach solution to the first synthetic extract resin. After adsorbing aluminum (Al) and iron (Fe) therein, the first synthetic extract resin to which the aluminum (Al) and iron (Fe) is adsorbed is collected.

In this step, when the reaction temperature is less than 35 ℃ because the temperature is too low, there is a fear that the reaction is not performed smoothly because the activity of the atoms is low. On the contrary, when the reaction temperature exceeds 55 ° C., the temperature does not significantly affect the activity of the extraction resin and the activities of the platinum group element ions and the metal element ions in the platinum scrap leaching liquor, so that the separation performance may not increase any more. However, it is not economical because the effect against temperature rise is insignificant.

Adsorption of platinum in the platinum scrap leachate to the second synthetic extraction resin

In the step of adsorbing platinum in the platinum scrap leachate to the second synthetic extracting resin (S140), the second synthetic extracting resin is added to the platinum scrap leachate in which the first synthetic extracting resin is collected, and the platinum scrap leachate is added to the second synthetic extracting resin. Pt is adsorbed.

In this step, it is preferable to add 5 to 10 g of the second synthetic extract resin per 100 ml of the platinum scrap leachate from which the first synthetic extract resin is collected. At this time, it was confirmed through experiments that the second synthetic extract resin exhibits the maximum extraction efficiency when added in the above range.

Desorption of platinum from the second synthetic extract resin

In the step S150 of desorbing platinum from the second synthetic extracting resin, after collecting the second synthetic extract resin adsorbed with platinum Pt, the platinum Pt is desorbed from the second synthetic extracting resin using a desorption solution. Recover platinum (Pt). At this time, the desorption solution may be used at least one of H ₂ O and 0.1 ~ 0.5M HCl.

Platinum recovery method from the platinum scrap leachate using the synthetic extract resin according to the embodiment of the present invention described above to separate the platinum (Pt) in the platinum scrap leachate (Pt, Rh, Fe, Al) as part of the valuable metal recovery Firstly, the first extraction resin is synthesized using an extractant D2EHPA (di-2-ethylhexylphosphoric acid) having excellent performance in extracting iron (Fe) and aluminum (Al), and the remaining rhodium (Rh) and platinum (Pt) In order to separate Pt, the separation experiment was performed using a second extraction resin synthesized using TBP (tri-butyl-phosphate) as an extractant. At this time, TBP showed excellent performance in selectively separating only platinum (Pt) among rhodium (Rh) and platinum (Pt), which are platinum group metals, but when used primarily in platinum scrap leachate, not only platinum (Pt) but also platinum scrap It was confirmed that 20 to 40% extraction of iron (Fe) and aluminum (Al) in the leach solution.

Therefore, in the present invention, firstly, iron (Fe) and aluminum (Al) are separated with the first synthetic extract resin synthesized using D2EHPA, and only platinum (Pt) among rhodium (Rh) and platinum (Pt) is used by using TBP. By separating using the synthesized second synthetic extract resin, it was proved that there is an effect that can maximize the platinum recovery.

Example

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Experimental material

For the synthesis of extracted resin, styrene monomer (KANTO CHEMICAL CO, INC, 99%) is used as a monomer, divinyl benzene (TOKYO CHEMICAL CO, LTD, 50%) is used as a crosslinking agent, and benzoyl peroxide (initiator) is used to form radicals. ACROS ORGANICS (99%) were used respectively. Polyvinyl alcohol 500 (DC Chemical INC) was used as a stabilizer, and toluene (Duksan pure chemical CO, LTD, 99%) and n-heptane (Duksan pure chemical CO, LTD, 99.5%) were used as swelling agents and pore-forming agents. Each was used. Di-2-ethylhexylphosphoric acid-D2EHPA (Luoyang Zhongda Chemical Co, Ltd, 95%) and tri-butyl-phosphate-TBP (Kanto chemical CO, INC, 95%) were used as extractants.

The synthesized extract resin was dried at 25 ° C. for 24 hours and then crushed and stored at 75 to 100 μm. For the preparation of the platinum scrap leachate for the separation experiment, H ₂ PtCl ₆ -5.7H ₂ O (Kojima chemical, 99.2%) and RhCl ₃ -3H ₂ O (Kojima chemical, 99%) were used as the platinum group elements. , AlCl ₃ (FLUKA, 98%) and FeCl ₃ (SIGMA, 100%) were used as aluminum (Al) and iron (Fe) metal elements. ICP-OES (inductively coupled plasma-optical emission spectrometer, DV2000 PerkinElmer Inc.) was used to analyze the concentration of elements in solution, and the particles of the extraction resin were scanned by scanning electron microscope (S-4700 Hitachi Inc.). The shape and distribution were measured. In addition, to investigate the molecular structure of the synthetic resin, fourier transform infrared spectroscopy, TravelIR II, Smiths Inc.).

Synthesis of Extraction Resin

Suspension polymerization was used for the synthesis of the extraction resin because the high purity polymer can be obtained when the suspension polymerization method is used, and because the operation method is convenient, it is also widely used industrially. In addition, it is advantageous for synthesizing the polymer support, and in particular, for the production of vinyl polymers such as polystyrene, poly (methacrylate), poly (vinyl chloride) and polyacrylonitrile in glass form.

Therefore, in order to synthesize the extraction resin was developed a synthetic method using a suspension polymerization method through which the extraction resin was synthesized.

In order to prepare the first synthetic extract resin, 560 g of distilled water, 110 g of styrene monomer, 110 g of crosslinking agent divinyl benzene, 75 g of extractant (D2EHPA) were added to a 2000 ml batch reactor, and heated to 80 ° C., using a lab-stirrer. The mixture was stirred and stirred at 300 rpm. Then, when the temperature was stabilized to 80 ℃, toluene 150g and n-heptane 50g were added as swelling agent and pore-forming agent, respectively. This may omit the process of separately swelling after the extraction resin synthesis due to the addition of swelling agent and pore-forming agent.

Thereafter, 5.6 g of stabilizer PVA was added, followed by 6 g of benzoyl peroxide. When the polymerization initiator was added, the amount of the reaction initiator was added three times at 1 hour intervals and then synthesized by maintaining the temperature and stirring speed for 12 hours.

Thereafter, the synthesized extract resin was filtered under pressure, completely dried at 25 ° C. for 24 hours, and then pulverized, and then screened and sealed to a particle size of 75 to 100 μm using a sieve.

On the other hand, the second synthetic extract resin was prepared in the same manner as the method for preparing the first synthetic extract resin except that TBP was used instead of D2EHPA as the extractant.

Separation experiment

H ₂ PtCl ₆ .5.7H ₂ O, AlCl ₃ , FeCl ₃ were dissolved in distilled water to prepare a mother liquor with a concentration of 1000 mg / l and RhCl ₃ · 3H ₂ O in distilled water to prepare a mother liquor with a concentration of 110 mg / l.

The separation experiment was performed using 150 ml of mother liquor prepared by diluting each mother liquor (concentrations of Pt, Al and Fe at 100 mg / l and Rh at 11 mg / l, respectively), and extracted resin synthesized using D2EHPA and TBP. 5wt% (7.5g of resin compared to 150ml solution) was added. 150 ml of solution and resin were added to a 250 ml beaker, stirred at a speed of 100 rpm, and 15 ml of sample was collected at one point during sampling. In order to reduce the experimental error and minimize the change of the high / liquid ratio, three extraction solutions were made with 150ml mixed solution. appear.

Experiments were carried out for each temperature of 25, 35, 45, 55 ℃ temperature, a total 90 minutes separation experiment. Samples were taken at intervals of 2 minutes up to 10 minutes after the separation experiment and at 5 minutes intervals up to 30 minutes, and at 10 minute intervals up to 90 minutes before the separation experiment. ICP-OES was used for Pt, Rh, Al, Fe concentration analysis in the separation solution, and scanning electron microscope was used to investigate the particle distribution and shape of the extract. On the other hand, all experiments were performed three times under the same conditions, and the analysis deviation by ICP-OES was very low as ± 0.5% for Pt, Rh, Al, and Fe. In addition, an infrared spectrometer (FT-IR) was used to compare the molecular structure of the extract resin synthesized using two kinds of extractant.

Evaluation of Separation Characteristics According to Extractant

It was confirmed that the particle shape and particle size of the extract resin synthesized using the extractant D2EHPA and TBP are not significantly different. Both extracting resins were synthesized by the same synthesis method, and the composition and composition of the synthetic material were also the same, and thus the particle size and shape were similarly synthesized. The addition method of BPO, which greatly affects the particle size and particle shape, was synthesized with BPO 3pot.

3 is a microstructure photograph showing a first synthetic extract resin powder prepared using D2EHPA, and FIG. 4 is a microstructure photograph showing a second synthetic extract resin powder prepared using TBP.

As shown in Figures 3 and 4, it was confirmed that the particle size can be adjusted to 20 ~ 40㎛ according to the addition method of the reaction initiator BPO when synthesizing the extraction resin using the two extractant. In addition, the extraction performance of the extraction resin synthesized with each extractant is determined by the method of adding the reaction initiator BPO, the reaction proceeds too fast when adding a certain amount of the reaction initiator all at once, divided into three or more times During the reaction, the reaction occurred so slowly that the particles were agglomerated and synthesized.

That is, in the case of the first synthetic extract resin powder synthesized using D2EHPA, it was confirmed that the particle size was uniformly synthesized with 20 to 30 μm. In addition, it was confirmed that the second synthetic extract resin powder synthesized using TBP had a particle size of 20 μm to 40 μm. As can be seen in the above experiment, it was confirmed that the particles were produced in uniform particle size and spherical shape according to the addition method of BPO, and the extraction efficiency was also excellent.

FIG. 5 shows the results of measuring the first and second synthetic extract resin powders prepared using D2EHPA and TBP using infrared spectroscopy, respectively.

5, the infrared spectrum of the two extraction resin was able to confirm that a particular peak matching, were able to identify all of the characteristic peak of the crosslinked polystyrene at 2900cm ^-1, 1000cm ^-1 in accordance with the extractant Inherent peaks were identified.

On the other hand, the separation experiment was carried out in a batch method in a 250ml beaker, the stirring speed was 100rpm, the experiment temperature was 25 ℃, pH was 2.6, and the composition of the element in the platinum scrap leachate mother liquor solution Pt (100mg / l ), Rh (11 mg / l), Fe (100 mg / l) and Al (100 mg / l) were titrated and performed.

Figure 6 is a graph showing the extraction performance of Fe and Al in the platinum scrap leachate mother liquor after the extraction resin synthesized using D2EHPA into the platinum scrap leachate mother liquor, Figure 7 is synthesized using TBP After extracting the resin into the platinum scrap leachate mother liquor solution from which Fe and Al were removed, it is a graph showing the extraction performance of Pt in the platinum scrap leachate mother solution.

As shown in Figure 6, the extraction experiment results Fe in the platinum scrap leachate using solution was extracted 100% by the first synthetic extract resin prepared using D2EHPA, it can be seen that 99.2% was extracted even in the case of Al there was.

On the other hand, as shown in Figure 7, as a result of performing a separation experiment to put the second synthetic extract resin prepared using TBP for separation of Rh and Pt remaining in the platinum scrap leachate mother liquor solution, only Pt 72% Was confirmed to be extracted.

Extraction performance according to temperature and amount of extraction resin added

Both extract resins synthesized using D2EHPA and TBP showed improved performance as the temperature increased, but the separation performance no longer increased at 55 ℃. This is because the activity of atoms increases with increasing temperature, but the separation performance increases, but the separation performance does not affect the activity of the extraction resin and the activities of the platinum group element metal and metal element ion in the mother liquor at a high temperature of 55 ° C. or higher. It is believed that this does not increase.

8 and 9 are graphs showing the extraction efficiency by temperature for the extraction resin synthesized using D2EHPA.

As shown in Figures 8 and 9, the extraction resin synthesized using D2EHPA 100% Fe was extracted in all the experiments for each temperature, 99.5% at 35 ℃, 99.7 at 45 ℃ Al It showed the separation performance of%, it was confirmed that the separation performance of up to 99.9% at 55 ℃.

On the other hand, Figures 10 and 11 are graphs showing the extraction efficiency for each temperature for the extraction resin synthesized using TBP.

10 and 11, in the case of the extraction resin synthesized using TBP, it was confirmed that the selective adsorption of Pt in the remaining Rh and Pt. In particular, the separation performance of 72% at 25 ℃, and 72.8% at 35 ℃, 73.5% of the separation at 45 ℃, it was confirmed that the separation performance of up to 74% at 55 ℃.

As can be seen from the above experimental results, it was confirmed that both extraction resins had a maximum extraction rate at 55 ° C. and the extraction rate did not rise or stop at higher temperatures. It is believed that the extraction rate decreases as the activity of the desorbed metal ions or platinum element ions increases significantly as the temperature increases, and the adsorbed Fe, Al and Pt ions may desorb.

On the other hand, Figure 12 shows the extraction rate according to the amount of each of the extraction resin synthesized using D2EHPA and TBP.

As shown in FIG. 12, in order to determine the extraction efficiency according to the addition amount of the extraction resin, the separation performance was examined by changing the addition amount of the extraction resin for each of the extraction resins synthesized with the two extraction agents. At this time, the extraction conditions are Pt 100 mg / l, Rh 11 mg / l, Fe 100 mg / l, Al 100 mg / l, Temp. : 55 ° C., Time: 90 min, Stirring rate: 100 rpm, pH: 2.5 (a, b), 2.3 (c).

As a result of the above experiments, it was confirmed that the extraction efficiency using D2EHPA showed 99.5 to 99.9% of maximum extraction efficiency when 3 ~ 5wt% was added. In the case of extracting resin using TBP, the maximum extraction rate was 74% at 5 ~ 10 wt%. It confirmed that it showed.

Pt Desorption Conditions Adsorbed on TBP Resin

Desorption experiments were performed in neutral and weakly acidic solutions to desorb Pt only from TBP extract resin from which Pt-only extracts were used. In the case of Pt metal itself, it is not dissolved in distilled water. However, in this study, H ₂ PtCl ₆ ㆍ 5.7H ₂ O was used to solvate to ionic state of PtCl ₆ ^{2 -} in distilled water. The desorption experiment was carried out using a column packed with 10 g of TBP extract resin (10 wt% of the extract resin).

13 is a view showing the recovery of Pt adsorbed on TBP resin according to the desorption solution. At this time, H ₂ O, 0.1M HCl, 0.5M HCl was used as the desorption solution.

As shown in FIG. 13, as a result of the desorption experiment, as a result of using H ₂ O (pH 7) as the desorption solution, it was confirmed that 99.79% of the Pt adsorbed on the TBP extract resin was desorbed. When 0.1 M HCl was used as the desorption solution, 97.77% of the adsorbed Pt was desorbed. When 0.5 M HCl was used as the desorption solution, 93.15% of the adsorbed Pt was desorbed. At this time, it is determined that adsorption / desorption is performed by adsorbing or detaching PtCl ₆ ^{2 −} from O bonds that are double bonds to TBP as an extractant. Adsorption is well performed in acidic solution when using TBP extractor, but it was confirmed through experiment that desorption was performed in weak acid and neutral solution, and the adsorption and desorption process is considered to be represented by the following Equation 1.

Equation 1: 2H ⁺ + PtCl ₆ ^2- + H ₂ O + TBP = O

PtCl₆TBP + H₂O

PtCl ₆ TBP + H ₂ O

In this case, the desorption is well performed in the neutral and weakly acidic solution, because the adsorption is performed in the acidic solution of the extractor TBP, but the adsorption rate decreases and the desorption rate increases as the pH is increased.

conclusion

Extraction resins were synthesized using two kinds of extractants (D2EHPA and TBP) to separate Pt from the platinum scrap leach mother liquor solution (Pt, Rh, Fe, Al). The following results were obtained through the separation experiment of first extracting Fe and Al from the platinum scrap leachate using the D2EHPA extract resin and selectively extracting only Pt using the TBP extract resin.

Reaction initiator (BPO) was added to both extracts using both extractants. This is confirmed by particle surface and morphology analysis through SEM. As a result, when the polymerization initiator is added all at once, the reaction proceeds too fast, so that the synthesis is not performed well or fine particles are synthesized and divided into three or more times. The reaction proceeds so slowly that the particles agglomerate and are not well synthesized. In addition, it could be confirmed that the particle shape and the particle size were not changed by the extractant but by the addition method of the reaction initiator.

Fe and Al extraction using D2EHPA extract resin showed excellent extraction performance of 100% Fe and 99.2% Al. In addition, by separating only Pt of Rh and Pt remaining in the platinum scrap leachate using the TBP extract resin, the adsorption rate was 72%. Pt adsorbed on the TBP extract resin was a weak acid and neutral solution as a desorption solution. As a result, the excellent desorption rate of 99.79% was confirmed. In addition, through the FT-IR analysis, in the present invention, the two peaks according to the extract (peak) and the peak (peak) according to the polystyrene (polystyrene) was confirmed.

In addition, as a result of the separation experiment to examine the effect of temperature on the extraction efficiency, it was confirmed that the extraction rate has a maximum at 55 ℃, which was adsorbed as the activity of metal ions and platinum ions increased significantly above 55 ℃. This is because Fe, Al, and Pt desorb.

In addition, in the present invention, it is determined that the extraction resin is synthesized using the extractant D2EHPA and TBP, and the platinum recovery from the platinum scrap leachate may be made very efficiently.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. These changes and modifications may be made without departing from the scope of the present invention. Accordingly, the scope of the present invention should be determined by the following claims.

S110: manufacturing steps of the first and second synthetic extract resin
S120: the first synthetic extract resin / platinum scrap leaching solution mixing step
S130: adsorbing aluminum and iron in the platinum scrap leach solution to the first synthetic extract resin
S140: adsorbing platinum in the platinum scrap leach solution to the second synthetic extract resin
S150: Desorption of platinum from the second synthetic extract resin
S111: mixing and stirring the first extract resin raw material
S112: adding swelling agent, pore former and stabilizer
S113: reaction initiator addition step
S114: Pressurized filtering / drying step of the first synthetic extract resin
S115: first synthetic extract resin powder grinding step

Claims (12)

(a) preparing a first synthetic resin and a second synthetic resin by synthesizing the first and second extracting resins by suspension polymerization;
(b) injecting the first synthetic extract resin into a platinum scrap leach solution;
(c) reacting the first synthetic extract resin and the platinum scrap leach solution at 35 to 55 ° C. while stirring to adsorb aluminum (Al) and iron (Fe) in the platinum scrap leach solution to the first synthetic extract resin, followed by Collecting the first synthetic extract resin to which (Al) and iron (Fe) are adsorbed;
(d) adsorbing platinum (Pt) in the platinum scrap leach solution to the second synthetic extract resin by adding a second synthetic extract resin to the platinum scrap leach liquid from which the first synthetic extract resin is collected; And
(e) recovering platinum (Pt) by desorbing platinum (Pt) from the second synthetic extract resin using a desorption solution after collecting the second synthetic extract resin to which the platinum (Pt) is adsorbed; Include,
In the step (a), the step of preparing the first synthetic extract resin or the second synthetic extract resin, (a-1) distilled water, styrene monomer (styrene monomer) as a monomer, divinyl benzene (crosslinking agent) And di-2-ethylhexylphosphoric acid (D2EHPA), which is a first extractant, into a reaction tank, or distilled water, styrene monomer, which is a monomer, divinyl benzene, a crosslinking agent, and TBP (tri, as a second extractant). -butyl-phosphate) was added to the reactor, followed by heating at a first temperature of 80 to 100 ° C. and stirring at a speed of 300 to 400 rpm, and (a-2) 75 to 85 ° C. lower than the first temperature. At the temperature maintained at the second temperature, adding a swelling agent, a pore former and a stabilizer to the reaction tank, and (a-3) BOP (benzoyl peroxide) as a reaction initiator in the reaction tank divided into 3 to 5 times Comprising 10 to 14 hours of synthesis,
The first synthetic extract resin is added to 3 ~ 5g per 100ml of the platinum scrap leachate, and the second synthetic extract resin is added to 5 ~ 10g per 100ml of the platinum scrap leachate from which the first synthetic extract resin is collected A method for recovering platinum from a platinum scrap leaching solution using a synthetic extract resin.
delete delete delete delete The method of claim 1,
The swelling agent is toluene (toluene), the pore forming agent is normal-heptane (n-heptane), and the stabilizer is a platinum scrap leaching solution using a synthetic extract resin, characterized in that each using polyvinyl alcohol (polyvinyl alcohol) Platinum recovery method.
delete The method of claim 1,
After the step (a-3),
(a-4) pressurizing and filtering the synthesized first extracting resin, and then drying the extract;
(a-5) A method for recovering platinum from platinum scrap leachate using a synthetic extract resin, characterized in that it further comprises the step of pulverizing the dried first synthetic extract resin powder to a particle size of 75 ~ 100㎛.
9. The method of claim 8,
In the step (a-4),
The drying is
Platinum recovery method from the platinum scrap leaching solution using a synthetic extract resin, characterized in that carried out for 20 to 30 hours at 20 ~ 40 ℃.
delete delete The method of claim 1,
In the step (d)
The desorption solution is
A method for recovering platinum from a platinum scrap leach solution using synthetic extract resins comprising at least one of H ₂ O and 0.1-0.5 M HCl.

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