Method for synergistically recovering valuable elements from waste ternary lithium battery black powder and spent automobile catalyst

Abstract

The invention provides a method for synergistically recovering valuable elements from waste ternary lithium battery black powder and a spent automobile catalyst, and belongs to the technical field of solid waste recycling. The method comprises the following steps: mixing waste ternary lithium battery black powder, a spent automobile catalyst, coke and a slag former, and sequentially pelletizing and smelting to obtain lithium oxide-containing dust, PGMs-nickel cobalt manganese and smelting slag; carrying out magnetic separation on the smelting slag, and merging the secondarily enriched PGMs-nickel-cobalt-manganese alloy into the PGMs-nickel-cobalt-manganese alloy in the step (1); the PGMs-nickel cobalt manganese alloy, a hydrochloric acid solution and a sodium chlorate solution are mixed and then subjected to acidolysis, the obtained mixed solution is subjected to extraction, reverse extraction and precipitation, and recovery of platinum group metal, lithium and nickel cobalt manganese is achieved. The collaborative recovery method is adopted, the recovery rate of the platinum group metal is larger than or equal to 98%, the recovery rate of lithium is larger than 92%, the recovery rate of nickel-cobalt-manganese resources is larger than or equal to 90%, a new trapping agent does not need to be added in the platinum group metal trapping process, and valuable elements are fully applied.

Description

Technical Field

[0001] The present invention relates to the technical field of solid waste resource utilization, and in particular to a method for collaboratively recovering valuable elements from waste ternary lithium battery black powder and failed automobile catalysts. Background Art

[0002] Failed ternary lithium batteries contain abundant valuable metal elements such as lithium, nickel, cobalt, and manganese. The potential resources are huge and the economic value of recycling is high. The mainstream recycling process of spent automotive catalyst materials is to burn organic matter and graphite at high temperature and recover valuable metals in the form of alloys. This method is simple and easy to operate, but it causes serious air pollution and huge energy consumption. Wet extraction emits Cl 2 、SO 2 and NO X , low leaching rate and other problems.

[0003] Automotive catalysts are known as mobile platinum group metal mines. my country's primary mineral resources of platinum group metals account for only 0.12% of the world's reserves. The overall external dependence is high, and the supply and demand are seriously unbalanced. Therefore, the recycling of PGMs is an important guarantee for domestic supply. There are three main methods for recycling waste automotive catalysts: metal capture method, chlorination volatilization method, and synergistic capture method. The metal capture method is the mainstream process, which uses base metals such as iron, copper, and bismuth as a single capture agent to capture PGMs in smelting slag at high temperature. After smelting is completed, the metal alloy is first obtained, and then the high-purity precious metal is obtained through refining.

[0004] At present, there are many studies on the recovery of valuable elements in ternary lithium battery black powder materials and the recovery of platinum group metals in waste catalysts, but they are all separately recovered for lithium, nickel cobalt manganese, platinum group metals and other components, such as: CN111690812A, CN110527846B, CN110527835B, CN111321298A, CN108559846B, CN114921653A, CN118547165A, CN118563117A, CN117904437A, CN117721319A. The core of the above patents is to optimize the technology and methods for obtaining a certain purity of recyclables, without involving collaborative recovery, and without considering energy consumption and the emission of pollutants in the recovery process. Therefore, it is of great significance to study a method for the collaborative recovery of valuable elements from waste ternary lithium battery black powder and failed automobile catalysts. Summary of the invention

[0005] The purpose of the present invention is to provide a method for collaboratively recovering valuable elements from waste ternary lithium battery black powder and failed automobile catalysts, so as to solve the problem in the prior art that waste ternary lithium battery black powder and failed automobile catalysts cannot be collaboratively recovered.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for synergistically recovering valuable elements from waste ternary lithium battery black powder and failed automobile catalyst, comprising the following steps:

[0008] (1) mixing waste ternary lithium battery black powder, spent automobile catalyst, coke and slag-making agent, and then sequentially performing pelletizing and smelting to obtain lithium oxide dust, PGMs-nickel-cobalt-manganese alloy and smelting slag;

[0009] (2) subjecting the smelting slag to magnetic separation, and incorporating the secondary enriched PGMs-nickel-cobalt-manganese alloy particles into the PGMs-nickel-cobalt-manganese alloy of step (1);

[0010] (3) mixing the PGMs-nickel-cobalt-manganese alloy, hydrochloric acid solution and sodium chlorate solution and then acid-lyzing the mixture to extract palladium and platinum in sequence to obtain a palladium-containing organic phase, a platinum-containing organic phase and a rhodium-containing solution;

[0011] (4) stripping and precipitating the palladium-containing organic phase and the platinum-containing organic phase respectively to obtain a palladium precipitate and a platinum precipitate; precipitating the rhodium-containing solution to obtain a rhodium precipitate and a rhodium precipitation residual solution;

[0012] (5) calcining the palladium precipitate, the platinum precipitate and the rhodium precipitate to obtain palladium powder, platinum powder and rhodium powder respectively;

[0013] (6) precipitating the residual solution of rhodium precipitation to obtain nickel carbonate, cobalt carbonate and manganese carbonate.

[0014] Preferably, in the step (1), the mass ratio of waste ternary lithium battery black powder, failed automobile catalyst, coke and slag-forming agent is 8-12:100-200:5-10:50-160; the slag-forming agent comprises one or more of limestone, iron oxide, boron oxide, fluorite and borax.

[0015] Preferably, in step (1), the smelting temperature is 1500-1800° C., and the smelting time is 1-4 hours.

[0016] Preferably, in step (2), the intensity of magnetic separation is 0.1-0.5T.

[0017] Preferably, in the step (3), the mass ratio of the hydrochloric acid solution to the sodium chlorate solution is 7-12:1, wherein the concentration of the hydrochloric acid solution is 3-5 mol / L, and the mass concentration of the sodium chlorate solution is 20-40%; and the mass volume ratio of the PGMs-nickel-cobalt-manganese alloy to the hydrochloric acid solution is 1 g:4-8 mL.

[0018] Preferably, in step (3), the acid hydrolysis temperature is 80-90°C.

[0019] Preferably, in step (3), the extractant for extracting palladium is diisoamyl sulfide (S201), and the extractant for extracting platinum is tributyl phosphate (TBP).

[0020] Preferably, in step (4), the palladium-containing organic phase is stripped with a thiourea solution, and the platinum-containing organic phase is stripped with a sodium hydroxide solution.

[0021] Preferably, in the step (5), the calcination treatment is carried out in a hydrogen atmosphere, the calcination treatment temperature is 600-700° C., and the calcination treatment time is 1-3 hours.

[0022] Preferably, in step (6), the precipitation comprises a first precipitation, a second precipitation and a third precipitation.

[0023] Beneficial effects of the present invention:

[0024] (1) The present invention uses graphite in waste ternary lithium battery black powder as a reducing agent and oxides such as nickel, cobalt and manganese as collectors, and reduces the nickel, cobalt and manganese elements therein to form alloy droplets through high-temperature smelting, which participates in the enrichment process of platinum group metals. The present invention realizes the resource utilization of graphite in ternary lithium battery black powder.

[0025] (2) The traditional method of recycling black powder from waste ternary lithium batteries consumes a lot of energy and produces pollutants. The present invention utilizes the high temperature reduction of volatile lithium during the recovery of spent automobile catalysts to increase the metal recovery rate, reduce the recovery cost, and shorten the recovery process.

[0026] (3) The smelting slag obtained by the present invention is recovered again after magnetic separation, and high-value platinum, palladium, rhodium and the like in the smelting slag are recovered, thereby effectively improving the recovery rate of platinum group metals.

[0027] (4) The present invention adopts a collaborative recovery treatment method, with a platinum group metal recovery rate of ≥98%, a lithium recovery rate of greater than 92%, a nickel-cobalt-manganese resource recovery rate of ≥90%, and the purity of nickel carbonate, cobalt carbonate and manganese carbonate higher than 90%. The platinum group metal capture process does not require the addition of new capture agents, and the valuable elements of platinum, palladium, rhodium, nickel, cobalt and manganese are fully utilized. In addition, the comprehensive recovery of valuable elements in waste ternary battery black powder and failed automobile catalysts and the collaborative treatment of solid wastes are achieved. DETAILED DESCRIPTION

[0028] The present invention provides a method for synergistically recovering valuable elements from waste ternary lithium battery black powder and failed automobile catalyst, comprising the following steps:

[0029] (1) mixing waste ternary lithium battery black powder, spent automobile catalyst, coke and slag-making agent, and then sequentially performing pelletizing and smelting to obtain lithium oxide dust, PGMs-nickel-cobalt-manganese alloy and smelting slag;

[0030] (2) subjecting the smelting slag to magnetic separation, and incorporating the secondary enriched PGMs-nickel-cobalt-manganese alloy particles into the PGMs-nickel-cobalt-manganese alloy of step (1);

[0031] (3) mixing the PGMs-nickel-cobalt-manganese alloy, hydrochloric acid solution and sodium chlorate solution and then acid-lyzing the mixture to extract palladium and platinum in sequence to obtain a palladium-containing organic phase, a platinum-containing organic phase and a rhodium-containing solution;

[0032] (4) stripping and precipitating the palladium-containing organic phase and the platinum-containing organic phase respectively to obtain a palladium precipitate and a platinum precipitate; precipitating the rhodium-containing solution to obtain a rhodium precipitate and a rhodium precipitation residual solution;

[0033] (5) calcining the palladium precipitate, the platinum precipitate and the rhodium precipitate to obtain palladium powder, platinum powder and rhodium powder respectively;

[0034] (6) precipitating the residual solution of rhodium precipitation to obtain nickel carbonate, cobalt carbonate and manganese carbonate.

[0035] In the present invention, in the step (1), the mass ratio of waste ternary lithium battery black powder, failed automobile catalyst, coke and slag-forming agent is 8-12:100-200:5-10:50-160, preferably 9-11:120-180:6-8:80-140; the slag-forming agent comprises one or more of limestone, iron oxide, boron oxide, fluorite and borax.

[0036] In the present invention, in the step (1), the smelting temperature is 1500-1800°C, preferably 1550-1750°C, more preferably 1600-1700°C, and the smelting time is 1-4h, preferably 2-4h, more preferably 3-4h.

[0037] In the present invention, the smelting slag is preferably crushed before magnetic separation.

[0038] In the present invention, in the step (2), the intensity of magnetic separation is 0.1 to 0.5 T, preferably 0.2 to 0.4 T, and more preferably 0.25 to 0.3 T.

[0039] In the present invention, in the step (3), the mass ratio of the hydrochloric acid solution to the sodium chlorate solution is 7 to 12:1, preferably 8 to 11:1, and more preferably 9 to 10:1; wherein the concentration of the hydrochloric acid solution is 3 to 5 mol / L, preferably 3.5 to 4.5 mol / L, and more preferably 4 mol / L; the mass concentration of the sodium chlorate solution is 20 to 40%, preferably 25 to 35%, and more preferably 30%; the mass volume ratio of the PGMs-nickel-cobalt-manganese alloy to the hydrochloric acid solution is 1 g: 4 to 8 mL, preferably 1 g: 5 to 7 mL, and more preferably 1 g: 6 mL.

[0040] In the present invention, in step (3), the temperature of the acid hydrolysis is 80-90°C, preferably 80°C, 85°C, 90°C, and more preferably 90°C.

[0041] In the present invention, in step (3), the extractant for extracting palladium is diisoamyl sulfide (S201), and the extractant for extracting platinum is tributyl phosphate (TBP).

[0042] In the present invention, the volume ratio of the extractant to the extracted liquid during extraction is 1:5-3.

[0043] In the present invention, the extraction is carried out in a three-stage extraction manner, and the total extraction rate exceeds 99%.

[0044] In the present invention, in the step (4), the palladium-containing organic phase is stripped with a thiourea solution, and the platinum-containing organic phase is stripped with a sodium hydroxide solution.

[0045] In the present invention, the palladium-containing organic phase is back-extracted with a thiourea solution to obtain a palladium-containing aqueous solution; the platinum-containing organic phase is back-extracted with a sodium hydroxide solution to obtain a platinum-containing aqueous solution.

[0046] In the present invention, the stripping is carried out in a three-stage stripping manner, and after the three-stage stripping, about 99% of the palladium and platinum are carried into the stripping agent.

[0047] In the present invention, the palladium-containing aqueous solution and the platinum-containing aqueous solution are adjusted for metal content before precipitation, wherein the adjusted metal content is 40 to 50 g / L. The present invention has no particular restrictions on the type of precipitant, as long as it is a precipitant that can precipitate palladium or platinum. In the embodiment of the present invention, ammonium chloride is preferably used as the precipitant.

[0048] In the present invention, in the step (5), the calcination treatment is carried out in a hydrogen atmosphere, the calcination treatment temperature is 600-700°C, preferably 620-680°C, and more preferably 650°C; the calcination treatment time is 1-3h, preferably 2h.

[0049] In the present invention, in the step (6), the precipitation comprises a first precipitation, a second precipitation and a third precipitation. First, the pH value of the rhodium precipitation residual solution is adjusted to 5-6.5, and carbonate is added for the first precipitation to obtain nickel carbonate and nickel precipitation residual solution; the pH value of the nickel precipitation residual solution is adjusted to 7-8, and carbonate is added for the second precipitation to obtain cobalt carbonate and cobalt precipitation residual solution; the pH value of the cobalt precipitation residual solution is adjusted to 8.5-10, and carbonate is added for the third precipitation to obtain manganese carbonate.

[0050] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0051] The main components of the waste ternary lithium battery black powder used in the embodiment of the present invention are shown in Table 1:

[0052] Table 1 Main components of black powder from waste ternary lithium batteries

[0053]

[0054]

[0055] The main components of the spent automobile catalyst used in the embodiments of the present invention are shown in Table 2:

[0056] Table 2 Main components of spent automobile catalysts

[0057] Element Content wt% <![CDATA[Al 2 THE 3 ]]> 39 <![CDATA[SiO 2 ]]> 34 MgO 13 <![CDATA[ZrO 2 ]]> 4 <![CDATA[CeO 2 ]]> 3 Pt 82g / t Pd 1548g / t R 189g / t

[0058] Example 1

[0059] Waste ternary lithium battery black powder, failed automobile catalyst, coke and limestone are mixed in a mass ratio of 10:100:6:80 to form balls (particle size is 15-20mm). The obtained balls are sent to an electric arc furnace via a conveyor belt and smelted at a temperature of 1650°C for 2h. The lithium oxide dust in the flue gas is recovered during the smelting process. The lithium oxide content is 87.3% and the lithium recovery rate is 93.2%. After the smelting, PGMs-nickel cobalt manganese alloy and smelting slag are obtained. The smelting slag is cooled and crushed, and magnetic separation is performed in a 0.2T magnetic field. The secondary enriched PGMs-nickel cobalt manganese alloy is combined with the PGMs-nickel cobalt manganese alloy obtained by smelting, and the remaining is tailings, wherein the content of platinum group elements in PGMs-nickel cobalt manganese alloy is 5.89%, and the content of platinum group elements in the tailings is 8.9g / t.

[0060] According to the mass volume ratio of PGMs-nickel cobalt manganese alloy and hydrochloric acid solution of 1g:6mL, PGMs-nickel cobalt manganese alloy and hydrochloric acid solution (concentration of 4mol / L) were mixed, heated to 90°C, and sodium chlorate solution (mass concentration of 30%) was added dropwise, wherein the mass ratio of hydrochloric acid solution to sodium chlorate solution was 9:1, until the PGMs-nickel cobalt manganese alloy was completely dissolved to obtain a mixed solution.

[0061] According to V O / V A =1:3 The mixed solution was subjected to three-stage extraction with S201. During the extraction process, the mixture was stirred for 5 minutes and then allowed to stand for 15 minutes. After the three-stage extraction, the two phases were separated to obtain a palladium-containing organic phase and a first raffinate. O / V A=1 Add thiourea solution (mass concentration is 5%) to the palladium-containing organic phase for three-stage stripping. During the stripping process, stir for 3 minutes and then stand for 15 minutes. After three-stage stripping, a palladium-containing aqueous solution is obtained. The palladium content in the palladium-containing aqueous solution is adjusted to 45 g / L. Ammonium chloride is added (the amount of ammonium chloride added is 100 g / L, that is, 100 g of ammonium chloride is added per liter of solution) and the solution is allowed to stand for 40 minutes to obtain a palladium precipitate.

[0062] According to V O / V A =1:3 The first raffinate and TBP were mixed for three-stage extraction. During the extraction process, the mixture was stirred for 5 minutes and then allowed to stand for 15 minutes. After the three-stage extraction, the two phases were separated to obtain a platinum-containing organic phase and a second raffinate. O / V A =1 Sodium hydroxide solution (mass concentration is 10%) is added to the platinum-containing organic phase for three-stage stripping. During the stripping process, the solution is stirred for 3 minutes and then allowed to stand for 15 minutes. After three-stage stripping, a platinum-containing aqueous solution is obtained. The platinum content in the platinum-containing aqueous solution is adjusted to 45 g / L. Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added and allowed to stand for 40 minutes to obtain a platinum precipitate.

[0063] Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added to the second raffinate to obtain rhodium precipitate and rhodium precipitate raffinate; the pH value of the rhodium precipitate raffinate is adjusted to 6 with sodium hydroxide solution, and sodium carbonate (the amount of sodium carbonate added is based on Ni 2+ and CO 3 2- The molar ratio of the nickel precipitate is 1:1.1, and nickel carbonate and a residual solution of nickel precipitation are obtained; the pH value of the residual solution of nickel precipitation is adjusted to 7 with a sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Co 2+ and CO 3 2- The molar ratio of Mn is 1:1.1, and cobalt carbonate and cobalt precipitation residual solution are obtained; the pH value of the cobalt precipitation residual solution is adjusted to 9 with sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Mn 2+ and CO 3 2- The molar ratio is 1:1.5 to obtain manganese carbonate and tail liquid.

[0064] The palladium precipitate, platinum precipitate and rhodium precipitate were calcined at 650° C. for 2 h in a hydrogen atmosphere to obtain palladium, platinum and rhodium. The purity of palladium, platinum and rhodium was 99.91%, the comprehensive recovery rate of palladium, platinum and rhodium was 98.1%, the recovery rate of nickel was 96.3%, the recovery rate of cobalt was 98.1%, and the recovery rate of manganese was 92.3%.

[0065] Example 2

[0066] Waste ternary lithium battery black powder, failed automobile catalyst, coke and limestone are mixed in a mass ratio of 10:130:8:100 to form balls (particle size is 15-20mm). The obtained balls are sent to an electric arc furnace via a conveyor belt and smelted at a temperature of 1750°C for 3 hours. The lithium oxide dust in the flue gas is recovered during the smelting process. The lithium oxide content is 85.3% and the lithium recovery rate is 96.2%. After the smelting, PGMs-nickel cobalt manganese alloy and smelting slag are obtained. The smelting slag is cooled and crushed, and magnetic separation is performed in a 0.3T magnetic field. The secondary enriched PGMs-nickel cobalt manganese alloy is combined with the PGMs-nickel cobalt manganese alloy obtained by smelting, and the remaining is tailings, wherein the content of platinum group elements in PGMs-nickel cobalt manganese alloy is 7.92%, and the content of platinum group elements in the tailings is 7.6g / t.

[0067] According to the mass volume ratio of PGMs-nickel cobalt manganese alloy and hydrochloric acid solution of 1g:8mL, PGMs-nickel cobalt manganese alloy and hydrochloric acid solution (concentration of 4mol / L) were mixed, heated to 85°C, and sodium chlorate solution (mass concentration of 30%) was added dropwise, wherein the mass ratio of hydrochloric acid solution to sodium chlorate solution was 9:1, until the PGMs-nickel cobalt manganese alloy was completely dissolved to obtain a mixed solution.

[0068] According to V O / V A =1:3 The mixed solution was subjected to three-stage extraction with S201. During the extraction process, the mixture was stirred for 4 minutes and then allowed to stand for 15 minutes. After the three-stage extraction, the two phases were separated to obtain a palladium-containing organic phase and a first raffinate. O / V A =1 Add thiourea solution (mass concentration is 5%) to the palladium-containing organic phase for three-stage stripping. During the stripping process, stir for 2 minutes and then stand for 17 minutes. After three-stage stripping, a palladium-containing aqueous solution is obtained. The palladium content in the palladium-containing aqueous solution is adjusted to 49 g / L. Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added and allowed to stand for 46 minutes to obtain a palladium precipitate.

[0069] According to V O / V A =1:3 The first raffinate and TBP were mixed for three-stage extraction. During the extraction process, the mixture was stirred for 4 minutes and then allowed to stand for 15 minutes. After the three-stage extraction, the two phases were separated to obtain a platinum-containing organic phase and a second raffinate. According to V O / V A =1 Sodium hydroxide solution (mass concentration 10%) was added to the platinum-containing organic phase for three-stage stripping. During the stripping process, the solution was stirred for 2 minutes and then allowed to stand for 17 minutes. A platinum-containing aqueous solution was obtained through three-stage stripping. The platinum content in the platinum-containing aqueous solution was adjusted to 49 g / L. Ammonium chloride (the amount of ammonium chloride added was 100 g / L) was added and allowed to stand for 40 minutes to obtain a platinum precipitate.

[0070] Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added to the above-mentioned second raffinate to obtain rhodium precipitate and rhodium precipitate raffinate; the pH value of the rhodium precipitate raffinate is adjusted to 6.5 with sodium hydroxide solution, and sodium carbonate (the amount of sodium carbonate added is based on Ni 2+ and CO 3 2- The molar ratio of the nickel precipitate is 1:1.1, and nickel carbonate and a residual solution of nickel precipitation are obtained; the pH value of the residual solution of nickel precipitation is adjusted to 7 with a sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Co 2+ and CO 3 2- The molar ratio of Mn is 1:1.1, and cobalt carbonate and cobalt precipitation residual solution are obtained; the pH value of the cobalt precipitation residual solution is adjusted to 8.7 with sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Mn 2+ and CO 3 2- The molar ratio is 1:1.5 to obtain manganese carbonate and tail liquid.

[0071] The palladium precipitate, platinum precipitate and rhodium precipitate were calcined at 650°C for 2h under hydrogen atmosphere to obtain palladium, platinum and rhodium. The purity of palladium, platinum and rhodium was 99.93%, the comprehensive recovery rate of palladium, platinum and rhodium was 98.07%, the recovery rate of nickel was 96.7%, the recovery rate of cobalt was 98.1%, and the recovery rate of manganese was 93.5%.

[0072] Example 3

[0073] Waste ternary lithium battery black powder, failed automobile catalyst, coke and boron oxide are mixed in a mass ratio of 10:150:10:80 to form balls (particle size is 15-20mm). The obtained balls are sent to an electric arc furnace via a conveyor belt and smelted at a temperature of 1700°C for 4 hours. During the smelting process, lithium oxide dust is recovered from the flue gas. The lithium oxide content is 86.7% and the lithium recovery rate is 95.6%. After the smelting, PGMs-nickel cobalt manganese alloy and smelting slag are obtained. The smelting slag is cooled and crushed, and magnetic separation is performed in a 0.25T magnetic field. The secondary enriched PGMs-nickel cobalt manganese alloy is combined with the PGMs-nickel cobalt manganese alloy obtained by smelting. The remaining is tailings, in which the content of platinum group elements in PGMs-nickel cobalt manganese alloy is 6.79%, and the content of platinum group elements in the tailings is 8.2g / t.

[0074] According to the mass volume ratio of PGMs-nickel cobalt manganese alloy and hydrochloric acid solution of 1g:4mL, PGMs-nickel cobalt manganese alloy and hydrochloric acid solution (concentration of 4mol / L) were mixed, heated to 80°C, and sodium chlorate solution (mass concentration of 30%) was added dropwise, wherein the mass ratio of hydrochloric acid solution to sodium chlorate solution was 11:1, until the PGMs-nickel cobalt manganese alloy was completely dissolved to obtain a mixed solution.

[0075] According to V O / V A =1:3 The mixed solution was subjected to three-stage extraction with S201. During the extraction process, the mixture was stirred for 3 minutes and then allowed to stand for 17 minutes. After the three-stage extraction, the two phases were separated to obtain a palladium-containing organic phase and a first raffinate. O / V A =1 Add thiourea solution (mass concentration is 5%) to the palladium-containing organic phase for three-stage stripping. During the stripping process, stir for 3 minutes and then stand for 15 minutes. After three-stage stripping, a palladium-containing aqueous solution is obtained. The concentration of palladium in the palladium-containing aqueous solution is adjusted to 42 g / L. Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added and the solution is allowed to stand for 38 minutes to obtain a palladium precipitate.

[0076] According to V O / V A =1:3 The first raffinate and TBP were mixed for three-stage extraction. During the extraction process, the mixture was stirred for 3 minutes and then allowed to stand for 17 minutes. After the three-stage extraction, the two phases were separated to obtain a platinum-containing organic phase and a second raffinate. O / V A =1 Sodium hydroxide solution (mass concentration 10%) was added to the platinum-containing organic phase for tertiary stripping. During the stripping process, the solution was stirred for 3 minutes and then allowed to stand for 15 minutes. A platinum-containing aqueous solution was obtained through tertiary stripping. The concentration of platinum in the platinum-containing aqueous solution was adjusted to 42 g / L. Ammonium chloride (the amount of ammonium chloride added was 100 g / L) was added and allowed to stand for 38 minutes to obtain a platinum precipitate.

[0077] Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added to the above-mentioned second raffinate to obtain rhodium precipitate and rhodium precipitate raffinate; the pH value of the rhodium precipitate raffinate is adjusted to 6.5 with sodium hydroxide solution, and sodium carbonate (the amount of sodium carbonate added is based on Ni 2+ and CO 3 2- The molar ratio of the nickel precipitate is 1:1.1, and nickel carbonate and a residual solution of nickel precipitation are obtained; the pH value of the residual solution of nickel precipitation is adjusted to 7 with a sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Co 2+ and CO 3 2-The molar ratio of Mn is 1:1.1, and cobalt carbonate and cobalt precipitation residual solution are obtained; the pH value of the cobalt precipitation residual solution is adjusted to 8.7 with sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Mn 2+ and CO 3 2- The molar ratio is 1:1.5 to obtain manganese carbonate and tail liquid.

[0078] The palladium precipitate, platinum precipitate and rhodium precipitate were calcined at 650°C for 2h under hydrogen atmosphere to obtain palladium, platinum and rhodium. The purity of palladium, platinum and rhodium was 99.90%, the comprehensive recovery rate of palladium, platinum and rhodium was 98.1%, the recovery rate of nickel was 97.8%, the recovery rate of cobalt was 98.6%, and the recovery rate of manganese was 92.4%.

[0079] Example 4

[0080] Waste ternary lithium battery black powder, failed automobile catalyst, coke and borax are mixed in a mass ratio of 10:120:10:110 to form balls (particle size is 15-20mm). The obtained balls are sent into an electric arc furnace via a conveyor belt and smelted at a temperature of 1600°C for 2h. During the smelting process, lithium oxide dust is recovered from the flue gas. The lithium oxide content is 89.7% and the lithium recovery rate is 93.1%. After the smelting, PGMs-nickel cobalt manganese alloy and smelting slag are obtained. The smelting slag is cooled and crushed, and magnetic separation is performed in a 0.25T magnetic field. The secondary enriched PGMs-nickel cobalt manganese alloy is combined with the PGMs-nickel cobalt manganese alloy obtained by smelting, and the remaining is tailings, wherein the content of platinum group elements in PGMs-nickel cobalt manganese alloy is 5.79%, and the content of platinum group elements in the tailings is 9.7g / t.

[0081] According to the mass volume ratio of PGMs-nickel cobalt manganese alloy and hydrochloric acid solution of 1g:5mL, PGMs-nickel cobalt manganese alloy and hydrochloric acid solution (concentration of 4mol / L) are mixed, heated to 80°C, and sodium chlorate solution (mass concentration of 30%) is added dropwise, wherein the mass ratio of hydrochloric acid solution to sodium chlorate solution is 8:1, until the PGMs-nickel cobalt manganese alloy is completely dissolved to obtain a mixed solution.

[0082] According to V O / V A =1:3 The mixed solution was subjected to three-stage extraction with S201. During the extraction process, the mixture was stirred for 4 minutes and then allowed to stand for 16 minutes. After the three-stage extraction, the two phases were separated to obtain a palladium-containing organic phase and a first raffinate. O / V A=1 Add thiourea solution (mass concentration is 5%) to the palladium-containing organic phase for three-stage stripping. During the stripping process, stir for 4 minutes and then stand for 14 minutes. After three-stage stripping, a palladium-containing aqueous solution is obtained. The palladium content in the palladium-containing aqueous solution is adjusted to 47 g / L. Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added and allowed to stand for 45 minutes to obtain a palladium precipitate.

[0083] According to V O / V A =1:3 The first raffinate and TBP were mixed for three-stage extraction. During the extraction process, the mixture was stirred for 4 minutes and then allowed to stand for 16 minutes. After the three-stage extraction, the two phases were separated to obtain a platinum-containing organic phase and a second raffinate. According to V O / V A =1 Sodium hydroxide solution (mass concentration 10%) was added to the platinum-containing organic phase for three-stage stripping. During the stripping process, the solution was stirred for 4 minutes and then allowed to stand for 14 minutes. A platinum-containing aqueous solution was obtained through three-stage stripping. The platinum content in the platinum-containing aqueous solution was adjusted to 47 g / L. Ammonium chloride (the amount of ammonium chloride added was 100 g / L) was added and allowed to stand for 45 minutes to obtain a platinum precipitate.

[0084] Ammonium chloride (the amount of ammonium chloride added is 100 g / L) is added to the second raffinate to obtain rhodium precipitate and rhodium precipitate raffinate; the pH value of the rhodium precipitate raffinate is adjusted to 6 with sodium hydroxide solution, and sodium carbonate (the amount of sodium carbonate added is based on Ni 2+ and CO 3 2- The molar ratio of the nickel precipitate is 1:1.1, and nickel carbonate and a residual solution of nickel precipitation are obtained; the pH value of the residual solution of nickel precipitation is adjusted to 7 with a sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Co 2+ and CO 3 2- The molar ratio of Mn is 1:1.1, and cobalt carbonate and cobalt precipitation residual solution are obtained; the pH value of the cobalt precipitation residual solution is adjusted to 9.2 with sodium hydroxide solution, and sodium carbonate is added (the amount of sodium carbonate added is based on Mn 2+ and CO 3 2- The molar ratio is 1:1.5 to obtain manganese carbonate and tail liquid.

[0085] The palladium precipitate, platinum precipitate and rhodium precipitate were calcined at 650° C. for 2 h in a hydrogen atmosphere to obtain palladium, platinum and rhodium. The purity of palladium, platinum and rhodium was 99.91%, the comprehensive recovery rate of palladium, platinum and rhodium was 98%, the recovery rate of nickel was 96.2%, the recovery rate of cobalt was 98.0%, and the recovery rate of manganese was 93.1%.

[0086] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for recovering valuable elements from waste ternary lithium battery black powder and failed automobile catalysts, characterized in that: The steps include: (1) mixing waste ternary lithium battery black powder, spent automobile catalyst, coke and slag-making agent, and then sequentially performing pelletizing and smelting to obtain lithium oxide dust, PGMs-nickel-cobalt-manganese alloy and smelting slag; (2) subjecting the smelting slag to magnetic separation, and incorporating the secondary enriched PGMs-nickel-cobalt-manganese alloy particles into the PGMs-nickel-cobalt-manganese alloy of step (1); (3) mixing the PGMs-nickel-cobalt-manganese alloy, the hydrochloric acid solution and the sodium chlorate solution and then acid-lyzing the mixture, and extracting palladium and platinum in sequence with the obtained mixed solution to obtain a palladium-containing organic phase, a platinum-containing organic phase and a rhodium-containing solution; (4) stripping and precipitating the palladium-containing organic phase and the platinum-containing organic phase respectively to obtain a palladium precipitate and a platinum precipitate; precipitating the rhodium-containing solution to obtain a rhodium precipitate and a rhodium precipitation residual solution; (5) calcining the palladium precipitate, the platinum precipitate and the rhodium precipitate to obtain palladium powder, platinum powder and rhodium powder respectively; (6) precipitating the residual solution of rhodium precipitation to obtain nickel carbonate, cobalt carbonate and manganese carbonate.

2. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 1, characterized in that: In the step (1), the mass ratio of waste ternary lithium battery black powder, failed automobile catalyst, coke and slag-forming agent is 8-12:100-200:5-10:50-160; the slag-forming agent comprises one or more of limestone, iron oxide, boron oxide, fluorite and borax.

3. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 1 or 2, characterized in that: In the step (1), the smelting temperature is 1500-1800° C., and the smelting time is 1-4 hours.

4. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 3, characterized in that: In the step (2), the intensity of magnetic separation is 0.1 to 0.5 T.

5. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 2 or 4, characterized in that: In the step (3), the mass ratio of the hydrochloric acid solution to the sodium chlorate solution is 7-12:1, wherein the concentration of the hydrochloric acid solution is 3-5 mol / L, and the mass concentration of the sodium chlorate solution is 20-40%; the mass volume ratio of the PGMs-nickel-cobalt-manganese alloy to the hydrochloric acid solution is 1 g:4-8 mL.

6. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 5, characterized in that: In the step (3), the acid hydrolysis temperature is 80 to 90°C.

7. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 2, 4 or 6, characterized in that: In the step (3), the extractant for extracting palladium is diisoamyl sulfide, and the extractant for extracting platinum is tributyl phosphate.

8. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 7, characterized in that: In the step (4), the palladium-containing organic phase is stripped with a thiourea solution, and the platinum-containing organic phase is stripped with a sodium hydroxide solution.

9. The method for recovering valuable elements by synergistically using waste ternary lithium battery black powder and spent automobile catalyst according to claim 6 or 8, characterized in that: In the step (5), the calcination treatment is carried out in a hydrogen atmosphere, the calcination treatment temperature is 600-700° C., and the calcination treatment time is 1-3 hours.

10. The method for recovering valuable elements by using waste ternary lithium battery black powder and spent automobile catalyst according to claim 9, characterized in that: In the step (6), the precipitation includes a first precipitation, a second precipitation and a third precipitation.

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