CN114672647A - Method for selectively and sequentially extracting palladium and platinum by using grape skin temperature control - Google Patents
Method for selectively and sequentially extracting palladium and platinum by using grape skin temperature control Download PDFInfo
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- CN114672647A CN114672647A CN202210311530.2A CN202210311530A CN114672647A CN 114672647 A CN114672647 A CN 114672647A CN 202210311530 A CN202210311530 A CN 202210311530A CN 114672647 A CN114672647 A CN 114672647A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A method for realizing selective adsorption and separation between platinum and palladium by using modified grape skin in combination with temperature regulation measures belongs to the field of adsorption materials. Filling the modified grape skin into an adsorption column, slowly and uniformly percolating a complex solution containing platinum, palladium, precious metal and iron, nickel, copper and zinc base metal multi-element impurity components through an adsorption column bed at the temperature of 25-45 ℃ and the hydrochloric acid concentration of 3-6M to adsorb and separate palladium ions in the complex solution; then collecting the percolate, heating to 75 ℃, and continuously percolating through another adsorption column bed filled with the modified grape skin to adsorb and trap platinum ions in the percolate; respectively obtaining desorption solution rich in palladium and desorption solution rich in platinum, and obtaining palladium powder and platinum powder with higher purity by a displacement reduction method. The invention uses the modified grape skin as an adsorbent, selectively adsorbs platinum and palladium, does not adsorb impurity ions such as nickel, iron, zinc, copper and the like, has high selectivity, and obtains the platinum and palladium with higher purity.
Description
Technical Field
The invention relates to a method for separating platinum and palladium, in particular to a method for realizing selective adsorption separation of platinum and palladium by utilizing modified grape skin in combination with temperature regulation.
Technical Field
The platinum group metals are low in storage amount and high in price, are widely applied to the fields of electronics, medical treatment, catalysts and the like, and are important research subjects in the aspects of extracting and recovering the platinum group metals from smelting associated ore electrolysis anode mud, waste electronic wastes or waste catalysts.
Because the properties of platinum group elements are similar, the platinum and palladium metallurgical processes in industry are often extracted and enriched simultaneously, and then the platinum or palladium simple substances with high purity are obtained respectively through subsequent refining and purification. This is suitable for the concentration of platinum and palladium with higher concentration, for example, the platinum and palladium can be separated and purified by using a repeated dissolution-precipitation method, but for the platinum and palladium solution with thinner concentration, the dissolution-precipitation method can be implemented only after the platinum and palladium solution is pre-enriched to a certain concentration, so that the process is very tedious. If the separation of the platinum and the palladium can be realized by adopting a method of selectively separating and extracting one of the platinum and the palladium from the beginning aiming at the platinum and palladium solution with dilute concentration, the platinum or the palladium after extraction can be respectively refined and purified, and the industrial practical value is very high. The industrial separation and recovery of platinum and palladium mainly comprises an extraction method, an adsorption method and a selective precipitation method.
Document 1 (nonferrous metals (smelting part), 2021(06):78-83) reports that, aiming at a low-grade platinum-containing feed liquid with high impurity content, a new refining process of ammonium chloride platinum precipitation → chlorination dissolution → hydrolysis impurity removal → ketoxime palladium removal → ammonium chloride platinum precipitation → formaldehyde reduction → nitric acid washing → high-purity sponge platinum is adopted, so that operations such as calcination by ammonium chloroplatinate and aqua regia dissolution are avoided, and a series of problems such as overproof palladium in sponge platinum caused by incomplete nitrate removal are solved. Document 2 (chinese resource comprehensive utilization, 2016,34(10):19-22.) reports that, because of the different solubility of ammonium chloroplatinate and ammonium chloropalladate in water, the platinum-palladium coprecipitate is boiled with water, the ammonium chloropalladate is dissolved in the liquid as much as possible, then the filtration is carried out, the palladium is extracted from the filtrate, and the platinum is extracted from the filter residue. The document 3 (journal of environmental science, 2008,28(1): 120-.
The method has the characteristics of long process flow, complex process, high pollution and poor platinum-palladium separation effect.
Disclosure of Invention
The invention aims to solve the key technical problem that the waste grape skin is used as a raw material, and the platinum-palladium can be efficiently adsorbed and extracted at 25 ℃ and a proper hydrochloric acid concentration on the premise of not adsorbing or slightly adsorbing Ni, Fe, Zn, Cu and other base metal ions after modification treatment, and platinum is adsorbed after the temperature is raised to over 75 ℃ aiming at the redundancy problem of the traditional platinum-palladium separation process. The method for selectively adsorbing and separating platinum and palladium by using the modified grape skin and combining the temperature regulation and control method has the advantages of high adsorption rate, good platinum and palladium separation effect, short flow, low cost and environmental friendliness.
The technical scheme of the invention is as follows:
a method for selectively and sequentially extracting palladium and platinum by using grape skin in combination with temperature control measures is characterized in that modified grape skin is filled in an adsorption column, and complex solution containing platinum-palladium noble metal and iron-nickel-copper-zinc base metal multi-element impurity components at the temperature of 25-45 ℃ and the hydrochloric acid concentration of 3M-6M is slowly and uniformly percolated through the adsorption column bed at the flow rate of 0.1-1mL/min to adsorb and separate palladium ions in the complex solution; then collecting the percolate, heating to 75 ℃, and continuously percolating through another adsorption column bed filled with the modified grape skin to adsorb and trap platinum ions in the percolate; after the two adsorption columns complete 1 round of adsorption, 1M HCl solution containing 1M thiourea is respectively introduced at the same percolation rate to respectively obtain desorption solution rich in palladium and platinum, and then the desorption solution rich in palladium and platinum is subjected to a displacement reduction method to obtain palladium powder and platinum powder with higher purity.
Further, the preparation method of the modified grape skin adsorbent comprises the following steps:
(1) crushing, juicing, washing, filtering and dehydrating the grape skin waste;
(2) the slag is prepared by the following steps of 1: adding water according to the weight ratio of 1, stirring, adjusting the pH value to 8-9 by using a 12M NaOH solution, continuously stirring at room temperature for 20-24 hours, and filtering;
(3) and then filtering and washing the grape skin adsorbent material for multiple times, drying and grinding the grape skin adsorbent material to obtain modified grape skin adsorbent material particles.
The principle of the invention lies in two points: on one hand, the grape skin contains a large amount of polyphenol substances, the surfaces of the polyphenols contain a large amount of hydroxyl functional groups, and the polyphenols have reducibility, are easy to reduce and adsorb noble metal ions such as platinum and palladium after being modified, and are difficult to adsorb impurity ions such as nickel, iron, zinc, copper and the like. On the other hand, at different temperatures, the difference of physicochemical properties such as the hydrolysis degree and the occurrence form of platinum and palladium in the solution is increased, and the high-temperature activation effect of the polyphenol components of the grape skin may be included, so that the adsorption difference of the polyphenol components of the grape skin is reflected. In conclusion, the reasons of the two aspects create favorable conditions for selectively adsorbing and separating platinum and palladium.
Compared with Pt (IV), Pd (II) has larger radius, smaller hydration radius and easier access to smaller gaps in the adsorption material. In addition, Pd (II) has higher electronegativity and higher ionic potential than Pt (IV), so that negatively charged palladium ions are more easily bound to the positively charged adsorbent surface by acid protonation. However, due to the high stability of pt (iv) in solution, reduction is more difficult. Therefore, the adsorbent has a good effect of adsorbing Pd (II), but has a poor effect of adsorbing Pt (IV).
Due to the high temperature condition, the method is beneficial to the exposure of a large amount of polyphenols in the adsorbent, enhances the adsorption effect of the adsorbent on platinum, and promotes different hydration degrees of platinum and palladium ions, thereby influencing the adsorption efficiency. Therefore, aiming at the difference of platinum-palladium adsorption rates of grape skins at different temperatures, the separation and recovery of platinum and palladium in the solution are realized by controlling the temperature. Compared with the prior art, the invention has the beneficial effects that:
(1) the grape skin adsorbent provided by the invention is simple in preparation process and low in preparation cost.
(2) The invention realizes the sequential and separate adsorption and extraction of palladium and platinum by using a grape skin combined adsorption temperature control method, thereby obtaining two solutions rich in palladium and platinum for further purification and refining. The separation operation between palladium and platinum is simple, the process flow is short, the cost is low, and the platinum-palladium separation effect is good.
(3) The grape skin adsorbent disclosed by the invention selectively adsorbs platinum and palladium, impurity ions such as nickel, iron, zinc, copper and the like are not adsorbed, the selectivity is high, and the purity of the obtained platinum and palladium is higher.
(4) The grape skin adsorbent is green and environment-friendly, is non-toxic and harmless, and does not generate peculiar smell in use.
(5) The grape skin biomass waste is modified and then is used as the adsorbent again, which is beneficial to the utilization of waste biomass materials.
Drawings
FIG. 1 shows the results of selective continuous column adsorption of palladium and desorption of palladium at 25 ℃ and 3M hydrochloric acid concentration using modified grape skin according to the present invention.
FIG. 2 shows the results of the present invention using modified grape skin to continue the adsorption of platinum in the residual mother liquor after the above extraction of palladium at 75 ℃ and 3M hydrochloric acid concentration, and the desorption of deplatinization.
Detailed Description
The first implementation mode comprises the following steps:
the following embodiments are provided to illustrate the principles and technical points of the present invention in more detail, and the disclosed embodiments are not intended to limit or restrict the scope of the invention covered by the disclosed principles and techniques.
Crushing, juicing and washing the grape skin waste, wherein the proportion of the grape skin waste residues is 1: adding water according to the weight ratio of 1, fully stirring and stirring at room temperature of 25 ℃, adjusting the pH value to 8-9 by using a 12M NaOH solution, continuously stirring for 20-24 hours at room temperature, and filtering; the grape skin is then washed several times with deionized water until the wash water is clear. And then, putting the cleaned mixture into an oven, drying for 12 hours at 353K, taking out the mixture, and grinding into particles with uniform size to obtain the modified grape skin adsorbent material particles.
Filling the modified grape skin into an adsorption column, slowly and uniformly percolating a complex solution containing platinum-palladium noble metal, iron-nickel-copper-zinc and other base metal multi-element impurity components at the temperature of 25 ℃ and the concentration of 3M hydrochloric acid through the adsorption column bed to adsorb and separate palladium ions in the complex solution; then the leachate is collected and heated to 75 ℃, and the leachate is continuously percolated through another adsorption column bed filled with modified grape skin to adsorb and trap platinum ions in the leachate. After the two adsorption columns complete 1 round of adsorption, 1M HCl solution containing 1M thiourea is respectively introduced at the same percolation rate to respectively obtain desorption solution rich in palladium and platinum, and then the palladium powder and the platinum powder with higher purity can be obtained by methods such as replacement reduction and the like.
The second embodiment:
crushing, juicing and washing the grape skin waste, wherein the proportion of the grape skin waste in the grape skin waste residues is 2: adding water according to the weight ratio of 1, fully stirring and stirring at room temperature of 25 ℃, adjusting the pH value to 7-8 by using a 12M NaOH solution, continuously stirring for 48-96 hours at room temperature, and filtering; the grape skin is then washed several times with deionized water until the wash water is clear. And then, putting the cleaned mixture into an oven, drying for 24 hours at 353K, taking out the mixture, and grinding into particles with uniform size to obtain the modified grape skin adsorbent material particles.
Filling the modified grape skin into an adsorption column, slowly and uniformly percolating a complex solution containing platinum-palladium noble metal, iron-nickel-copper-zinc and other base metal multi-element impurity components at the temperature of 30 ℃ and the concentration of 4M hydrochloric acid through the adsorption column bed to adsorb and separate palladium ions in the complex solution; then the leachate is collected and heated to 80 ℃, and the leachate is continuously percolated through another adsorption column bed filled with modified grape skin to adsorb and trap platinum ions in the leachate. After the two adsorption columns complete 1 round of adsorption, 1M HCl solution containing 1M thiourea is respectively introduced at the same percolation rate to respectively obtain desorption solution rich in palladium and platinum, and then the palladium powder and the platinum powder with higher purity can be obtained by methods such as replacement reduction and the like.
The third embodiment is as follows:
crushing, juicing and washing the grape skin waste, wherein the weight of the grape skin waste residues is 3: adding water according to the weight ratio of 1, fully stirring and stirring at room temperature of 25 ℃, adjusting the pH value to 9-10 by using a 12M NaOH solution, continuously stirring for 24-48 hours at room temperature, and filtering; the grape skin is then washed several times with deionized water until the wash water is clear. And then, putting the cleaned mixture into an oven, drying for 12 hours at 353K, taking out the mixture, and grinding into particles with uniform size to obtain the modified grape skin adsorbent material particles.
Filling the modified grape skin into an adsorption column, slowly and uniformly percolating a complex solution containing platinum-palladium noble metal, iron-nickel-copper-zinc and other base metal multi-element impurity components at the temperature of 25 ℃ and the concentration of 6M hydrochloric acid through the adsorption column bed to adsorb and separate palladium ions in the complex solution; then the leachate is collected and heated to 75 ℃, and the leachate is continuously percolated through another adsorption column bed filled with modified grape skin to adsorb and trap platinum ions in the leachate. After the two adsorption columns complete 1 round of adsorption, 1M HCl solution containing 1M thiourea is respectively introduced at the same percolation rate to respectively obtain desorption solution rich in palladium and platinum, and then the palladium powder and the platinum powder with higher purity can be obtained by methods such as replacement reduction and the like.
Claims (2)
1. A method for selectively and sequentially extracting palladium and platinum by using grape skin under temperature control is characterized in that modified grape skin is filled in an adsorption column, complex solution containing platinum-palladium precious metal and iron-nickel-copper-zinc base metal multi-element impurity components at the temperature of 25-45 ℃ and the hydrochloric acid concentration of 1-6M is slowly and uniformly percolated through the adsorption column bed at the flow rate of 0.1-1mL/min to adsorb and separate palladium ions in the complex solution; then collecting the percolate, heating to 75 ℃, and continuously percolating through another adsorption column bed filled with the modified grape skin to adsorb and trap platinum ions in the percolate; after the two adsorption columns complete 1 round of adsorption, 1M HCl solution containing 1M thiourea is respectively introduced at the same percolation rate to respectively obtain desorption solution rich in palladium and platinum, and then the desorption solution rich in palladium and platinum is subjected to a displacement reduction method to obtain palladium powder and platinum powder with higher purity.
2. The method for selectively and sequentially extracting palladium and platinum by using grape skin under controlled temperature according to claim 1, wherein the modified grape skin adsorbent is prepared by the following steps:
(1) crushing, juicing, washing, filtering and dehydrating the grape skin waste;
(2) the slag is prepared by the following steps of 1: adding water according to the weight ratio of 1, stirring, adjusting the pH value to 8-9 by using a 12M NaOH solution, continuously stirring at room temperature for 20-24 hours, and filtering;
(3) and then filtering and washing the grape skin adsorbent material for multiple times, drying and grinding the grape skin adsorbent material to obtain modified grape skin adsorbent material particles.
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| CN202210311530.2A CN114672647B (en) | 2022-03-28 | 2022-03-28 | Method for selectively and sequentially extracting palladium and platinum by using grape skin temperature control |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614836A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal palladium by persimmon tannin-containing metal adsorbent |
| CN102614837A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal gold by persimmon tannin-containing metal adsorbent |
| CN102614835A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Persimmon tannin-containing metal adsorbent and preparation method thereof |
| JP2016047505A (en) * | 2014-08-28 | 2016-04-07 | 元基 井上 | Noble metal adsorbent using polyphenol derived from grape seeds as raw material |
| JP2019072722A (en) * | 2019-01-30 | 2019-05-16 | 学校法人 明治薬科大学 | Method for producing noble metal adsorbent and recovery method of noble metals |
| CN114146693A (en) * | 2021-12-08 | 2022-03-08 | 上海交通大学 | Grape skin adsorbent for adsorption removal of cadmium ions, preparation method and application thereof |
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2022
- 2022-03-28 CN CN202210311530.2A patent/CN114672647B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614836A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal palladium by persimmon tannin-containing metal adsorbent |
| CN102614837A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Method for adsorbing and recovering precious metal gold by persimmon tannin-containing metal adsorbent |
| CN102614835A (en) * | 2011-01-28 | 2012-08-01 | 华中农业大学 | Persimmon tannin-containing metal adsorbent and preparation method thereof |
| JP2016047505A (en) * | 2014-08-28 | 2016-04-07 | 元基 井上 | Noble metal adsorbent using polyphenol derived from grape seeds as raw material |
| JP2019072722A (en) * | 2019-01-30 | 2019-05-16 | 学校法人 明治薬科大学 | Method for producing noble metal adsorbent and recovery method of noble metals |
| CN114146693A (en) * | 2021-12-08 | 2022-03-08 | 上海交通大学 | Grape skin adsorbent for adsorption removal of cadmium ions, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 董泽宏: "《饮食精粹新编 卷3 秋篇》", 31 March 2019, 中国协和医科大学出版社 * |
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