CN113293301B - Method for recovering platinum group metals from metal carrier waste automobile exhaust catalyst - Google Patents

Method for recovering platinum group metals from metal carrier waste automobile exhaust catalyst Download PDF

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CN113293301B
CN113293301B CN202110559263.6A CN202110559263A CN113293301B CN 113293301 B CN113293301 B CN 113293301B CN 202110559263 A CN202110559263 A CN 202110559263A CN 113293301 B CN113293301 B CN 113293301B
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pgms
solution
alkali
metal carrier
automobile exhaust
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CN113293301A (en
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丁云集
张深根
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University of Science and Technology Beijing USTB
Shunde Graduate School of USTB
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University of Science and Technology Beijing USTB
Shunde Graduate School of USTB
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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
    • C22B7/001—Dry processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/026—Recovery of noble metals from waste materials from spent catalysts
    • 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
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/048—Recovery of noble metals from waste materials from spent catalysts
    • 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
    • C22B7/001—Dry processes
    • C22B7/002—Dry processes by treating with halogens, sulfur or compounds thereof; by carburising, by treating with hydrogen (hydriding)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • 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

The invention relates to the technical field of Platinum Group Metal (PGMs) recovery, and provides a method for recovering platinum group metals from a metal carrier waste automobile exhaust catalyst. The method comprises the following steps: crushing and shearing the metal carrier waste automobile exhaust catalyst into pieces, and then selectively dissolving Al in the pieces by alkali fusion or alkali dissolution2O3Coating to realize metal carriers, PGMs and Al2O3The coating is separated efficiently, the flaky metal carrier is sold after being cleaned, and the enriched PGMs are separated and purified to obtain Pt, Pd and Rh products with the purity of more than 99.99 percent. The invention realizes the high-efficiency recovery of PGMs without dissolving carriers, has the characteristics of low material consumption and energy consumption, high recovery rate of PGMs, low cost and the like, and is suitable for industrial production.

Description

Method for recovering platinum group metals from metal carrier waste automobile exhaust catalyst
Technical Field
The invention belongs to the field of regeneration of platinum group metals, and particularly relates to a method for recovering platinum group metals from a metal carrier waste automobile exhaust catalyst.
Background
As one of the largest application areas for platinum group metals, automobile exhaust catalysts consume 45% platinum, 65% palladium, and 85% rhodium annually. Therefore, the waste automobile exhaust catalysts are also the most important secondary resources of platinum group metals. China is the country with the largest automobile output and the largest reserved quantity, in 2020, the reserved quantity of motor vehicles in China exceeds 3.5 million, the scrappage is about 1000 thousands, the resource quantity of PGMs reaches 15-20 tons, and the economic price exceeds 100 million yuan.
The main methods for recovering platinum group metals from the scrapped automobile exhaust catalyst include a plasma smelting method, a pyrogenic chlorination and volatilization method, a metal trapping method, a pressure cyaniding method, an active component dissolving method and the like. The method mainly aims at catalysts of cordierite carriers, and the technology is mature, but the method is not suitable for metal carrier automobile exhaust catalysts. At present, about 15 million metal carrier failure automobile exhaust catalysts wait for treatment every year, and the platinum group metal reserves cannot be ignored.
The Chinese patent of invention (application number: 201510285196.8) discloses a spent metal carrier automobile exhaust catalyst which is directly melted at high temperature, then rapidly cooled or atomized to obtain alloy with fine particles, then acid is added to selectively leach base metals, and platinum group metal concentrate is obtained through filtration and washing, so that the platinum group metals are efficiently enriched. The method utilizes the metal carrier as the platinum group metal trapping agent, does not need to add any trapping agent, has simple process flow operation, high platinum group metal recovery rate but low enrichment ratio, high consumption of subsequent base metal leaching materials, large wastewater amount and heavy environmental burden. In order to insolubilize the metal carrier, the Chinese patent application No. 201410476555.3 discloses that platinum group metals are separated from the iron carrier by crushing and ultrasonic treatment to obtain powder containing platinum group metals, then the powder is roasted at high temperature, and finally HCl + Cl is used in a reaction kettle2Leaching out platinum group metals. Although the method does not use dissolved iron carrier, the efficiency of stripping platinum group metals by the ultrasonic method is low, and the recovery rate is low.
Disclosure of Invention
Aiming at the problems of high carrier total-dissolved material consumption and energy consumption, low ultrasonic-acid leaching recovery rate and the like in the existing metal carrier waste automobile exhaust catalyst recovery process, the invention provides a low-cost, high-efficiency and green method for stripping platinum group metals.
The invention adopts the following technical scheme:
a method for recovering platinum group metals from metal carrier waste automobile exhaust catalysts is characterized by comprising the following steps:
(1) crushing and shearing: firstly, crushing and shearing a metal carrier waste automobile exhaust catalyst into pieces;
(2) alkali fusion or alkali dissolution: mixing the flaky waste catalyst with alkali, placing the mixture in a furnace for alkali fusion roasting, and then soaking in water; or directly adding the flaky waste catalyst into alkali liquor to dissolve and leach without roasting;
(3) enrichment and separation: separating insoluble flaky metal carrier from the leaching solution, and washing for sale; filtering and separating the leachate and the PGMs concentrate;
(4) and (3) purification: separating and purifying the PGMs enrichment substance to obtain Pt, Pd and Rh products.
Further, the waste automobile exhaust catalyst in the step (1) is cut into 1-20cm2The sheet of (4).
Further, the alkali in the step (2) is any one or more than two of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Further, when roasting is needed in the step (2), the mass ratio of alkali to the waste automobile exhaust catalyst in the alkali fusion process is 0.5:1-2:1, the temperature is 600-1000 ℃, and the alkali fusion time is 30-240 min.
Further, when the roasting is not performed in the step (2), the solid-to-liquid ratio in the alkali dissolution process is 1:3-1:10, the temperature is 30-95 ℃, and the alkali dissolution time is 30-180 min.
Further, the separation and purification steps of the PGMs concentrate are as follows:
acid hydrolysis: firstly, aqua regia or HCl + NaClO is adopted3Dissolving the PGMs enrichment substance to obtain a PGMs solution;
impurity removal: removal of Fe from PGMs solution by cation exchange resin3+、Al3+、Na+Plasma impurity ions;
purifying Pd: conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 0.1-2.0mol/L, wherein the volume ratio of an organic phase to a solution is 0.5:1-2:1, and the extraction temperature is 20-60 ℃; then 0.1-2.0mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 2-4 times, and finally 99.99 percent Pd is obtained by reduction with formaldehyde;
and fourthly, purifying Pt: adjusting raffinate H of Pd+Extracting Pt with tributyl phosphate at concentration of 2.0-6.0mol/L at 40-70 deg.C, wherein the volume ratio of organic phase to solution is 2:1-6: 1; then 2.0-6.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 2-4 times, and finally 99.99 percent of Pt is obtained by reduction with formaldehyde;
and fifthly, purifying Rh: precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 2-3 times; after washing (NH)4)RhCl6Calcining for 2-4h at the temperature of 600-.
Further, the recovery of PGMs using the method is greater than 99%.
According to the invention, by analyzing the occurrence state and the loading form of the platinum group metal in the metal carrier waste automobile exhaust catalyst, a method for stripping the platinum group metal by adopting an alkali fusion or alkali dissolution method is provided, so that the high-efficiency low-cost recovery of the platinum group metal is realized, the metal carrier is prevented from being dissolved, the material consumption and the energy consumption are low, the environment is friendly, and a new idea and a new method are provided for the recovery of the platinum group metal of the metal carrier waste catalyst.
The principle of the invention is as follows:
based on the characteristics of the preparation process of the metal carrier automobile exhaust catalyst, namely that PGMs are loaded on Al on the surface layer of the metal carrier2O3The method provided by the invention utilizes the characteristic to selectively dissolve Al by an alkali fusion or alkali dissolution method2O3The metal carrier and the PGMs do not react with alkali to realize PGMs, the metal carrier and Al2O3The coating is separated efficiently, the dissolution of the metal carrier is avoided, and the recovery rate of PGMs is improved.
The invention has the beneficial effects that:
(1) the method realizes the full-component resource utilization of the metal carrier waste automobile exhaust catalyst;
(2) the method adopts an alkali fusion or alkali dissolution method to selectively dissolve Al2O3Coating realizes PGMs, metal carrier and Al2O3The coating is separated efficiently, and the method has the advantages of low cost, low material consumption and energy consumption, high PGMs separation effect and the like;
(3) the enrichment multiple of PGMs in the PGMs enrichment substance obtained by the method is high, and the material consumption and energy consumption of subsequent separation and purification are reduced;
(4) the direct yield of the extracted and purified PGMs is high, and the purity of the obtained PGMs is over 99.99 percent.
Drawings
FIG. 1 is a process flow diagram of a method for full component utilization of a metal carrier exhaust catalyst of an automobile according to an embodiment of the invention.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be noted that technical features or combinations of technical features described in the following embodiments should not be considered as being isolated, and they may be combined with each other to achieve better technical effects. In the drawings of the embodiments described below, the same reference numerals appearing in the respective drawings denote the same features or components, and may be applied to different embodiments.
The method for utilizing all components of the metal carrier waste automobile exhaust catalyst is shown in a process flow chart of figure 1, and comprises the steps of crushing and shearing the metal carrier waste automobile exhaust catalyst into pieces, and then selectively dissolving Al in the pieces of the waste catalyst through alkali fusion or alkali dissolution2O3Coating to realize metal carriers, PGMs and Al2O3The coating is separated efficiently, the flaky metal carrier is sold after being cleaned, and the enriched PGMs are separated and purified to obtain Pt, Pd and Rh products with the purity of more than 99.99 percent.
The following detailed description of the implementation of the present invention is made with reference to specific embodiments:
example 1
Shearing the metal carrier waste automobile exhaust catalyst into 1cm2The flaky object is evenly mixed with sodium hydroxide with the mass ratio of 0.5:1, and the mixture is roasted at 600 ℃ for 240 min. Dissolving the roasted product at 30 ℃ in a solid-to-liquid ratio of 1:3 to obtain the PGMs enrichment substance and the metal carrier, wherein the dissolving time is 180 min. Dissolving PGMs with aqua regia at 80 deg.C, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 0.1mol/L, wherein the volume ratio of an organic phase to a solution is 0.5:1, and the extraction temperature is 20 ℃; then back extracting with 0.1mol/L ammonia water, repeatedly extracting for 4 times, and finally using formaldehydeReduction gave 99.99% Pd. Adjusting raffinate H of Pd+The concentration is 2.0mol/L, tributyl phosphate is adopted to extract Pt, the volume ratio of an organic phase to a solution is 2:1, and the extraction temperature is 40 ℃; then 2.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 2 times, and finally 99.99 percent of Pt is obtained by reduction with formaldehyde; precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 600 deg.C for 2h, reducing with hydrogen to obtain Rh powder, repeatedly boiling Rh powder with HCl and HF for 3 times, washing with deionized water, and oven drying to obtain 99.99% Rh.
Example 2
Shearing the metal carrier waste automobile exhaust catalyst into 5cm2The flaky object is evenly mixed with potassium hydroxide with the mass ratio of 1:1, and the mixture is roasted for 200min at 700 ℃. Dissolving the roasted product at 50 ℃ in a solid-to-liquid ratio of 1:4 to obtain the PGMs enrichment substance and the metal carrier, wherein the dissolving time is 140 min. Dissolving PGMs with aqua regia at 90 deg.C, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 0.5mol/L, wherein the volume ratio of an organic phase to a solution is 1:1, and the extraction temperature is 30 ℃; then 0.5mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 4 times, and finally, 99.99 percent Pd is obtained by reduction with formaldehyde. Adjusting Pd extraction raffinate H+Extracting Pt with tributyl phosphate at the concentration of 3.0mol/L, wherein the volume ratio of the organic phase to the solution is 3:1, and the extraction temperature is 50 ℃; then 3.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 3 times, and finally 99.99 percent of Pt is obtained by reduction with formaldehyde; precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 700 deg.C for 3h, reducing with hydrogen to obtain Rh powder, repeatedly boiling Rh powder with HCl and HF for 3 times, washing with deionized water, and oven drying to obtain 99.99% Rh.
Example 3
Shearing the metal carrier waste automobile exhaust catalyst into 10cm2Sheet-like article ofMixing with sodium carbonate in the mass ratio of 3:1, and roasting the mixture at 800 ℃ for 120 min. Dissolving the roasted product at 30 ℃ in a solid-to-liquid ratio of 1:5 to obtain the PGMs enrichment substance and the metal carrier, wherein the dissolving time is 180 min. Dissolving PGMs with aqua regia at 95 deg.C, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 2.0mol/L, wherein the volume ratio of an organic phase to a solution is 2:1, and the extraction temperature is 60 ℃; then 2.0mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 4 times, and finally, 99.99 percent Pd is obtained by reduction with formaldehyde. Adjusting raffinate H of Pd+Extracting Pt with tributyl phosphate at a concentration of 5.0mol/L, wherein the volume ratio of the organic phase to the solution is 5:1, and the extraction temperature is 60 ℃; then, 6.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 3 times, and finally, 99.99 percent of Pt is obtained by reduction with formaldehyde; precipitating Rh from the Pt raffinate by using saturated ammonium chloride solution to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining for 4h at 1000 ℃, then reducing by hydrogen to obtain Rh powder, repeatedly boiling the Rh powder for 2 times by HCl and HF respectively, washing by deionized water, and drying to obtain 99.99% Rh finally.
Example 4
Shearing the metal carrier waste automobile exhaust catalyst into 15cm2The flaky substance is evenly mixed with potassium carbonate with the mass ratio of 2:1, and the mixture is roasted for 30min at 1000 ℃. Dissolving the roasted product at 60 ℃ in a solid-to-liquid ratio of 1:3.5 to obtain PGMs (PGMs) enrichment and metal carriers, wherein the dissolving time is 100 min. Dissolving PGMs with aqua regia at 70 deg.C, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 1.5mol/L, wherein the volume ratio of an organic phase to a solution is 1.5:1, and the extraction temperature is 45 ℃; then 1.5mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 3 times, and finally 99.99 percent Pd is obtained by reduction with formaldehyde. Adjusting raffinate H of Pd+The concentration is 4.0mol/L, tributyl phosphate is adopted to extract Pt, and the volume ratio of the organic phase to the solution is 51, extracting at 60 ℃; then, back extraction is carried out by adopting 4.0mol/L hydrochloric acid, repeated extraction is carried out for 3 times, and finally, 99.99 percent of Pt is obtained by reduction by using formaldehyde; precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 900 deg.C for 3h, reducing with hydrogen to obtain Rh powder, repeatedly boiling Rh powder with HCl and HF for 3 times, washing with deionized water, and oven drying to obtain 99.99% Rh.
Example 5
Shearing the metal carrier waste automobile exhaust catalyst into 20cm2The flake is dissolved and selectively stripped PGMs by sodium hydroxide solution with the solid-to-liquid ratio of 1:10 at the temperature of 30 ℃, and the alkali dissolution time is 180 min. Dissolving PGMs enriched substance at 90 deg.C with hydrochloric acid and sodium chlorate, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 0.5mol/L, wherein the volume ratio of an organic phase to a solution is 0.5:1, and the extraction temperature is 35 ℃; then 0.5mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 3 times, and finally 99.99 percent Pd is obtained by reduction with formaldehyde. Adjusting raffinate H of Pd+Extracting Pt with the concentration of 3.0mol/L by using tributyl phosphate, wherein the volume ratio of an organic phase to a solution is 4:1, and the extraction temperature is 70 ℃; then 3.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 3 times, and finally 99.99 percent of Pt is obtained by reduction with formaldehyde; precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 700 deg.C for 3h, reducing with hydrogen to obtain Rh powder, repeatedly boiling Rh powder with HCl and HF for 3 times, washing with deionized water, and oven drying to obtain 99.99% Rh.
Example 6
Shearing the metal carrier waste automobile exhaust catalyst into 8cm2The flake is dissolved and selectively stripped PGMs by sodium hydroxide solution with the solid-to-liquid ratio of 1:8 at the temperature of 40 ℃, and the alkali dissolution time is 150 min. Dissolving PGMs concentrate with hydrochloric acid and sodium chlorate at 80 deg.C, and reusing 732 cation exchange resinFat removal of Fe from PGMs solution3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 1.2mol/L, wherein the volume ratio of an organic phase to a solution is 1:1, and the extraction temperature is 55 ℃; then 1.7mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 3 times, and finally 99.99 percent Pd is obtained by reduction with formaldehyde. Adjusting raffinate H of Pd+Extracting Pt with tributyl phosphate at a concentration of 4.5mol/L, wherein the volume ratio of the organic phase to the solution is 6:1, and the extraction temperature is 40 ℃; then 2.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 3 times, and finally 99.99 percent of Pt is obtained by reduction with formaldehyde; precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 900 deg.C for 2h, reducing with hydrogen to obtain Rh powder, repeatedly boiling Rh powder with HCl and HF for 3 times, washing with deionized water, and oven drying to obtain 99.99% Rh.
Example 7
Shearing the metal carrier waste automobile exhaust catalyst into 8cm2The flake is dissolved with potassium hydroxide solution with a solid-to-liquid ratio of 1:5 at 60 ℃ for selective stripping of PGMs, and the alkali dissolution time is 100 min. Dissolving PGMs enriched substance with hydrochloric acid and sodium chlorate at 70 deg.C, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 0.2mol/L, wherein the volume ratio of an organic phase to a solution is 2:1, and the extraction temperature is 35 ℃; then 1.4mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 3 times, and finally, 99.99 percent Pd is obtained by reduction with formaldehyde. Adjusting raffinate H of Pd+The concentration is 2.5mol/L, tributyl phosphate is adopted to extract Pt, the volume ratio of an organic phase to a solution is 3:1, and the extraction temperature is 50 ℃; then, back extraction is carried out by adopting 4.0mol/L hydrochloric acid, repeated extraction is carried out for 3 times, and finally, 99.99 percent of Pt is obtained by reduction by using formaldehyde; precipitating Rh from the Pt raffinate by using saturated ammonium chloride solution to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 1000 deg.C for 2 hr, and introducing hydrogenReducing to obtain Rh powder, repeatedly boiling the Rh powder with HCl and HF for 3 times, washing with deionized water, and drying to obtain 99.99% Rh.
Example 8
Shearing the metal carrier waste automobile exhaust catalyst into 12cm2The flake is dissolved and selectively stripped PGMs by sodium hydroxide solution with the solid-to-liquid ratio of 1:3 at the temperature of 95 ℃, and the alkali dissolution time is 40 min. Dissolving PGMs enriched substance at 70 deg.C with hydrochloric acid and sodium chlorate, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 0.8mol/L, wherein the volume ratio of an organic phase to a solution is 1.5:1, and the extraction temperature is 25 ℃; then 2.0mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 3 times, and finally, 99.99 percent Pd is obtained by reduction with formaldehyde. Adjusting raffinate H of Pd+Extracting Pt with the concentration of 3.5mol/L by using tributyl phosphate, wherein the volume ratio of an organic phase to a solution is 4:1, and the extraction temperature is 40 ℃; then, 5.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 2 times, and finally, 99.99 percent of Pt is obtained by reduction with formaldehyde; precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 800 deg.C for 3h, reducing with hydrogen to obtain Rh powder, repeatedly boiling Rh powder with HCl and HF for 3 times, washing with deionized water, and oven drying to obtain 99.99% Rh.
Example 9
Shearing the metal carrier waste automobile exhaust catalyst into 14cm2The flake is dissolved and selectively stripped PGMs by sodium hydroxide solution with the solid-to-liquid ratio of 1:8 at the temperature of 30 ℃, and the alkali dissolution time is 180 min. Dissolving PGMs enriched substance at 70 deg.C with hydrochloric acid and sodium chlorate, and removing Fe from PGMs solution with 732 cation exchange resin3+、Al3+、Na+And plasma impurity ions.
Conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 1.6mol/L, wherein the volume ratio of an organic phase to a solution is 1:1, and the extraction temperature is 55 ℃; then back extracting with 1.8mol/L ammonia water, and repeatedly extractingTaking 3 times, and finally reducing by formaldehyde to obtain 99.99 percent Pd. Adjusting raffinate H of Pd+Extracting Pt with tributyl phosphate at a concentration of 4.5mol/L, wherein the volume ratio of the organic phase to the solution is 6:1, and the extraction temperature is 40 ℃; then 2.5mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 3 times, and finally 99.99 percent of Pt is obtained by reduction with formaldehyde; precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 3 times; after washing (NH)4)RhCl6Calcining at 700 deg.C for 3h, reducing with hydrogen to obtain Rh powder, repeatedly boiling Rh powder with HCl and HF for 3 times, washing with deionized water, and oven drying to obtain 99.99% Rh.

Claims (1)

1. A method for recovering platinum group metals from metal carrier waste automobile exhaust catalysts is characterized by comprising the following steps:
(1) crushing and shearing: firstly, crushing and shearing a metal carrier waste automobile exhaust catalyst into pieces;
(2) alkali fusion/alkali dissolution: mixing the flaky waste catalyst with alkali, placing the mixture in a furnace for alkali fusion roasting, and then soaking in water; or directly adding the flaky waste catalyst into the alkali liquor to dissolve and leach without roasting;
(3) enrichment and separation: separating insoluble flaky metal carrier from the leaching solution, and washing for sale; filtering and separating the leachate and the PGMs concentrate;
(4) and (3) purification: separating and purifying the PGMs enrichment substance to obtain Pt, Pd and Rh products;
the waste automobile exhaust catalyst in the step (1) is sheared into 1-20cm2The sheet of (1);
purifying the PGMs enriched material in the step (4) to obtain Pt, Pd and Rh products with the concentration of more than 99.99%;
the alkali in the step (2) is any one or more than two of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
when roasting is needed in the step (2), the mass ratio of alkali to the waste automobile exhaust catalyst in the alkali fusion process is 0.5:1-2:1, the temperature is 600-;
when roasting is not performed in the step (2), the solid-to-liquid ratio in the alkali dissolution process is 1:3-1:10, the temperature is 30-95 ℃, and the alkali dissolution time is 30-180 min;
the specific purification step for separating the PGMs enrichment substance in the step (4) is as follows:
acid hydrolysis: firstly, aqua regia or HCl + NaClO is adopted3Dissolving the PGMs enrichment substance to obtain a PGMs solution;
impurity removal: removal of Fe from PGMs solution by cation exchange resin3+、Al3+、Na+Impurity ions;
purifying Pd: conditioning H with purified PGMs solution+Extracting Pd with diisoamyl sulfide at the concentration of 0.1-2.0mol/L, wherein the volume ratio of an organic phase to a solution is 0.5:1-2:1, and the extraction temperature is 20-60 ℃; then 0.1-2.0mol/L ammonia water is adopted for back extraction, repeated extraction is carried out for 2-4 times, and finally 99.99 percent Pd is obtained by reduction with formaldehyde;
and fourthly, purifying Pt: adjusting raffinate H of Pd+Extracting Pt with tributyl phosphate at the concentration of 2.0-6.0mol/L, wherein the volume ratio of the organic phase to the solution is 2:1-6:1, and the extraction temperature is 40-70 ℃; then 2.0-6.0mol/L hydrochloric acid is adopted for back extraction, repeated extraction is carried out for 2-4 times, and finally 99.99 percent of Pt is obtained by reduction with formaldehyde;
and fifthly, purifying Rh: precipitating Rh from Pt raffinate by using saturated solution of ammonium chloride to obtain (NH)4)RhCl6Washing with anhydrous ethanol for 2-3 times; after washing (NH)4)RhCl6Calcining for 2-4h at the temperature of 600-;
the recovery of PGMs using the method is greater than 99%.
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CN114606392A (en) * 2022-03-16 2022-06-10 贵研资源（易门）有限公司 Method for separating platinum group metal-containing coating in waste VOCs metal carrier catalyst
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