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WO2024058441A1 - Procédé de récupération de métal du groupe du platine à partir de déchets de catalyseur en utilisant du biocyanure et du liquide ionique - Google Patents

Procédé de récupération de métal du groupe du platine à partir de déchets de catalyseur en utilisant du biocyanure et du liquide ionique Download PDF

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WO2024058441A1
WO2024058441A1 PCT/KR2023/012145 KR2023012145W WO2024058441A1 WO 2024058441 A1 WO2024058441 A1 WO 2024058441A1 KR 2023012145 W KR2023012145 W KR 2023012145W WO 2024058441 A1 WO2024058441 A1 WO 2024058441A1
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Prior art keywords
platinum group
cyanide
specifically
platinum
biocyanide
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Korean (ko)
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김현중
사디아일야스
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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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
    • 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
    • C22B11/08—Obtaining noble metals by cyaniding
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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

Definitions

  • This disclosure relates to a process for recovering platinum group metals from spent catalysts using biocyanide and ionic liquids. More specifically, the present disclosure relates to a process of bioleaching platinum group metals contained in a spent catalyst using biocyanide produced from microorganisms and then recovering the platinum group metals with high purity using an organophosphorus ionic liquid as an extractant. It's about.
  • catalytic converters Due to the recently strengthened regulation of polluting gases, catalytic converters have become mandatory to treat exhaust gases emitted from various vehicles.
  • precious metals specifically platinum (Pt) and palladium, are used as catalyst components. (Pd) etc. are applied.
  • spent catalytic converters are processed through a pyrometallurgical process, where the precious metals are collected in alloy form using collector metals or collector metals such as Cu 0 and Fe 0 .
  • collector metals or collector metals such as Cu 0 and Fe 0 .
  • this process is not only difficult to see as a direct extraction method, but is also energy-intensive and involves isolating relatively low weight precious metals after subsequent chemical leaching (or elution), as well as producing large amounts of 2 Tea waste is produced in the form of slag.
  • the slag produced in this way exhibits high alkalinity and is therefore not suitable for landfill.
  • the problem of emitting a large amount of carbon dioxide has been pointed out, and after the alloy is reprocessed and separated from the collected metal, it must be treated with individual precious metal salts.
  • the platinum recovery rate is about 80 to 94%
  • the palladium recovery rate is about 80 to 96%. Therefore, there is a problem that greatly increases the processing cost of the entire recycling process.
  • bioleaching-based technology does not specifically mention a method of recovering platinum group metals from cyanide leachate.
  • a method of precipitating them through the addition of ion exchange resin and sulfide such as sodium sulfide (NaHS) is also known (for example, U.S. Patent No. 7544231).
  • NaHS sodium sulfide
  • an environmentally friendly method is provided to effectively recover platinum group metals while minimizing the use of toxic substances at a lower cost compared to the prior art.
  • Another embodiment of the present disclosure seeks to provide a method for recycling the residue generated after recovering platinum group metals from a spent catalyst using microorganisms.
  • a method for recovering platinum group metals from a spent catalyst containing a is provided.
  • the platinum group-containing spent catalyst may contain at least one platinum group metal selected from the group consisting of platinum and palladium.
  • the platinum group-containing spent catalyst may not contain rhodium.
  • the platinum group-containing spent catalyst may be provided in step a) in the form of particles or pulverized material having a particle size range of 350 ⁇ m or less.
  • the total content of platinum group metal in the platinum group-containing spent catalyst may range from 0.005 to 0.4% by weight.
  • the platinum group-containing spent catalyst contains platinum and palladium, and the contents of platinum and palladium may be in the range of 0.003 to 0.15% by weight and 0.002 to 0.1% by weight, respectively.
  • the pH of the aqueous solution containing biocyanide in step a) may range from 9.5 to 14, and the concentration of cyanide (CN - ) may range from 2 to 6 g/L.
  • the step of trapping or collecting the solution containing biocyanide into an alkaline solution and concentrating or accumulating it may be further included.
  • the pH of the platinum group-containing cyanide leachate formed in step a) may range from 9 to 12.5.
  • the organophosphorus ionic liquid used in step b) may include a phosphonium-based cationic group represented by the following general formula 1, and an anionic group selected from the group consisting of halide, sulfide, and nitrate. there is:
  • R 1 to R 4 are each an alkyl group having 35 to 56 carbon atoms.
  • the molecular weight (M w ) of the organophosphorus-based ionic liquid used in step b) may range from 200 to 900.
  • step c) may be performed by stripping.
  • the step of separating the organophosphorus ionic liquid from the extract remaining after recovery of the platinum group metal in step c) and reusing it as an extractant in step b) may further be included.
  • the process for recovering platinum group metals from spent catalysts uses a green biogenic cyanide solution based on bioleaching or biohydrometallurgical mechanisms, compared to conventional techniques (pyrometallurgical processes, chemical wet metals using acids). It can dramatically solve problems pointed out in the smelting process (in particular, emissions of harmful gases or toxic substances, slag production, high energy consumption, etc.). Furthermore, by performing a liquid-liquid extraction method using a specific extractant, platinum group metals can be easily separated from the platinum group-containing leachate produced through biocyanide-based leaching, and further, individual platinum group metals can be recovered with high purity. It provides advantages that can be done. In particular, because it is environmentally friendly, low energy-intensive, and highly efficient, it is consistent with the ESG strategies of related companies and is expected to be widely commercialized in the future.
  • 1 is a process diagram showing a schematic process sequence for recovering platinum group metals from spent catalysts
  • FIG. 2 is a process diagram showing an exemplary process for recovering platinum group metals from spent catalyst
  • Figure 3 is a diagram showing an example of an apparatus for performing a cyanide production experiment using bacteria
  • Figure 4 is a graph showing the results of measuring the number of C. violaceum cells in YP medium supplemented with 2.0 g/L glycine in biocyanide over time in batch mode;
  • Figure 5 shows the time course of the preparation of biocyanide solution using a NaOH trapping solution of 4.0 mol/L and YP medium with a glycine concentration of 2.0 g/L in (a) batch mode and (b) continuous mode, respectively.
  • This is a graph showing the accumulation and pH change of biogenic cyanide
  • Figure 6 is a graph showing the effect of temperature on the pressurized biocyanation reaction of Pt and Pd from a spent catalytic converter at conditions of CN - concentration of 2.9 g/L, pO 2 of 10.5 bar, initial pH of 11.2 and 60 minutes;
  • Figure 7 shows the effect of oxygen partial pressure (pO 2 ) on the pressurized biocyanation reaction of Pt and Pd from a spent catalytic converter at a temperature of 150 °C, CN concentration of 2.9 g/L, initial pH of 11.2, and 60 min. It is a graph representing;
  • Figure 8 is a graph showing the effect of biocyanide concentration on the pressurized biocyanation reaction of Pt and Pd from a spent catalytic converter under conditions of temperature of 150 °C, pO 2 of 14 bar, initial pH of 11.2 and 60 minutes;
  • Figure 9 shows the effect of ionic liquid concentration on the extraction of Pt and Pd from (a) cyanide leachate under certain conditions (O:A, 1; pH, 10.8; contact time, 10 min; and temperature, 25°C). Graph showing the impact, and (b) D vs. It is a log plot of P-IL;
  • FIG. 10 shows the platinum group metal-containing solution (leaching solution) for Pt-Pd extraction under given conditions (O:A, 1; P-IL concentration, 0.15 mol/L; contact time, 10 min; and temperature, 25 °C). This is a graph showing the effect of pH;
  • Figure 11 shows the effect of temperature on (a) Pt-Pd extraction under given conditions (O:A, 1; P-IL concentration, 0.15 mol/L; solution pH, 10.4; and contact time, 10 min).
  • Graph, and (b) logK ex vs. is the Van't Hoff plot for 1/T;
  • Figure 12 is a graph showing the effect of the concentration of NH 4 SCN on the stripping behavior of Pt and Pd in the ionic liquid phase under certain conditions (O:A, 1; contact time, 10 min; and temperature, 25 °C). ;
  • Figure 13 shows the concentration of S(CH 2 CH 2 OH) 2 for Pt-stripping in the Pd-depleted ionic liquid phase under given conditions (O:A, 1; contact time, 10 min; and temperature, 25 °C). This is a graph showing the impact of;
  • Figure 14 is (a) a graph showing the behavior of leaching Pt and Pd from a spent catalytic converter using the biocyanide solution accumulated in the recycled raffinate after performing the (Pt, Pd) extraction process using P-IL, and (b) a graph showing the results of evaluating the reusability of ionic liquid in a (Pt,Pd) extraction cycle from a cyanide leaching solution; and
  • Figure 15 is a graph showing the results of an experiment on biodegradation of cyanide in a bleed solution using C. violaceum drained from the bioreactor after being used to produce biocyanide.
  • Platinum group metal broadly includes the six metal elements belonging to the platinum group: platinum, palladium, rhodium, ruthenium, iridium, and osmium. It can be understood as referring to platinum and/or palladium in a narrow sense.
  • Bioleaching may generally refer to a process of dissolving a metal from a mineral source by microorganisms, and specifically to a process of converting a solid metal to a water-soluble form.
  • “Culture medium” may refer to an aqueous solution of nutrients available for cell growth.
  • Extraction can mean transferring a particular component, specifically a metal, from one phase to another.
  • “Stripping” may refer to a process of separating or removing a specific metal from a liquid medium or solvent
  • selective stripping may refer to a process of separating or removing a specific metal from a liquid medium or solvent containing a plurality of metals. can do.
  • contact may also be understood to include not only direct contact, but also contact through the intervention of other components or members.
  • a process of bioleaching and solvo-chemical extraction using microorganisms is provided to separate and recover platinum group metals from a spent catalyst containing platinum group metals,
  • the schematic process is as shown in Figure 1.
  • platinum group-containing spent catalyst can be used as a starting material.
  • platinum group-containing spent catalysts are available from various fields such as the automotive and chemical industries, and may typically be derived from catalytic converters (e.g., catalytic converters of automobiles).
  • the content of the platinum group metal in the spent catalyst is not particularly limited, but the content (based on element) of the platinum group metal in the spent catalyst is, for example, about 0.005 to 0.4% by weight, specifically about 0.01 to 0.01% by weight. It may range from 0.3% by weight, more specifically about 0.011 to 0.15% by weight.
  • the spent catalyst may contain platinum and/or palladium among the platinum group metals.
  • the spent catalyst may simultaneously contain platinum and palladium, where the content (based on element) of platinum (Pt) is, for example, about 0.003 to 0.15% by weight, specifically about 0.005 to 0.1% by weight. %, more specifically, it may be around 0.08% by weight, and the content of palladium (Pd) (based on element) is, for example, about 0.002 to 0.1% by weight, specifically about 0.004 to 0.05% by weight, more specifically about It may be in the range of around 0.04% by weight.
  • the weight ratio of platinum/palladium may range, for example, from about 0.1 to 3, specifically from about 0.3 to 2.5, and more specifically from about 0.5 to 2.1.
  • the spent catalyst may further contain other components in addition to platinum group metals, such as alumina, magnesia, silica, zirconia, titania, calcium oxide, etc., and the content of additional components or metals (element Standard) may be, for example, in the range of about 60% by weight or less, specifically about 40% by weight or less, and more specifically about 20% by weight or less.
  • platinum group metals such as alumina, magnesia, silica, zirconia, titania, calcium oxide, etc.
  • the spent catalyst may be substantially free of rhodium.
  • platinum group-containing catalysts that do not contain rhodium are typically available from old generation catalysts of automobile vehicles, more specifically second generation catalysts of automobile vehicles, etc. These composition characteristics can affect the Pt and Pd extraction process using ionic liquid, the reuse process of cyanide leachate remaining after use, and the biodegradation process of cyanide remaining in the solution, which is discharged in a certain amount prior to the cyanide leachate reuse process. there is. However, it does not exclude the presence of trace amounts of rhodium in the form of impurities, for example, it may be contained in less than about 0.0004% by weight, specifically less than about 0.0001% by weight.
  • rhodium may act as an impurity during the extraction of Pt and Pd, lowering the purity of Pt and Pd to be recovered, and as the recycling process of raffinate generated during the extraction process is repeated, rhodium may accumulate in the solution. , it may be advantageous to contain as little rhodium as possible.
  • the content of platinum group components in the above-described spent catalyst may be understood as illustrative, and may vary depending on the source.
  • the spent catalyst may be provided in the form of particles or pulverized material.
  • the particle size or size of the pulverized material or particles determines effective contact with the biocyanide solution described later, flow characteristics in the reactor, etc. It can be determined by taking into account, for example, about 350 ⁇ m or less, specifically about 250 ⁇ m or less, more specifically about 100 to 200 ⁇ m, and particularly specifically about 120 to 180 ⁇ m.
  • waste catalyst derived from a waste catalyst converter for automobiles it may be provided in a pulverized form after the catalyst layer has been peeled off. At this time, for grinding, means known in the art can be used.
  • the grinding means may be a roller grinder, vibrating mill, ball mill, pot mill, hammer mill, pulverizer, gyratory grinder, gyratory mill, etc., but is not limited thereto, and may be two or more of the listed types. It can also be pulverized by combining.
  • the platinum group-containing spent catalyst may optionally undergo an alkali pretreatment step.
  • This alkaline pretreatment can be performed to remove carbonaceous substances in the spent catalyst (or spent catalyst particles) and various impurities that may inhibit subsequent biocyanation.
  • the alkaline treatment may be performed by contacting the spent catalyst with an alkali-containing solution (specifically, an aqueous solution), wherein the alkaline component is at least one selected from sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc. You can.
  • the concentration of the alkaline solution may be adjusted, for example, in the range of about 1 to 5 mol/L, specifically about 1.5 to 4 mol/L, and more specifically about 2 to 3 mol/L.
  • the pretreatment temperature may be adjusted, for example, to at least about 60°C, specifically about 70 to 98°C, and more specifically about 80 to 95°C.
  • the pretreatment time is not particularly limited, but may be adjusted, for example, in the range of about 30 to 200 minutes, specifically about 40 to 100 minutes, and more specifically about 50 to 80 minutes.
  • a step of synthesizing cyanide that is, biocyanide (HCN)
  • HCN biocyanide
  • a solution specifically an aqueous solution
  • microorganisms can be selected from species capable of producing cyanide by metabolic action.
  • the cyanide-producing microorganism may be at least one selected from species belonging to Betaproteobacteria, Gammaproteobacteria, etc., such as Chromobacterium violaceum , Pseudomonas fluorescens , It may be at least one selected from Pseudomonas plecoglossicida , Bacillus megaterium, etc., and in particular, it may be a type that can produce cyanide through oxidative decarboxylation of glycine.
  • Chromobacterium violaceum which belongs to Gram-negative beta-probacteria and promotes oxidase reaction, can be used as the spoilage bacteria.
  • the types listed above may be understood as illustrative purposes.
  • the medium may be a growth medium, specifically YP medium supplemented with glycine.
  • the concentration of glycine in the medium may be, for example, in the range of about 0.5 to 5 g/L, specifically about 1.5 to 3.5 g/L, and more specifically about 2 to 2.5 g/L. Since the components of the medium used for microbial growth in this embodiment are known in the art, separate detailed description will be omitted.
  • the pH of the growth medium can be adjusted in consideration of microbial characteristics, and may be, for example, at least about 7, specifically about 8 to 9, and more specifically about 8.5.
  • the culture temperature is not particularly limited, but may be typically adjusted in the range of about 20 to 40°C, more typically about 25 to 35°C.
  • the concentration of microorganisms in the initial growth medium may range, for example, from at least about 10 5 CFU/mL, specifically about 10 6 to 10 9 CFU/mL, and more specifically about 10 7 to 10 8 CFU/mL. However, this can be understood as an example.
  • the culture of microorganisms may be performed under the supply of an oxygen-containing gas, for example, air, and the culture may be performed using a bioreactor illustratively equipped with an aeration facility.
  • the concentration of cyanide after culturing may range, for example, from about 900 to 1200 mg/L, specifically from about 950 to 1100 mg/L, and more specifically from about 1000 to 1100 mg/L.
  • a concentration or accumulation step may be performed to increase the concentration of biocyanide produced by microbial culture.
  • cyanide (HCN) produced using an alkaline solution specifically, an aqueous solution
  • HCV cyanide
  • the alkaline component in the alkaline solution may be at least one selected from, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc., and its concentration may be, for example, about 1 to 8 mol. /L, specifically, can be adjusted in the range of about 1.5 to 6 mol/L, more specifically about 3 to 5 mol/L, but this can be understood as an example.
  • the principle of cyanide trapping is to utilize the phenomenon that the vapor density of cyanide (HCN) (0.94) is lower than the vapor density of air (1.0). To achieve this, aeration is applied as much as possible to push the HCN toward the alkaline solution. It is desirable to have it done.
  • cyanide trapping may be performed according to Scheme 1 below.
  • the trapping time is, for example, about 20 to 120 hours, specifically about 40 to 110 hours, more specifically about 60 to 105 hours, more specifically about 90 to 100 hours, considering the desired concentration of biocyanide. It can be adjusted appropriately within the time range.
  • the concentration of cyanide or cyanide ions (i.e., CN - ) concentrated or accumulated into the alkaline solution as described above is, for example, about 2 to 6 g/L, specifically about 3 to 5 g/L, more specifically It can increase to a range of about 4 to 4.5 g/L.
  • concentration of cyanide is below a certain level, there is a limit to increasing the leaching rate during bioleaching in the downstream stage, and if it exceeds a certain level, the leaching rate will no longer increase, so concentration It may be advantageous to appropriately adjust the degree.
  • the pH of the concentrated cyanide solution may range, for example, from about 9.5 to 14, specifically from about 10 to 12, and more specifically from about 10.5 to 11.5.
  • the production of biocyanide and the concentration or accumulation of cyanide using an alkaline solution may be performed in a batch or continuous manner, but biocyanide is produced in a relatively short period of time. Considering that it is generated in a section, continuous mode may be advantageous.
  • the obtained biocyanide-containing solution or concentrated (accumulated) biocyanide-containing solution is supplied to a lixiviant medium to remove platinum group metals from the platinum group-containing spent catalyst.
  • a leaching step is performed.
  • the platinum group metal in the spent catalyst may form a form combined with cyanide ions, for example, a complex.
  • the amount of spent catalyst in the biocyanide-containing solution is, for example, about 2 to 40 g/100 mL, specifically about It can be adjusted in the range of 5 to 25 g/100 mL, more specifically about 10 to 20 g/100 mL.
  • the bioleaching process may be performed under stirring conditions.
  • the stirring speed may be adjusted in the range of about 100 to 400 rpm, specifically about 200 to 250 rpm, but this is for illustrative purposes. It can be understood as
  • the leaching time may be determined considering the maximum leaching of Pt and Pd, for example, about 30 to 360 minutes, specifically about 30 to 120 minutes, and more specifically about 60 to 90 minutes. You can.
  • bioleaching may be set to elevated temperature conditions and increased oxygen pressure (pO 2 ) conditions.
  • the leaching temperature may be adjusted, for example, in the range of about 100 to 200 °C, specifically about 120 to 180 °C, and more specifically about 140 to 160 °C.
  • the leaching temperature is too low or too high, it may act as a factor in reducing the leaching rate, so it may be advantageous to appropriately adjust it within the above-mentioned range.
  • the above-described leaching temperature can be changed depending on other conditions, such as cyanide concentration, leaching time, oxygen pressure, etc.
  • the leaching rate may tend to increase as the pressure during bioleaching, specifically the oxygen pressure (or oxygen partial pressure) increases, for example, at least about 8 bar, specifically about 10 bar. It can be adjusted in the range of from about 18 bar to about 18 bar, more specifically about 12 to 16 bar. However, at excessively high oxygen pressure (or partial pressure), the increase in leaching rate is insignificant and may actually act as a factor in reducing the economic feasibility of the process, so it may be advantageous to adjust it appropriately within the above-mentioned range.
  • the leaching rate of the platinum group metals is, for example, at least about 90%, specifically at least about 92%, more specifically at least It may be about 95%.
  • the cyanide solution from which the platinum group has been leached may exhibit basicity.
  • the pH of the platinum group-containing leachate is, for example, about 9 to 12.5, specifically about 10 to 12, more specifically about 10.2 to 11.5, In particular, it may range from about 10.5 to 11, and this can be understood as an example.
  • the platinum group-containing cyanide leachate produced by bioleaching contains other components (for example, Al 2 O 3 , MgO, SiO 2 , ZrO 2 , CaO, TiO 2 , etc.), a step of selectively separating and recovering the platinum group metal is performed using a solvo-chemical method.
  • platinum group metals in the leachate are selectively moved into the extract by liquid-liquid extraction, thereby forming a platinum group-rich extract and a platinum group-depleted raffinate.
  • a water-insoluble organophosphorous ionic liquid may be used as the extractant.
  • organophosphorus-based ionic liquids are environmentally friendly because they are not flammable, unlike existing extractants, and also have good mass transfer and loading capacity.
  • the phosphorus-based ionic liquid may contain a phosphonium-based cationic group represented by General Formula 1 below.
  • R 1 to R 4 are each an alkyl group having 35 to 56 carbon atoms, specifically 38 to 50 carbon atoms, and more specifically 40 to 48 carbon atoms.
  • the anion constituting the phosphonium-based ionic liquid it may be at least one selected from halide, sulfide, nitrate, etc.
  • the halide may be at least one selected from fluoride, chloride, bromide, iodide, etc., and more specifically, may be chloride (Cl - ).
  • the molecular weight (M w ) of the above-described phosphonium-based ionic liquid may range, for example, from about 200 to 900, specifically from about 300 to 800, and more specifically from about 400 to 700. .
  • M w molecular weight
  • a representative phosphonium-based ionic liquid may be trihexyl(tetradecyl)phosphonium chloride, which exhibits anion exchange properties and is contained in the cyanide leachate. It can be particularly advantageous for extracting platinum group metals.
  • the organophosphorus ionic liquid may be applied to the extraction process in a mixed form with an aromatic solvent, taking into account the dielectric constant of the solvent, metal affinity, and affinity with the ionic liquid and aqueous solution.
  • the aromatic solvent that can be used is an aromatic solvent having 7 to 12 carbon atoms, specifically 8 to 11 carbon atoms, and more specifically, about 10 carbon atoms, for example, Solesso100. It may be commercially available as Solvesso150, Solvesso200, ExxolD80, etc.
  • the concentration of the organophosphorus extractant is, for example, at least about 0.08 mol/L, specifically at least about 0.1 mol/L, more specifically about 0.12 to 0.3 mol/L, especially specifically about 0.14 to 0.2 mol/L.
  • the concentration of the organophosphorus extractant is, for example, at least about 0.08 mol/L, specifically at least about 0.1 mol/L, more specifically about 0.12 to 0.3 mol/L, especially specifically about 0.14 to 0.2 mol/L.
  • an organometallic complex is formed between the cyanide of a platinum group metal (specifically Pt and/or Pd) and the ionic liquid in the extract, specifically phosphonium-based ionic liquid. It is believed that the metal moves from the aqueous phase to the organic phase by ion exchange between the anion of the phonium-based ionic liquid and the metal ion (specifically, the anion combining platinum and cyanide group).
  • the structure of the organometallic complex according to the ion exchange reaction may be expressed as Formula 1 below.
  • the extraction conditions are not particularly limited, but the volume ratio of organic phase to aqueous phase is about 1:5 to 5:1, specifically about 1:3 to 3:1, more specifically about 1:2. It can be adjusted in the range of 2:1.
  • the equilibration time may be, for example, in the range of about 2 to 30 minutes, specifically about 5 to 15 minutes, and more specifically about 5 to 10 minutes.
  • the extraction temperature may be, for example, around 20 to 40°C, specifically around 22 to 35°C, more specifically around 24 to 30°C, particularly around 25°C.
  • platinum group-depleted raffinate aqueous phase
  • organophosphorus ionic liquid as it contains cyanide
  • it can be used to leach platinum group metals from the spent catalyst.
  • it can be recycled as a solution containing biocyanide, and/or as a solution containing biocyanide concentrated (or accumulated) by an alkaline solution (trapping or collection solution).
  • cyanide can be decomposed by microorganisms that can be used to produce the aforementioned biocyanide, and can be discharged outside the process or system after going through the decomposition process.
  • recovering platinum group metals from a platinum group-rich extract may be performed.
  • the recovered platinum group metal may be a single platinum group metal or a combination of at least two types of platinum group metals.
  • this specific example does not exclude the recovery of a combination of two or more platinum group metals, for example, a combination of Pt and Pd, considering the usability, it is better to recover each platinum group metal contained in the spent catalyst with high purity. It can be advantageous. From this perspective, the following description will focus on methods for recovering a plurality of platinum group metals contained in the extract, specifically Pt and Pd.
  • selective stripping may be performed to recover a plurality of platinum group metals contained in the extract (i.e., organophosphorus-based ionic liquid).
  • the platinum group metals extracted in the extract (organic phase) are platinum (Pt) and palladium (Pd)
  • a solution specifically an aqueous solution
  • a compound i.e., stripping agent
  • Pt and Pd can each be recovered by contacting them with a platinum group-containing extract (oil phase), individually or sequentially.
  • an aqueous solution of a stripping agent that has water miscibility and selectivity for palladium can be used.
  • These stripping agents may be selected from thiol compounds that have selectivity in forming Pd complexes.
  • the Pd-selective stripping agent may be, for example, a thiocyanate compound.
  • Such a thiocyanate compound may be, for example, at least one selected from ammonium thiocyanate (NH 4 SCN), sodium thiocyanate (NaSCN), potassium thiocyanate (KSCN), etc., and specifically, ammonium thiocyanate (NaSCN). It may be a cyanate (NH 4 SCN) compound.
  • the concentration of the aqueous solution of the stripping agent selective for palladium can be adjusted so that the Pd stripping rate is maximum and at the same time the Pt stripping rate is minimum, for example at least about 0.7 mol/L, specifically at least about 0.8 mol/L. to 3 mol/L, more specifically about 1.2 to 2.6 mol/L, and particularly specifically about 1.8 to 2.3 mol/L.
  • the volume ratio of the organic phase to the water phase during palladium stripping is about 1:5 to 5:1, specifically about 1:3 to 3:1, more specifically about 1:2 to 2:1. It can be adjusted within a range.
  • the stripping temperature may be, for example, about 20 to 40° C., specifically about 22 to 35° C., more specifically about 24 to 30° C., and particularly specifically about 25° C.
  • the contact time is specifically limited. Although not guaranteed, it can be appropriately adjusted, for example, in the range of about 2 to 30 minutes, specifically about 5 to 15 minutes, and more specifically about 5 to 10 minutes.
  • the stripping rate of palladium may be at least about 90%, specifically at least about 95%, and more specifically at least about 98%.
  • the stripping rate of platinum may be, for example, less than about 3%, specifically less than about 2.5%, and more specifically less than about 2%.
  • the organic phase i.e., the palladium-depleted fraction in which most of the platinum (Pt) is contained in the organophosphorus ionic liquid, can be subjected to additional stripping to recover platinum (second stripping step).
  • the platinum stripping agent should be selected from types that are easy to form a Pt complex and have properties that can move Pt from the organic phase to the aqueous phase. You can.
  • thioalcohol can be used, specifically 2,2-thiodiethanol (S(CH 2 CH 2 OH) 2 ), Beta-rhodinol, (S)-3,7- It may be at least one selected from dimethyl-6-often-1-ol, etc., and specifically may be 2,2-thiodiethanol (S(CH 2 CH 2 OH) 2 ).
  • the concentration of the aqueous solution of the stripping agent selective for platinum is determined taking into account the maximum stripping rate of Pt, for example at least about 0.8 mol/L, specifically at least about 1 to 3 mol/L, more specifically about It can be adjusted in the range of 1.2 to 2.2 mol/L, particularly about 1.4 to 2 mol/L.
  • the volume ratio of organic phase to aqueous phase during platinum stripping is about 1:5 to 5:1, specifically about 1:3 to 3:1, more specifically about 1:2 to 2:1. It can be adjusted within a range.
  • the stripping temperature may be, for example, about 20 to 40° C., specifically about 22 to 35° C., more specifically about 24 to 30° C., and particularly specifically about 25° C.
  • the contact time is specifically limited. Although not guaranteed, it can be appropriately adjusted, for example, in the range of about 2 to 30 minutes, specifically about 5 to 15 minutes, and more specifically about 5 to 10 minutes.
  • the stripping rate of platinum may be at least about 90%, specifically at least about 95%, and more specifically at least about 98%.
  • each stripping solution can recover high purity platinum group metals, specifically platinum and palladium, through methods known in the art, such as precipitation and salt formation.
  • a platinum group metal-containing stripping solution specifically a platinum-containing solution and a palladium-containing solution, respectively, for example, ammonium salt, sulfide salt, etc.
  • the concentration of the added component may be determined depending on the amount of platinum group metal in the stripping solution, for example, about 0.01 to 0.05 mol/L, specifically about 0.02 to 0.04 mol/L, More specifically, it may range from about 0.02 to 0.03 mol/L.
  • the above numerical range may be understood as illustrative.
  • the temperature conditions for forming the precipitate are not particularly limited, but may be adjusted, for example, to a range of about 20 to 100°C, specifically about 30 to 80°C, and more specifically about 40 to 50°C.
  • the extract remaining after the stripping process can be recycled after the separation process and reused as an extractant in the extraction step before the stripping step.
  • the ionic liquid can be separated by contacting it with an aqueous solution of at least one acid selected from strong acids, such as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, etc.
  • the concentration of the acid aqueous solution may be adjusted in the range of, for example, about 3 to 9 mol/L, specifically about 4 to 8 mol/L, and more specifically about 5 to 7 mol/L, but the acid used It can be changed depending on the type, etc.
  • a spent catalytic converter (5 kg) for a vehicle obtained from a domestic disposal company was used.
  • the collected catalyst was finely ground to a size of approximately 150 ⁇ m using a gyratory crusher and ball mill.
  • the contents of platinum and palladium among the platinum group metals were 756 ppm and 367.5 ppm, respectively.
  • platinum group metals were recovered from spent catalyst by performing the critical steps of the process shown in FIG. 2.
  • biocyanide production and concentration (accumulation) experiments were performed using the setup device shown in FIG. 3.
  • cyanide-producing bacteria C. violaceum DSM30191
  • YP medium 10 g peptone, 5 g yeast extract, and 1.0 L distilled water
  • Approximately 10 6 CFU/mL was inoculated.
  • Cyanide synthesis was performed in a bioreactor (equipped with a stirrer to provide agitation at 300 rpm), and air was constantly supplied through an aerator at a flow rate of 3.0 mL/s. The bioreactor was maintained at 30°C over 120 hours.
  • 4.0 mol/L NaOH solution was used as an alkali collection means for concentrating (accumulating) the synthesized biocyanide.
  • concentration of biocyanide was analyzed by titration against a standard AgNO 3 solution, and cells were counted by the drop plate method on nutrient agar using plates incubated at 30°C for 24 hours.
  • the cell number increased from 10 6 CFU/mL to 10 9 CFU/mL within 36 hours after incubation and was maintained until 12 hours thereafter. Then, as a result of 120 hours of incubation, it decreased to 10 7 CFU/mL.
  • biocyanide accumulation into the alkaline solution started after 12 hours (10 6 mg/L CN - ) and progressed over 48 hours, with a maximum accumulation of 1.05 g/L CN - reached, and then began to decrease.
  • cyanide (HCN) synthesis was performed using YP medium supplemented with 2.0 g/L glycine and through a continuous process capable of accumulating higher concentrations of cyanide ions under conditions with a retention time of 24 hours.
  • HCN cyanide
  • Figure 5b the highest concentration of 4.17 g/L CN - was reached after 96 hours in the alkaline collection solution with a pH of 10.7.
  • the CN - ion concentration decreased to 3.8 g/L after 120 hours, which is believed to be because some of the CN - ions were converted to HCN as the pH decreased to about 10 (pKa, 9.3).
  • the solution was collected by filtration using a 0.45 ⁇ m membrane filter, and the collected filtrate was analyzed for Pt-Pd using ICP-plasma mass spectrometry (ICP-MS; MSS 01, SPECTRO Analytical Instruments GmbH, Germany). Analysis was performed.
  • ICP-MS ICP-plasma mass spectrometry
  • the metal leaching rate was calculated according to Equation 1 below.
  • M IS and M LL are the metal content in the solid sample and the metal content in the leachate, respectively.
  • the leaching rate of Pt and Pd in the cyanide-containing solution at a high temperature of 100°C was found to be 85% or less. However, at 150 °C, the leaching rate reached a maximum of 91% Pt and 94% Pd. Thereafter, as the temperature increased, the leaching rate decreased, reaching a maximum of 87% Pt and 81% Pd at 250°C. This decrease behavior is believed to be due to the decomposition of cyanide due to an increase in the hydrolysis rate at higher temperatures, as shown in Schemes 2 and 3 below.
  • the bioleaching experiment was performed according to the experimental procedure according to Example 2, except that the bioleaching was performed while changing the partial pressure of oxygen (pO 2 ) in the range of 3.5 to 17.5 bar (temperature of 150°C, 2.9 g/L). CN - concentration, initial pH of 11.2 and 60 min). The results are shown in Figure 7.
  • pO 2 partial pressure of oxygen
  • a bioleaching experiment was performed according to the experimental procedure according to Example 2, except that the bioleaching was performed while changing the biocyanide (CN - ) concentration in the range of 0.23 to 4.17 g/L (temperature of 150°C, pO 2 of 14 bar, initial pH of 11.2 and 60 min). The results are shown in Figure 8.
  • the Pt leaching rate (43% to >95%) and Pd leaching rate (52% to 96%) also increased.
  • the residual cyanide concentration increased from 0.032 g/L to >1.0 g/L.
  • the maximum leaching rate was observed in the cyanide-containing solution at a concentration of 2.9 g/L CN - .
  • the stock leachate (Pt, 157.5 mg/L and Pd, 77.6 mg/L) was used in the subsequent separation (liquid-liquid extraction) process.
  • Trihexyl(tetradecyl)phosphonium chloride a phosphonium-based ionic liquid
  • C10 aromatic solvent
  • PH 10.8 cyanide leachate
  • the platinum group metals (Pt and Pd) were extracted.
  • the organic to aqueous phase ratio (O:A) was 1, and the contact was made at 25°C for 10 minutes. The results are shown in Figure 9.
  • the logarithmic distributions Pt and Pd showed a relationship between log[P-IL] and a straight line with a slope value of about 2.
  • the slope value indicates that 2 molecules of ionic liquid are involved per mole of Pt and Pd extraction complexes. Based on this relationship, the extraction reaction can be represented by Schemes 6 and 7 below.
  • the extraction experiment was performed according to the experimental procedure according to Example 5, except that the liquid-liquid extraction was performed while changing the pH of the platinum group metal-containing solution (leaching solution) in the range of 10.4 to 11.2 (O:A, 1 ; P-IL concentration, 0.15 mol/L; contact time, 10 min; and temperature, 25 °C). The results are shown in Figure 10. At this time, the extraction rate was calculated according to Equation 2 below.
  • V org and V aq are the volumes of the organic phase and the aqueous phase, respectively.
  • the Pt-Pd loaded ionic liquid was contacted with various concentrations of NH 4 SCN aqueous solution (0.25 to 2.0 mol/L) (O:A, 1; contact time, 10 min; and temperature, 25° C.). The results are shown in Figure 12. At this time, the stripping rate was calculated according to Equation 3 below.
  • CS org and CS aq are the metal concentrations after stripping in the organic phase and aqueous phase, respectively.
  • the NH 4 SCN solution showed the selective recovery ability of Pd over Pt. Specifically, as the NH 4 SCN concentration increased from 0.25 mol/L to 1.0 mol/L, the Pd-stripping rate increased significantly from 68% to >94%. Afterwards, stripping hardly progressed, showing a stripping rate of over 98% in a 2.0 mol/L NH 4 SCN solution, and at this time, Pt was less than 3%.
  • the selectivity achieved in thiocyanate stripping comes from the fact that the Pd-compound has a larger charge density due to the larger size of Pt(CN) 4 2- than that of Pd(CN) 4 2- . It is believed to be caused by The reaction involved in Pd-stripping using NH 4 SCN solution can be expressed in Scheme 8 below.
  • the Pd-depleted ionic liquid was contacted with various concentrations of S(CH 2 CH 2 OH) 2 aqueous solution (0.25 to 2.0 mol/L) (O:A, 1; contact time, 10 min; and temperature, 25 °C. ). The results are shown in Figure 13.
  • the Pt stripping rate reached about 90% in a 1.0 mol/L S(CH 2 CH 2 OH) 2 solution and about 96% in a 1.5 mol/L S(CH 2 CH 2 OH) 2 solution. % has been reached. However, even if the S(CH 2 CH 2 OH) 2 concentration was further increased, no significant increase in the stripping rate was observed.
  • the coordination substitution reaction of Pt-stripping using S(CH 2 CH 2 OH) 2 can be represented by Scheme 9 below.
  • the leaching rates of Pt and Pd were both about 95%, confirming the recyclability of the residual cyanide solution.

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Abstract

La présente invention concerne un procédé de récupération d'un métal du groupe du platine avec un rendement élevé en utilisant un liquide ionique à base de phosphore organique en tant qu'agent d'extraction, après la biolixiviation du métal du groupe du platine contenu dans des déchets de catalyseur en utilisant du biocyanure produit à partir de micro-organismes.
PCT/KR2023/012145 2022-09-14 2023-08-17 Procédé de récupération de métal du groupe du platine à partir de déchets de catalyseur en utilisant du biocyanure et du liquide ionique Ceased WO2024058441A1 (fr)

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KR100781670B1 (ko) * 2006-08-16 2007-12-03 희성촉매 주식회사 극소량의 로듐 또는 로듐을 포함하지 않는 내연기관배기가스 정화용 촉매
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KR102542074B1 (ko) * 2022-09-14 2023-06-13 한양대학교 산학협력단 바이오시안화물 및 이온성 액체를 이용하여 폐촉매로부터 백금족 금속을 회수하는 공정

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JP2012532989A (ja) * 2009-07-07 2012-12-20 サイテク・テクノロジー・コーポレーシヨン 水溶液から金属を回収する方法
KR102542074B1 (ko) * 2022-09-14 2023-06-13 한양대학교 산학협력단 바이오시안화물 및 이온성 액체를 이용하여 폐촉매로부터 백금족 금속을 회수하는 공정

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