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EP4642935A1 - Compositions et procédés de lixiviation de métaux de haute valeur - Google Patents

Compositions et procédés de lixiviation de métaux de haute valeur

Info

Publication number
EP4642935A1
EP4642935A1 EP23911135.4A EP23911135A EP4642935A1 EP 4642935 A1 EP4642935 A1 EP 4642935A1 EP 23911135 A EP23911135 A EP 23911135A EP 4642935 A1 EP4642935 A1 EP 4642935A1
Authority
EP
European Patent Office
Prior art keywords
alkanediyl
solvent
value metal
leach composition
leach
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23911135.4A
Other languages
German (de)
English (en)
Inventor
Mohammad DOOSTMOHAMMADI
Sanaz MOGHADAM ZADEH
Ryan John ROBERTS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ph7 Technologies Inc
Original Assignee
Ph7 Technologies Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ph7 Technologies Inc filed Critical Ph7 Technologies Inc
Publication of EP4642935A1 publication Critical patent/EP4642935A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • 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
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/16—Sintering; Agglomerating
    • 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
    • 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
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/028—Flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0288—Applications, solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0488—Flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • 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

  • the present disclosure generally relates to metallurgical recycling, and in particular to compositions and methods for leaching and recovering high value metals from a variety of sources.
  • High-value metals such as gold, silver, copper, and the platinum group metals (PGMs) hold immense economic, technological, and political significance. Economically, these metals play a vital role in global trade and finance.
  • Gold often viewed as a store of value, influences international currency markets and is held as a reserve asset by central banks.
  • the PGMs particularly platinum and palladium, are essential in catalytic converters, which help reduce vehicle emissions and improve air quality, contributing to the automotive industry's sustainability.
  • Silver is used in a wide range of industrial applications, including electronics and solar panels. Copper is a critical component in infrastructure development, electrical wiring, and renewable energy technologies.
  • Ion-exchange and solvent extraction methods play a crucial role in metal recovery. They use selective resins or solvents to separate and recover metals from solution after leaching or other chemical processes. Electrowinning and electrorefining are electrochemical processes that allow for the extraction and purification of metals like gold, silver, and copper from solution or impure sources.
  • the present disclosure provides leach compositions and methods of using the leach compositions to leach and extract various high-value metals
  • the leach compositons and methods described in the present disclosure overcome many of the deficiencies with prior approaches, for example they provide higher overall recovery efficiency, with lower energy input, and with less use of eniromentally unfavorable chemicals.
  • the disclosure provides leach compositions for leaching a high-value metal from a high-value metal source material.
  • the leach composition can include a solvent; an oxidizing agent; and a halogen salt; wherein the solvent comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, a ketone, a carboxylic acid, an ester, a carbonate ester, and combinations thereof; and wherein the alcohol, the ether, the ketone, a carboxylic acid, an ester, a carbonate ester are optionally substituted with one or more group independently selected from a Cl- C5 alkyl, a hydroxy group, and combinations thereof.
  • the leach composition can include a ligand.
  • the oxidizing agent is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof; and the halogen salt is present at a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof.
  • the oxidizing agent is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof;
  • the halogen salt is present at a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof;
  • the ligand is selected from the group consisting of sodium acetate, sodium citrate, ethylenediaminetetraacetic acid (EDTA), and combinations thereof.
  • the disclosure provides methods of extracting a high-value metal from a high-value metal source material.
  • the method can include contacting the high-value metal source material with a leach composition according to any one of claims 90-153 for a first period of time to form a high-value metal slurry; filtering the high-value metal slurry to remove impurities from the high-value metal slurry that are insoluble in the leach composition to form a pregnant solution; and extracting the high value metal from the pregnant solution, thereby forming a spent leach composition.
  • FIG. 1 is flow chart of a leaching process for high-value metals according to certain aspects of the disclosure.
  • FIG. 2 is a flow chart of an extraction process for high-value metals according to certain aspects of the disclosure.
  • FIGS. 3A-3C are graphs of time-dependent dissolution of the high-value metals platinum (FIG. 3A), palladium (FIG. 3B), and rhodium (FIG. 3C) plotted as the amount of dissolved metal (PPM) in the lixiviant solution as a function of time (hours) for the disclosed methods and compositions as compared to using aqua regia as the lixiviant.
  • FIG. 4 is a bar graph of the amount of platinum recovered (Pt Recovery %) and the amount of oxidant used in the leach composition (oxidant weight %) for examples of leaching platinum according to the disclosed methods and compositions.
  • FIG. 5 is a flow chart of an in-site halogen gas production for use in an extraction process for high-value metals according to certain aspects of the disclosure.
  • Sources of high-value metals are varied and numerous, from ore deposits to electronic waste, to catalyst waste and other types of industrial waste streams and from photovoltaic cells and printed circuit boards to mining tailings.
  • the complexities can include managing varying grades of source material and often in complex mixtures of components and including hazardous materials, the demands for greater separation and energy efficiency, and the need for environmentally friendly approaches have proven challenging for existing methods to overcome.
  • the disclosure provides leach compositions for leaching a high-value metal from a high-value metal source material.
  • the leach composition can include a solvent; an oxidizing agent; and a halogen salt; wherein the solvent comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, a ketone, a carboxylic acid, an ester, a carbonate ester, and combinations thereof; and wherein the alcohol, the ether, the ketone, a carboxylic acid, an ester, a carbonate ester are optionally substituted with one or more group independently selected from a Cl- C5 alkyl, a hydroxy group, and combinations thereof.
  • the leach composition can include a ligand.
  • the oxidizing agent is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof; and the halogen salt is present at a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof.
  • the oxidizing agent is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof;
  • the halogen salt is present at a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof;
  • the ligand is selected from the group consisting of sodium acetate, sodium citrate, ethylenediaminetetraacetic acid (EDTA), and combinations thereof.
  • the disclosure provides methods of extracting a high-value metal from a high-value metal source material.
  • the method can include contacting the high-value metal source material with a leach composition according to any one of claims 90-153 for a first period of time to form a high-value metal slurry; filtering the high-value metal slurry to remove impurities from the high-value metal slurry that are insoluble in the leach composition to form a pregnant solution; and extracting the high value metal from the pregnant solution, thereby forming a spent leach composition.
  • ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and subrange is explicitly recited.
  • a numerical range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the indicated range.
  • the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and the range less than ‘y’.
  • the range can also be expressed as an upper limit e.g., ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of Tess than x’, less than y’, and Tess than z’.
  • the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y’, and ‘greater than z’.
  • the term “about” can include traditional rounding according to significant figures of the numerical value.
  • the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values includes “about ‘x’ to about ‘y’”.
  • Source materials for high-value metals can in principal include any material that contains high-value metals.
  • the high-value metal source material can include ore deposits, electronic waste (E-Waste), industrial waste, catalytic converters, battery waste, waste from photovoltaic solar panels, printed circuit boards (PCBs), mining concentrates, or mining tailings.
  • E-Waste electronic waste
  • PCBs printed circuit boards
  • mining concentrates or mining tailings.
  • Each source material presents unique challenges in recovering high-value metals, with considerations related to scale, costs, complexity, and environmental concerns.
  • the methods and compositions described herein can enable the efficient extraction of these valuable metals while addressing environmental and economic sustainability.
  • the source material can include ore deposits.
  • Ore deposits are primary sources for high-value metals like gold, silver, copper, platinum, and palladium. These deposits vary widely in terms of metal concentrations and ore grades.
  • High-value metals including copper, gold, silver, and the platinum group metals (PGMs), are typically mined from various types of ore deposits and geological settings.
  • Major mining operations extract significant volumes of ore, ranging from thousands to millions of tons annually while smaller operations can process .
  • the methods include processing ore deposits ranging from 500 tons to 5 million tons of ore per day, from 500 tons to 500,000 tons of ore per day, from 500 tons to 100,000 tons or ore per day, from 500 tons to 50,000 tons of ore per day, or from 500 tons to 5,000 tons of ore per day.
  • Ore types can often be characterized based on the chemical composition. Each type of ore presents its unique set of challenges and opportunities for metal extraction, with factors like ore composition, economic viability, and environmental considerations influencing the choice of extraction method.
  • Oxide Ores can often be characterized based on the chemical composition.
  • the high-value metal source can include an oxide ore.
  • Oxide ores typically contain high-value metals like copper and occasionally gold and silver. Copper oxide ores, such as malachite and cuprite, are commonly found. Other common metals include aluminum, iron, tin, and chromium. Oxide ores are relatively abundant and can be found worldwide. Bauxite, an aluminum oxide ore, is often found in tropical regions, while hematite, an iron oxide, is widespread.
  • the conventional extraction of high-value metals from oxide ores involves methods like smelting, leaching, or solvent extraction-electrowinning (SX-EW). Challenges for conventional approaches can include impurities in the ore, energy-intensive processes, and environmental concerns related to waste disposal and emissions.
  • the high-value metal source can include a sulfide ore.
  • Sulfide ores are known for containing valuable metals such as copper, gold, silver, and occasionally PGMs like platinum, palladium, rhodium, iridium, and ruthenium.
  • sulfide ores often include base metals like lead, zinc, and nickel.
  • Copper sulfide ores, particularly chalcopyrite, are common. Sulfide ores are abundant globally and found in various geological settings. Chalcopyrite, for instance, is found in multiple countries.
  • Conventional extraction methods for sulfide ores include froth flotation, smelting, and hydrometallurgical processes. Challenges for conventional methods encompass the need for selective flotation due to similar sulfide minerals, refractory ore characteristics, sulfur emissions, and environmental impacts.
  • the high-value metal source can include a chromite ore.
  • Chromite ores primarily contain chromium, a high-value metal critical in various industries. Iron and PGMs may also be present in some chromite deposits. Chromite ores are relatively abundant but primarily used for chromium extraction. They are often associated with layered intrusions in igneous rocks. The primary conventional extraction method for chromium is reduction, typically employing the alumino-thermic process. High energy requirements and environmental concerns regarding hexavalent chromium compounds are key challenges in this approach to processing chromite ores.
  • the high-value metal source can include a carbonate ore.
  • Carbonate ores while less common than oxide or sulfide ores, can contain high-value metals like copper. These ores can also include metals such as iron and other elements. Carbonate ores are typically found in sedimentary environments. Smelting and other extraction methods are conventionally utilized for metal recovery. Challenges with these conventional approaches to carbonate ores can arise from impurities and complex mineral compositions.
  • the high-value metal source can include a silicate ore.
  • Silicate ores can contain high-value metals like lithium, crucial for lithium-ion batteries, as well as common elements like iron. These ores are less common but are used for specific metals such as lithium. Silicate ores are associated with igneous or metamorphic rocks. Conventional lithium extraction involves acid leaching and evaporation processes. Challenges in this convention processing of silicate ores can include impurities and complex mineralogy, necessitating specialized extraction methods.
  • the high-value metal source can include a phosphate ore.
  • Phosphate ores primarily contain phosphorus, and while not high-value metals, phosphorus is essential for fertilizer production. Phosphate ores are relatively common and are primarily found in sedimentary environments. Conventional extraction methods involve chemical processing to produce phosphoric acid and fertilizers. A significant challenge in phosphate ore processing is environmental concerns related to phosphate runoff, which can lead to water pollution.
  • Ore grades can be used to refer to the concentration of valuable metals within the ore. Ore grades for precious metals like silver and gold and for platinum group metals are typically expressed in grams per ton (g/t) or ounces per ton (oz/ton). For high-value main group metals like copper, the ore grades are often expressed in a percentage, which is a weight percentage of the main group metal as compared to the weight of the ore. Depending on the quality of the source, the ore grades for high-value metals can vary significantly.
  • Ore grades for gold can, in some aspects, range from less than 1 gram per ton (g/t) to more than 5 g/t.
  • an ore containing gold will be said to be high-grade when the gold is present in the ore in an amount greater than 5 g/t, e.g. up to about 20 g/t or more.
  • an ore containing gold will be said to be low-grade when the gold is present in the ore in an amount of about 1 g/t or less.
  • Ore grades for silver can, in some aspects, range from less than 30 gram per ton (g/t) to more thanl 50 g/t.
  • an ore containing silver will be said to be high-grade when the silver is present in the ore in an amount greater than 150 g/t, e.g. up to about 500 g/t or more.
  • an ore containing silver will be said to be low-grade when the silver is present in the ore in an amount of about 30 g/t or less.
  • Ore grades for copper can, in some aspects, range from less than 0.5% to more than 3%.
  • an ore containing copper will be said to be high-grade when the copper is present in the ore in an amount greater than 2%, e.g. up to about 8% or more.
  • an ore containing copper will be said to be low-grade when the copper is present in the ore in an amount of about 0.5%, or 0.1%, or less.
  • Ore grades for platinum can, in some aspects, range from less than 2 gram per ton (g/t) to more than 10 g/t.
  • an ore containing platinum will be said to be high-grade when the platinum is present in the ore in an amount greater than 10 g/t, e.g. up to about 100 g/t or more.
  • an ore containing platinum will be said to be low-grade when the platinum is present in the ore in an amount of about 2 g/t, about 1 g/t, or less.
  • Ore grades for palladium can, in some aspects, range from less than 1 gram per ton (g/t) to more than 5 g/t.
  • an ore containing palladium will be said to be high-grade when the palladium is present in the ore in an amount greater than 5 g/t, e.g. up to about 50 g/t, 100 g/t, or more.
  • an ore containing palladium will be said to be low-grade when the palladium is present in the ore in an amount of about 1 g/t, about 0.5 g/t, or less.
  • Rhodium ore is exceptionally rare, and as such, there are limited sources of information on its typical concentrations in different ore grades. Rhodium is often found in low concentrations, even in high-grade PGM ores. Ore grades for rhodium can, in some aspects, range from less than 0.2 gram per ton (g/t) to more than 1 g/t. As used herein, an ore containing rhodium will be said to be highgrade when the rhodium is present in the ore in an amount greater than 0.8 g/t or 1 g/t, e.g. up to about 1.5 g/t or more. As used herein, an ore containing rhodium will be said to be low-grade when the rhodium is present in the ore in an amount of about 0.5 g/t or less.
  • Ruthenium ore is exceptionally rare, and as such, there are limited sources of information on its typical concentrations in different ore grades. Ruthenium is often found in low concentrations, even in high-grade PGM ores. Ore grades for ruthenium can, in some aspects, range from less than 0.2 gram per ton (g/t) to more than 1 g/t. As used herein, an ore containing ruthenium will be said to be high-grade when the ruthenium is present in the ore in an amount greater than 0.8 g/t or 1 g/t, e.g. up to about 1.5 g/t or more.
  • an ore containing ruthenium will be said to be low-grade when the ruthenium is present in the ore in an amount of about 0.5 g/t or less.
  • Iridium ore is exceptionally rare, and as such, there are limited sources of information on its typical concentrations in different ore grades. Iridium is often found in low concentrations, even in high-grade PGM ores. Ore grades for iridium can, in some aspects, range from less than 0.2 gram per ton (g/t) to more than 1 g/t.
  • an ore containing iridium will be said to be highgrade when the iridium is present in the ore in an amount greater than 0.8 g/t or 1 g/t, e.g. up to about 1.5 g/t or more.
  • an ore containing iridium will be said to be low-grade when the iridium is present in the ore in an amount of about 0.5 g/t or less.
  • Selenium ore is exceptionally rare, and as such, there are limited sources of information on its typical concentrations in different ore grades. Selenium is often found in low concentrations, even in high-grade PGM ores. Ore grades for selenium can, in some aspects, range from less than 0.2 gram per ton (g/t) to more than 1 g/t. As used herein, an ore containing selenium will be said to be high-grade when the selenium is present in the ore in an amount greater than 0.8 g/t or 1 g/t, e.g. up to about 1.5 g/t or more. As used herein, an ore containing selenium will be said to be low-grade when the selenium is present in the ore in an amount of about 0.5 g/t or less.
  • Gold concentrations in e-waste typically range from 0.1 to 1.5 grams per ton (g/t). This range covers various electronic devices, including circuit boards, connectors, and memory chips. High-end devices like computer motherboards tend to have higher gold content. Silver is commonly found in e-waste, with concentrations ranging from 5 to 100 g/t. It is present in various components, including connectors, switches, and some printed circuit boards. Copper is one of the most abundant metals in e-waste. Its concentrations can range from 10% to 30% by weight in some components, such as wires and connectors. Palladium is a valuable metal found in e-waste, primarily in ceramic capacitors and some electronic components. Its concentrations typically range from 1 to 5 g/t.
  • Industrial waste which can contain high-value metals such as platinum, palladium, rhodium, gold, and silver, is generated across various industries. Production volumes of industrial waste vary significantly by industry and location.
  • the industrial waste includes catalytic converters from automobiles.
  • the industrial waste includes catalysts from industrial waste streams. Challenges in industrial waste recycling include identifying and isolating valuable metals within mixed waste, handling hazardous materials, and ensuring efficient recovery. Recovery methods may involve hydrometallurgical or pyrometallurgical processes, depending on the specific metals and waste characteristics.
  • Platinum is often found in industrial waste in trace amounts, typically ranging from 5 parts per billion (ppb) to 5 parts per million (ppm). It is associated with various industrial catalysts and can be recovered from waste streams generated by industries like petroleum refining and chemical manufacturing. Palladium concentrations in industrial waste can vary from 5 ppb to 50 ppm. It is commonly used in catalytic converters in the automotive industry, and waste from automotive manufacturing and repair processes may contain higher concentrations of palladium. Rhodium is relatively rare in industrial waste and is typically found in trace amounts, often in the 5 ppb to 1 ppm range. It is used in catalytic converters and certain chemical processes. Gold concentrations in industrial waste can vary widely depending on the specific industry.
  • gold can be found in the range of 0.1 to 1 g/t or even higher. In other industrial waste streams, gold may be present in lower concentrations, typically ranging from 5 ppb to 5 ppm. Silver is used in various industrial applications, and its concentrations in waste can vary. In some industrial processes, silver waste may contain concentrations in the range of 1 to 10 g/t. In other cases, it may be present in lower concentrations, from 5 ppb to 5 ppm.
  • Mining concentrates are the valuable portions of mined ore that have undergone processing to remove unwanted materials, leaving a concentrated product rich in desired minerals or metals.
  • the goal of ore processing is to separate valuable minerals from the ore matrix, which often contains a mixture of minerals and gangue (unwanted material).
  • the process of creating mining concentrates involves various techniques, such as crushing, grinding, gravity separation, flotation, and magnetic separation. These processes are used to concentrate the valuable minerals, resulting in a product that contains a significantly higher percentage of the target metals or minerals. Concentrations of high-value metals in mining concentrates can be quite high.
  • Mining tailings waste materials left over from mining operations, can still contain high-value metals like gold, silver, copper, and sometimes platinum group metals (PGMs).
  • Tailings volumes depend on the scale of mining operations. Challenges include reprocessing tailings to recover metals, addressing environmental issues, and developing cost-effective methods. Recovery methods vary but may include gravity separation, flotation, and hydrometallurgical processes adapted to the specific tailings composition.
  • the concentration ranges of gold, silver, copper, and platinum group metals (PGMs) found in mining tailings can vary significantly depending on the type of ore that was processed, the extraction methods used, and the specific mineral composition of the tailings.
  • tailings from gold and silver mining operations can contain relatively high concentrations of gold or silver, ranging from a 2 grams per ton (g/t) to 10 g/t.
  • gold and silver concentrations are typically much lower, often in the range of 1 g/t or less.
  • copper concentrations can range from 10% on or higher and down to around 0.5% or lower.
  • PGM concentrations in mining tailings can vary significantly based on the specific ore and mining method. In some cases, tailings from PGM mining operations may contain higher PGM concentrations, with individual PGMs like platinum, palladium, and rhodium ranging from a few g/t to over 10 g/t.
  • the present disclosure pertains to a solvent leach composition
  • a solvent leach composition comprising at least one solvent, at least one oxidizing agent, and at least one halogen salt.
  • the solvent leach composition further comprises at least one ligand.
  • the disclosed solvent leach compositions are useful in the disclosed methods and processes to extract high value metals from high value metal material using the disclosed leaching methods.
  • the solvent or solvents in the solvent leach composition comprise a green (non-toxic and biodegradable), nonaqueous solvent.
  • the disclosed solvent leach composition maximizes the solubility of the leached high value metals, including, but not limited, to PGMs, copper, gold, and silver.
  • the oxidizing agent(s) in the solvent leach composition react with the halogen salts present in same, and that an in situ oxidation occurs and as a result halogen compounds are formed, at least in part, that act as strong oxidizing agents for high value metals in the high value metal material used in the disclosed methods.
  • the present disclosure pertains to disclosed stable solvent leach compositions comprising a disclosed solvent leach composition, wherein the pH of the solvent leach composition is adjusted to a pH value greater than about 5, thereby providing the stable solvent leach composition.
  • the pH of the solvent leach composition is adjusted to a pH from about 5 to about 12.
  • the pH of the solvent leach composition is adjusted to a pH from about 5 to about 10.
  • the pH of the solvent leach composition is adjusted to a pH from about 5 to about 8.
  • the pH of the solvent leach composition is adjusted to a pH from about 5 to about 7.
  • the oxidizing agent include, but is not limited, to ozone, chlorine, bromine, a bromate salt, a perbromate salt, hydrogen peroxide, a chlorate salt, a chlorite salt, a perchlorate salt, an organic peroxyacid, a superoxide, a peroxide-superoxide, an organic peroxyacid (and a salt thereof), a peroxyhydrate, a water-soluble organic peroxide, a nitrosodisulfonate, a hypochlorite, a hypobromite, chlorine dioxide, a chloroamine, a chloroamide, a chlorosulfamide, a bromoamine, a bromoamide, a bromosulfamide, a chlorosulfonic acid, a bromosulfonic acid, an inorganic oxidizing agent, and combinations thereof.
  • the oxidizing agent include, but is not limited, to chlorine, bromine, a bromate salt, a perbromate salt, hydrogen peroxide, a chlorate salt, a chlorite salt, a perchlorate salt, and combinations thereof.
  • the oxidizing agent is selected from lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof.
  • the oxidizing agent is a lithium salt.
  • a lithium salt can be used due to the relatively small ionic radius lithium, and accordingly, the greater solubility of lithium in a disclosed solvent.
  • the oxidizing agent is selected from sodium bromate, potassium bromate, and combinations thereof.
  • the oxidizing agent can be an alkaline salt such as a calcium salt, e.g., calcium bromate.
  • an oxidizing agent that is a calcium salt is believed to be able to precipitate from the solvent leach composition while bonding with impurities that are obtained in the disclosed methods.
  • the oxidizing agent can include, but is not limited to, an organic peroxyacid, a superoxide, a peroxide-superoxide, an organic peroxyacid (and a salt thereof), a peroxyhydrate, a water-soluble organic peroxide, a nitrosodisulfonate, a hypochlorite, a hypobromite, chlorine dioxide, a chloroamine, a chloroamide, a chlorosulfamide, a bromoamine, a bromoamide, a bromosulfamide, a chlorosulfonic acid, a bromosulfonic acid, and combinations thereof.
  • oxidizing agent can include one or more inorganic oxidizing agents.
  • the inorganic oxidizing is an inorganic peroxide (or salt thereof), an inorganic peroxyacid (or salt thereof), and combinations thereof.
  • the oxidizing agent can include one or more acids...
  • the oxidizing agent is present in the solvent leach composition at a concentration from about 0.01 grams/liter to about 250 grams/liter based on the total volume of the solvent leach composition. In a still further aspect, the oxidizing agent is present in the solvent leach composition at a concentration from about 0.1 grams/liter to about 100 grams/liter based on the total volume of the solvent leach composition. In a yet further aspect, the oxidizing agent is present in the solvent leach composition at a concentration from about 2 grams/liter to about 20 grams/liter based on the total volume of the solvent leach composition.
  • the halogen salt is an alkali metal bromide salt, an alkali chloride salt, an alkaline earth bromide salt, an alkaline earth chloride salt, and combinations thereof.
  • the halogen salt is selected from an alkali metal bromide salt, an alkali chloride salt, and combinations thereof.
  • the halogen salt is selected from sodium chloride, potassium chloride, sodium bromide, potassium bromide, lithium bromide, and combinations thereof.
  • the halogen salt comprises a first halogen salt comprising calcium cation and a halide anion and optionally a second halogen salt selected from sodium chloride, potassium chloride, sodium bromide, potassium bromide, lithium bromide, and combinations thereof.
  • the halogen salt comprises a halogen salt comprising a calcium cation and a halide anion, e.g., calcium bromide or calcium chloride.
  • a calcium salt can react with impurities such as sulfides formed using the disclosed methods with a high value metal material and/or if mineral acids are used in the disclosed method, e.g., sulfuric acid or hydrochloric acid) used as a further reagent in the disclosed methods.
  • impurities such as sulfides formed using the disclosed methods with a high value metal material and/or if mineral acids are used in the disclosed method, e.g., sulfuric acid or hydrochloric acid
  • cations having a smaller ionic radius, e.g., lithium cations, smaller size cations, such as lithium can have higher solubility in the solvent of the solvent leach composition.
  • a halogen salt comprising a cation which forms an insoluble salt
  • a cation that can be essentially precipitated completely from reaction mixture of the disclosed methods, e.g., a calcium salt.
  • the anion in the halogen salt can be selected to also have a size appropriate to the cation used.
  • the smaller halide anion such as a bromide and chloride can be used when the cation is lithium.
  • the amount of the halogen salt in the solvent leach composition is sufficient to solubilize high value metal halide complexes from the high value metal material used in the disclosed method, as well as maintain a ORP sufficiently high to maintain the high value metal obtained from the high value metal material in an ionic form in the reaction mixture.
  • the halogen salt is present in an amount from about 0.01 M to about 2.0 M based on the volume of the solvent leach composition.
  • the halogen salt is present in an amount from about 0.1 M to about 1.0 M based on the volume of the solvent leach composition.
  • the halogen salt is present in an amount from about 0.2 M to about 0.5 M based on the volume of the solvent leach composition.
  • the disclosed leach composition comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, a ketone, a carboxylic acid, an ester, a carbonate ester, and combinations thereof; and wherein the alcohol, an ether, a ketone, a carboxylic acid, an ester, a carbonate ester are optionally substituted with one or more group independently selected from a Cl- C5 alkyl, a hydroxy group, and combinations thereof.
  • the solvent comprises one or more alcohol-based and ether-based solvents, e.g., including, but not limited, to 3 -methoxy-3 -methyl- 1 -butanol or MMB.
  • the at least one solvent comprises a Cl -CIO alkyl compound comprising at least one hydroxy group and/or at least one ether moiety.
  • the at least one solvent comprises an alcohol-based solvent such as ethanol, methanol; glycol group alcohols; and combinations thereof.
  • the solvent comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, a ketone, and combinations thereof.
  • the solvent comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, and combinations thereof.
  • the solvent comprises a solvent selected from water, an alcohol, an ether, a ketone, and combinations thereof.
  • the solvent comprises a solvent selected from a polyethylene glycol, an alcohol, an ether, a ketone, and combinations thereof.
  • the solvent does not comprise water.
  • the solvent comprises a solvent selected from water, a CH3-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-CH3, CH3-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-OH, HO-CH2-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-OH, and combinations thereof;wherein the solvent is optionally substituted with one or more group independently selected from hydroxyl and C1-C5 alkyl; wherein the total number carbon residues is ten or less; and wherein each of m and n is independently selected from 0 and 1.
  • the solvent comprises a solvent selected from a CH3-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-CH3, CH3-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n- OH, HO-CH2-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-OH, and combinations thereof; wherein the solvent is optionally substituted with one or more group independently selected from hydroxyl and C1-C5 alkyl; wherein the total number carbon residues is ten or less; and wherein each of m and n is independently selected from 0 and 1.
  • the solvent comprises a solvent selected from a from a structure represented by a formula: combinations thereof.
  • the solvent is a compound having a structure represented by a formula: combinations thereof.
  • the solvent is 3-methoxy-3-methyl-l -butanol or MMB, i.e., a compound having a structure represented by a formula:
  • the polyethylene glycol has an average molecular weight from about 200 g/mol to about 20,000 g/mol. In a still further aspect, the polyethylene glycol has an average molecular weight from about 600 g/mol to about 4,000 g/mol. In a yet further aspect, the polyethylene glycol has an average molecular weight from about 1,000 g/mol to about 3,000 g/mol. In an even further aspect, the polyethylene glycol has an average molecular weight from about 1,500 g/mol to about 2,500 g/mol. In a still further aspect, the polyethylene glycol has an average molecular weight from about 1,900 g/mol to about 2,100 g/mol.
  • the solvent, or mixture of solvents is capable of effecting dissolution of at least one oxidizing agent used in the disclosed methods.
  • a material or compound, such as a solvent capable of effecting a chemical or physical process, such as dissolution of a material
  • the solvent is capable of effecting dissolution of at least one high value metal obtained using the disclosed methods.
  • the solvent is capable of effecting dissolution of at least one halide salt used in the disclosed methods.
  • the solvent is capable of effecting dissolution of at least one ligand used in the disclosed methods.
  • the solvent is capable of both effecting dissolution of at least one oxidizing agent used in the disclosed methods and effecting dissolution of at least one high value metal obtained using the disclosed methods.
  • the solvent is capable of both effecting dissolution of at least one oxidizing agent used in the disclosed methods and at least one halide salt used in the disclosed methods.
  • the solvent is capable of both effecting dissolution of at least one oxidizing agent used in the disclosed methods and effecting dissolution of at least one ligand used in the disclosed methods.
  • the solvent is capable of effecting dissolution of at least one oxidizing agent used in the disclosed methods, effecting dissolution of at least one halide salt used in the disclosed methods, and effecting dissolution of at least one high value metal obtained using the disclosed methods.
  • the solvent is capable of effecting dissolution of at least one oxidizing agent used in the disclosed methods, effecting dissolution of at least one halide salt used in the disclosed methods, and effecting dissolution of at least one ligand used in the disclosed methods.
  • the solvent is capable of effecting dissolution of at least one oxidizing agent used in the disclosed methods, effecting dissolution of at least one ligand used in the disclosed methods, and effecting dissolution of at least one high value metal obtained using the disclosed methods.
  • the solvent is capable of effecting dissolution of at least one oxidizing agent used in the disclosed methods, effecting dissolution of at least one halide salt used in the disclosed methods, effecting dissolution of at least one ligand used in the disclosed methods, and effecting dissolution of at least one high value metal obtained using the disclosed methods.
  • the solvent, or mixture of solvents is capable of effecting both the solubility, i.e., dissolution, and the stability of various components used in or formed in the disclosed methods.
  • the solvent, or mixture of solvents is capable of effecting dissolution of at least one oxidizing agent in the method, at least one halide salt in the method, and/or one or more high value metal obtained, as well as effecting the stability of various reagents or materials in course of carrying out the disclosed methods, e.g., stability of at least one oxidizing agent in the method, at least one halide salt in the method, and/or one or more high value metal obtained.
  • the solvent, or mixture of solvents can particularly facilitate the in situ and gradual formation of effective oxidation reaction conditions.
  • the disclosed solvent leach compositions accordingly, provide for improved control of the oxidizing agent and overall oxidation reaction, which in turn allows the disclosed methods to minimize chemical consumption to reducing the overall cost of leaching a high value metal from a high value metal material.
  • the solvent, or mixture of solvents is not reactive with other reagents, e.g., oxidizing agent and/or halide salts, used in the disclosed methods, and essentially acts as a medium for dissolution of reagents and high value metals.
  • reagents e.g., oxidizing agent and/or halide salts
  • the solvent further comprises water.
  • water concentration can be in the range from about 1 wt% to about 99 wt% based on the total solvent mass with the remainder of the solvent being one or a mixture of a disclosed solvent such as an alcohol- based or an ether-based solvent.
  • water concentration can be in the range from about 40 wt% to about 70 wt% based on the total solvent mass with the remainder of the solvent being one or a mixture of a disclosed solvent such as an alcohol-based or an ether-based solvent.
  • water concentration can be in the range from about 45 wt% to about 55 wt% based on the total solvent mass with the remainder of the solvent being one or a mixture of a disclosed solvent such as an alcohol-based or an ether-based solvent.
  • a disclosed solvent such as an alcohol-based or an ether-based solvent.
  • water can be added to the solvent mixture as long as the water content does not negatively impact the efficiency and recovery rate of the high value metal.
  • water can be added to the solvent mixture as long as the water content does not negatively impact the efficiency and recovery rate of the high value metal.
  • the solvent is water.
  • the use of a solvent that consists essentially of water provides an environment in which the oxidizing agents and halide salts used in the solution leach composition are highly soluble in the solvent, thereby enabling in situ oxidation in the solution mixture.
  • the solvent is water.
  • a solvent that consists essentially of water provides an environment in which the oxidizing agents, halide salts, and ligands used in the solution leach composition are highly soluble in the solvent, thereby enabling in situ oxidation in the solution mixture.
  • the solvent does not comprise water and is used without aqueous dilution.
  • the ligand is is a compound according to the following formula or a sodium or calcium salt thereof where each occurrence of Ri, R2, and R3 is independently selected from the group consisting of H, alkyl, heteroalkyl, -R4CO(OH), and -R5N( s)(R7) so long as at least one of Ri, R2, or R3 is - R4CO(OH); where each occurrence of Re and R7 is independently selected from the group consisting of H, alkyl, heteroalkyl, -R4CO(OH), and -R8N(R9)(RIO) so long as at least one of R6 and R7 is -R4CO(OH); where each occurrent of Rs and Rs is independently a Cl -Cl 2 substituted or unsubstituted alkyl, a C1-C12 substituted or unsubstituted heteroalkyl, or a a C1-C12 substituted or unsubstituted cycloalky
  • the ligand is selected from the group consisting of sodium acetate, sodium citrate, oxalate, malonate, tartrate, gluconate, nitrilotriacetic acid, phthalate, citramalate, ethylenediaminetetraacetic acid (EDTA), diaminoethanetetraacetic acid (CDTA), trans- 1,2- Diaminocyclohexanetetraacetic acid (DCTA), nitrilotriacetic acid, N- hydroxy ethylethylenediaminetriacetic acid (HEDTA), iminodiacetic acid (IDHA), propylenediaminetetraacetic acid (PDTA), sodium and calcium salts of any of the foregoing, and combinations thereof.
  • EDTA ethylenediaminetetraacetic acid
  • CDTA diaminoethanetetraacetic acid
  • DCTA trans- 1,2- Diaminocyclohexanetetraacetic acid
  • HEDTA N- hydroxy e
  • the ligand is selected from sodium acetate, sodium citrate, ethylenediaminetetraacetic acid (i.e. EDTA), and combinations thereof.
  • the present disclosure pertains to methods and processes to recover high value metals from a high value metal material using the disclosed leaching method, the method comprising the steps of contacting a high value metal material with a disclosed solvent leach composition thereby forming a high value metal slurry comprising a high value metal pregnant leach solution and insoluble impurities, filtering insoluble impurities from the high value metal slurry, and extracting high value metals from the high value metal pregnant leach solution.
  • the high value metal material may be a precious metal material including primary resources such as a mining extract including concentrates, ores, such as sulfide or oxide ores, or tailings, or secondary resources such as recycled materials including spent catalysts such as spent automotive catalysts, precious metal-bearing membranes such as hydrogen membrane fuel cells, hydrogen electrolysis, precious metal-bearing electrodes such as mixed-metal-oxides (MMO), electronic wastes, spark plugs, precious metal-bearing sensors, alloys, and recycled dental equipment.
  • primary resources such as a mining extract including concentrates, ores, such as sulfide or oxide ores, or tailings
  • secondary resources such as recycled materials including spent catalysts such as spent automotive catalysts, precious metal-bearing membranes such as hydrogen membrane fuel cells, hydrogen electrolysis, precious metal-bearing electrodes such as mixed-metal-oxides (MMO), electronic wastes, spark plugs, precious metal-bearing sensors, alloys, and recycled dental equipment.
  • MMO mixed-metal-
  • the high value metal material may be a copper material including primary resources such as mining extracts including concentrates, ores, such as sulfide and oxide ores including covellite and chalcopyrite, or tailing, or secondary resources such as recycled materials including electronic wastes, printed circuit boards (i.e. PCB), compute processing boards, graphic cards, data processing boards, electric cables, copper-bearing sensors, alloys, and recycled electric and electronic equipment.
  • primary resources such as mining extracts including concentrates, ores, such as sulfide and oxide ores including covellite and chalcopyrite, or tailing
  • secondary resources such as recycled materials including electronic wastes, printed circuit boards (i.e. PCB), compute processing boards, graphic cards, data processing boards, electric cables, copper-bearing sensors, alloys, and recycled electric and electronic equipment.
  • PCB printed circuit boards
  • the disclosed methods can be used for the dissolution of high value metals.
  • high value metals include the elements Cu, Au, Ag, Pd, Pt, Ir, Rh, Ru, and Os; and that the platinum group metals (“PGM” or “PGMs”) include Pd, Pt, Ir, Rh, Ru, and Os.
  • the present disclosure pertains to methods for leaching and extracting a high value metal from a high value metal material, the method comprising: preparing a disclosed solvent leach composition; contacting the high value metal material with the solvent leach composition, thereby forming a high value metal slurry; filtering the high value metal slurry to obtain a filtrate comprising a high value metal pregnant leach solution and a solid retained by the filter comprising insoluble impurities; and extracting the high value metal from the high value metalpregnant solution.
  • the present disclosure pertains to methods for leaching and extracting a high value metal from a high value metal material, the method comprising: providing a disclosed stable solvent leach composition; adjusting the pH of the stable solvent composition to a pH below about 4; contacting the high value metal material with the solvent leach composition, thereby forming a high value metal slurry; filtering the insoluble impurities from the slurry; and extracting the high value metal from the high value metal-pregnant solution; wherein the high value metal slurry comprises a high value metal-pregnant solution and insoluble impurities; and wherein the high value metal slurry comprises from about 1 wt% to about 50 wt% high value metal material.
  • the high value metal slurry comprises from about 10 wt% to about 20 wt% high value metal material.
  • the leaching method is performed by immersing the high value metal material in a solvent leach composition containing the solvent, the halogen salt and the oxidizing agent or agents.
  • the solvent leach composition may further comprise a ligand. The resulting mixture is agitated to conduct an agitated leaching process. Subsequently, in the resulting mixture, the high value metals are oxidized and form high value metal salts, which are soluble in the solvent leach composition.
  • soluble halides in the solvent leach composition can react with the oxidizing agents directly to create a stronger oxidant (e.g., bromine) to oxidize high value metals in the high value metal material and convert them to charged ions and subsequently produce soluble high value metal salts soluble in the solvent leach composition.
  • a stronger oxidant e.g., bromine
  • the solution oxidation reduction potential can be above about 400 mV as measured using a standard Silver/Silver Chloride electrode . This ORP amount is enough to convert the high value metals into an ionic form to generate a soluble complex with halide ions present in the solution.
  • the solvent leach composition selectively dissolves the resulting high value metal salts and leaves other elements, metals, and materials behind in solid form.
  • the ORP can be from about 400 mV to about 900 mV. In a still further aspect, the ORP can be from about 600 mV to about 900 mV. In a yet further aspect, the ORP can be from about 700 mV to about 800 mV.
  • the ORP can be different based on the high value material and the concentration of the high value metal in the high value metal material.
  • the ORP for electronic waste material can be about 800 mV, whereas for low-grade copper ores the ORP can be about 500mV to about 600 mV.
  • the disclosed methods can use injection or mixing into a reaction mixture one or more oxidizing agent as disclosed herein, either in lieu or in addition to the in situ oxidation reaction as described herein.
  • solid residues in the slurry can comprise solid residues that are carried forward into a reaction mixture from the high value metal material (i.e., are present prior to the disclosed methods for leaching and extraction) and/or arise during the course of the reaction of the disclosed methods as precipitates from said reaction.
  • the resulting solid residues comprising impurities can be substantially free of high value metals.
  • the leaching stage includes a filtering step wherein the slurry is filtered to separate the high value metal pregnant leach solution from the solid residues.
  • the solid residues may be washed using an organic solvent or water, for example.
  • the high value metal pregnant leach solution and the solid residues may be weighed and assayed using, for example, X-ray fluorescence (XRF) spectrometry. Completing the mass balance can provide values for high value metal recovery and dissolution efficiency of the solvent. In the examples below, some extraction values are presented.
  • XRF X-ray fluorescence
  • the leaching solution temperature, pH, stirring speed, pulp density (which is the amount of solid high value metal material in the solution), ORP, pressure, and the time for which the high value metal material is in contact with the solvent leach composition are important parameters that should be monitored or controlled through the leaching process. The impact of some of these parameters on high value metal extraction is described in the provided examples.
  • the solvent leach composition is prepared by mixing the solvent, halogen salts, and oxidizing agents.
  • the solvent leach composition is prepared by mixing the solvent, at least a halogen salt, at least an oxidizing agent, and at least a ligand.
  • the solvent leach composition is stable enough to host the reactions occurring in the reaction mixture of the disclosed methods. Without wishing to be bound by a particular theory, it is believed that the solvent leach composition does not comprise reactions of the oxidizing agent-halogen salt oxidation reactions and the reactions that occur after the addition of the high value metal material in step 120. Also, the solvent can maximize the solubility of reagents and oxidants and reactions products which will increase the efficiency of extraction while minimizing the off-gassing and evaporation of chemicals, which will decrease the cost of extraction dramatically.
  • the solvent leach composition increases the solubility and stability of oxidants and reagents in their oxidizing phase, which subsequently will facilitate controlling the amount of oxidants required in the leaching process and will help develop in-situ and gradual oxidation, which will minimize chemical consumption in the process and will reduce the high value metal recovery costs dramatically.
  • the high value metal material preferably in powdered form
  • the solvent leach composition e.g., added to, or submerged into, the prepared solvent leach composition in a suitable reactor/reaction vessel.
  • the high value metal-containing substance may be in chunks and any other form except fine powders.
  • lower size substances tend to yield higher efficiencies and metal recovery rates mainly due to decreased passivation layer, increased permeability, and increased surface area, for example.
  • use of the disclosed methods for particularly leaching Rh and Ru-containing materials can utilize small-size powders such as submicron powders of the high value metal material.
  • the high value metal material may be a primary resource such as a mining extract including concentrates, ores, such as sulfide or oxide ores, or tailings, or secondary resources such as recycled materials including spent catalysts such as spent automotive catalysts, precious metal-bearing membranes such as hydrogen membrane fuel cells, hydrogen electrolysis, precious metal-bearing electrodes such as mixed-metal-oxides (MMO), electronic wastes, spark plugs, electronic wastes, PCBs, compute processing boards, graphic cards, data processing boards, high value metal-bearing sensors, alloys, and recycled dental equipment.
  • a primary resource such as a mining extract including concentrates, ores, such as sulfide or oxide ores, or tailings
  • secondary resources such as recycled materials including spent catalysts such as spent automotive catalysts, precious metal-bearing membranes such as hydrogen membrane fuel cells, hydrogen electrolysis, precious metal-bearing electrodes such as mixed-metal-oxides (MMO), electronic wastes, spark plugs, electronic wastes, PCBs
  • the leaching process there are no particular limitations on the carbon contents in the high value metal material as the leaching process can operate in low temperatures (thus, not burning the carbon content and not incurring ashing or calcining, for example). Moreover, carbon does not participate in the reactions during the leaching process 100 and remains intact.
  • step 130 the mixture of the solvent leach composition and the high value metal material is agitated, for example, using a magnet stirrer, and the actual leaching reactions take place.
  • the solvent leach composition may be agitated for 0.5 to 96 hours and preferably for 8 to 24 hours.
  • the presence of existing oxidants in the solvent leach composition causes high value metal oxidation and the formation of high value metal salts which are soluble in the solvent leach composition.
  • the solvent leach composition selectively dissolves the resulting high value metal salts and leaves other elements, metals, and materials behind in solid form.
  • Acids may be added to the mixture comprising the solvent leach composition and the high value metal-containing substance to decrease the pH and to maximize the efficiency of the reactions.
  • a variety of acids including mineral acids, organic acids, and mixtures thereof, may be used during step 130.
  • the acid that is added can be selected from hydrobromic acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, and combinations thereof.
  • the acid that is added can be selected from sulfuric acid, hydrochloric acid, acetic acid, citric acid, and mixtures thereof.
  • the acid can be chosen that is relatively safe for production processes and/or introduces minimal impurities to the solvent leach composition.
  • the acid may be diluted or concentrated. Concentrated acids may be preferable since they will not affect or minimize the water mass balance of the whole leaching process 100.
  • the pH during step 130 is generally between 0 to 5 and preferably between 1 to 3.
  • the selection of the acid may depend on the choice of used oxidizing agents and halogen salts, and potential ligands. For example, in case bromate or hypobromate is used in the solvent leach composition, the pH will be around 3 and stronger acids may be used. Alternatively, if chlorine derivatives are used, the pH of the solvent leach composition may drop to between 0 to 1 and weaker acids may be used.
  • the ORP can be greater than or equal to about 400 mV. In a further aspect, the ORP can be greater than or equal to about 600 mV. In some instances, an ORP greater than or equal to 600 mV may be useful in order to more fully oxidize the high value metals in the high value metal material. In a still further aspect, the ORP can be from about 400 mV to about 900 mV. In a yet further aspect, the ORP can be from about 600 mV to about 900 mV. In an even further aspect, the ORP can be from about 700 to 800 mV.
  • an ORP greater than or equal to about 900 mV may result in oxidization of other components of the solvent leach composition, including water, which in turn, may increase the acidity of the solvent leach composition. In some instances, it may be desirable to minimize oxidation of other components in the solvent leach composition, such as water, in order to provide an improved process environment, including from a safety perspective.
  • step 140 the leaching slurry is filtered, and the liquid solution and solid residues are separated from each other.
  • the slurry is passed through a filter (including, but not limited to, polypropylene or polyvinyl chloride-based filters) having a pore size from about 1 pm to about 25 pm.
  • the filter has a pore size from about 5 pm to about 10 pm.
  • the flow of the slurry through the filter may be by gravity, however, in some instances the filtration can be carried out using a vacuum or positive pressure.
  • the leaching method 100 can be part of a high value metal extraction process.
  • Figure 2 shows a flowchart of a high value metal extraction process 200.
  • the extraction process 200 comprises a substance preparation stage 210, a leaching stage 220, and an extraction stage 230.
  • the substance preparation stage 210 one or more high value metal material, such as mining extracts or spent automotive catalysts, are prepared, for example, by being ground to fine powders.
  • the leaching stage 220 the prepared substance is added to the solvent leach composition to leach the high value metal(s) and obtain a high value metal pregnant leach solution.
  • the leaching stage 220 may include a continuous tank leaching step 222 wherein a continuous feed of prepared substances may be leached continuously.
  • the leaching stage 220 further includes a filtration step 224, similar to the filtration step 140 under Figure 1, wherein the leaching slurry is filtered, and the high value metal pregnant leach solution and solid residues are separated from each other.
  • the solid residues i.e. leach tailings
  • the solid residues may be further processed.
  • the solid residues may be monitored for any harmful substances and may be disposed of or prepared for further material extraction.
  • the solid residues may contain secondary high value metals which may be recovered through a secondary process such as a secondary leaching process.
  • the high value metal-pregnant leach solution primarily comprise copper, whereas the remaining solid residues may contain silver or other precious metals which may be recovered through a further leach process.
  • high value metal pregnant leach solution may be stored, for example in a high value metal pregnant leach solution storage tank, for later high value metal extraction.In the extraction stage 230, the high value metal is extracted from the high value metal pregnant leach solution.
  • the high value metal extraction stage 230 may include a solvent extraction-electrowinning (referred to as SX/EW hereafter) step 232 which results in the extraction of the high value metal in the form of high value metal cathode 234.
  • SX/EW process may comprise a solvent extraction stage (SX) in which the high value metal pregnant leach solution is contacted with an extractant, such as an organic solvent, to create a high-grade high value metalbearing solution with high concentrations of high value metal ions, while leaving a high value metalbarren phase.
  • SX solvent extraction stage
  • the high value metal-barren phase which may contain the remains of the solvent leach composition, may be purified and recycled in a solvent purification stage 240 for reuse in the leaching stage 220.
  • the recycled solvent can be reused to dissolve high value metals from new high value metal material.
  • the high-grade high value metal-bearing solution is then advanced to an electrowinning stage (EW) where high value metal ions in the solution are electrochemically reduced to metallic cathodes 234.
  • EW electrowinning stage
  • the high value metal extraction process 200 can further include a high value metal refinement stage, wherein the high value metal is refined.
  • each stage of the high value metal extraction process 200 can be carried out in a separate and distinct physical location from another stage.
  • the preparation stage 210 can further include preparing the solvent leach composition as explained previously.
  • the solvent leach composition may be prepared by mixing the mentioned solvents, oxidizing agents, a halide salt, and potentially a ligand.
  • the pH of the prepared solvent leach composition can be increased by, for example, adding a hydroxide salt, such as an alkali hydroxide such as sodium hydroxide.
  • a hydroxide salt such as an alkali hydroxide such as sodium hydroxide.
  • the oxidizing agents in the solvent leach composition can be temporarily deactivated until the pH is lowered below 5.
  • any suitable acid may be added to the solvent leach composition to reduce the pH levels to 0 to 5 and start the in-situ reactions with the high value metal-containing substances.
  • the leaching method 100 may vary from the agitated leaching process as described in Figure 1 and 2.
  • heap leaching and vat leaching methods can be used, in which the solvent leach composition, after being prepared in a step similar to step 110, can be added to the high value metal material rather than the high value metal material being added to the prepared solvent leach composition.
  • the solvent leach composition is initially sprinkled or deposited on the high value metal material and then flows through the high value metal material, for example using gravity.
  • the solvent leach composition may flow through the high value metal material for long periods such as weeks or months.
  • the methods include a batch leaching method for high-value metals.
  • the batch leaching methods can involve the processing of a finite amount of ore or source material in discrete batches, as opposed to continuous methods.
  • the batch leaching methods can include a commution of the source material. Commution can include grinding, crushing, milling, and combinations thereof. The process can begin with the crushing of source material to achieve a consistent particle size.
  • the methods can include agglomeration of the high-value metal source material.
  • the crushed source material can in some aspects be agglomerated by mixing it with a binder, such as lime or cement, to improve permeability and ensure uniform flow of leach solution.
  • the methods can then include contacting the leach compostion with the source material in a batch reactor or tank.
  • the source material and leach composition are allowed to react for a specified period, often ranging from several hours to a few days. During this time, the leach composition dissolves the high-value metals from the source materials.
  • the methods can include solid-liquid separation to separate the liquid phase (pregnant solution) from the solid phase (residue insoluble material).
  • the methods can include a continuous leaching process.
  • Continuous recovery methods for high-value metals typically involve continuous processing systems that continuously extract metals from ore or other source materials. These methods are often used in industrial- scale operations to achieve efficient and consistent metal recovery.
  • CVL Continuous Vat Leaching
  • the methods can include a heap leaching method.
  • Heap leaching is a common method used for extracting high-value metals such as gold and copper from low-grade ores. The process involves stacking ore in a heap on an impermeable liner, irrigating it with a leach solution, and allowing the metals to dissolve over time.
  • the methods can include commution of the high-value metal source material; and/or agglomeration of the high-value metal source material. For example, the source materials can be crushed and combined with a binder, often a cement or lime, to improve the permeability of the heap and enhance metal recovery.
  • An impermeable liner often made of synthetic materials like HDPE (High- Density Polyethylene) or clay, can be placed at the base of the leach pad to prevent the leach solution from seeping into the ground.
  • the agglomerated ore can then be stacked in a heap on top of the liner.
  • the heap is typically built in lifts or layers, with each layer compacted to ensure good contact between the ore particles.
  • the leach solution is allowed to percolate downward through the heap, dissolving the target metals from the source material particles as it passes through.
  • the term “comprising” is intended to include examples and aspects encompassed by the terms “consisting essentially of’ and “consisting of.” Similarly, the term “consisting essentially of’ is intended to include examples encompassed by the term “consisting of. [0142] As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
  • references to "a" chemical compound refers to one or more molecules of the chemical compound rather than being limited to a single molecule of the chemical compound. Furthermore, the one or more molecules may or may not be identical, so long as they fall under the category of the chemical compound. Thus, for example, "a" chemical compound is interpreted to include one or more molecules of the chemical, where the molecules may or may not be identical (e.g., different isotopic ratios, enantiomers, and the like).
  • platinum group metal and “PGM” can be used interchangeably, and refer to one or more metals including Pd, Pt, Ir, Rh, Ru, and Os.
  • alkyl as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, w-propyl, isopropyl, /?-butyl, isobutyl, s-butyl, Z-butyl, n- pentyl, isopentyl, .s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like.
  • the alkyl group can be cyclic or acyclic.
  • the alkyl group can be branched or unbranched.
  • the alkyl group can also be substituted or unsubstituted.
  • the alkyl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl, sulfo-oxo, or thiol, as described herein.
  • a “lower alkyl” group is an alkyl group containing from one to six (e.g., from one to four) carbon atoms.
  • alkyl group can also be a Cl alkyl, C1-C2 alkyl, C1-C3 alkyl, C1-C4 alkyl, C1-C5 alkyl, C1-C6 alkyl, C1-C7 alkyl, C1-C8 alkyl, C1-C9 alkyl, C1-C10 alkyl, and the like up to and including a C1-C24 alkyl.
  • alkyl is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group.
  • halogenated alkyl or “haloalkyl” specifically refers to an alkyl group that is substituted with one or more halide, e.g., fluorine, chlorine, bromine, or iodine.
  • the term “monohaloalky 1” specifically refers to an alkyl group that is substituted with a single halide, e.g. fluorine, chlorine, bromine, or iodine.
  • polyhaloalkyl specifically refers to an alkyl group that is independently substituted with two or more halides, i.e. each halide substituent need not be the same halide as another halide substituent, nor do the multiple instances of a halide substituent need to be on the same carbon.
  • alkoxyalkyl specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below.
  • aminoalkyl specifically refers to an alkyl group that is substituted with one or more amino groups.
  • hydroxyalkyl specifically refers to an alkyl group that is substituted with one or more hydroxy groups.
  • alkanediyl refers to a divalent saturated aliphatic group, with one or two saturated carbon atom(s) as the point(s) of attachment, a linear or branched, cyclo, cyclic or acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen.
  • the groups, — CH2 — (methylene), — CH2CH2 — , — CH2C(CH3)2CH2 — , and — CH2CH2CH2 — are non-limiting examples of alkanediyl groups.
  • ether as used herein is represented by the formula A 3 OA 2 , where A 1 and A 2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein.
  • polyether as used herein is represented by the formula — (A 1 O-A 2 O) a — , where A 1 and A 2 can be, independently, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and “a” is an integer of from 1 to 500.
  • Examples of poly ether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.
  • R 1 ,” “R 2 ,” “R 3 ,”... “R n ,” where n is an integer, as used herein can, independently, possess one or more of the groups listed above.
  • R 1 is a straight chain alkyl group
  • one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halide, and the like.
  • a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group.
  • an alkyl group comprising an amino group the amino group can be incorporated within the backbone of the alkyl group.
  • the amino group can be attached to the backbone of the alkyl group.
  • the nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.
  • the term “substituted” is contemplated to include all permissible substituents of organic compounds.
  • the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds.
  • Illustrative substituents include, for example, those described below.
  • the permissible substituents can be one or more and the same or different for appropriate organic compounds.
  • the heteroatoms, such as nitrogen can have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms.
  • substitution or “substituted with” include the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. It is also contemplated that, in certain aspects, unless expressly indicated to the contrary, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).
  • compounds of the disclosure may contain “optionally substituted” moieties.
  • substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
  • an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
  • Combinations of substituents envisioned by this disclosure are preferably those that result in the formation of stable or chemically feasible compounds.
  • individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).
  • a residue of a chemical species refers to the moiety that is the resulting product of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the moiety is actually obtained from the chemical species.
  • an ethylene glycol residue in a polyester refers to one or more - OCH2CH2O- units in the polyester, regardless of whether ethylene glycol was used to prepare the polyester.
  • a sebacic acid residue in a polyester refers to one or more -CO(CH2)8CO- moieties in the polyester, regardless of whether the residue is obtained by reacting sebacic acid or an ester thereof to obtain the polyester.
  • organic residue defines a carbon containing residue, i.e., a residue comprising at least one carbon atom, and includes but is not limited to the carbon-containing groups, residues, or radicals defined hereinabove.
  • Organic residues can contain various heteroatoms, or be bonded to another molecule through a heteroatom, including oxygen, nitrogen, sulfur, phosphorus, or the like. Examples of organic residues include but are not limited alkyl or substituted alkyls, alkoxy or substituted alkoxy, mono or di- substituted amino, amide groups, etc.
  • Organic residues can preferably comprise 1 to 18 carbon atoms, 1 to 15, carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms.
  • an organic residue can comprise 2 to 18 carbon atoms, 2 to 15, carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, 2 to 4 carbon atoms, or 2 to 4 carbon atoms.
  • a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible isomer, e.g., each enantiomer and diastereomer, and a mixture of isomers, such as a racemic or scalemic mixture.
  • Compounds described herein can contain one or more asymmetric centers and, thus, potentially give rise to diastereomers and optical isomers.
  • the present disclosure includes all such possible diastereomers as well as their racemic mixtures, their substantially pure resolved enantiomers, all possible geometric isomers, and pharmaceutically acceptable salts thereof. Mixtures of stereoisomers, as well as isolated specific stereoisomers, are also included. During the course of the synthetic procedures used to prepare such compounds, or in using racemization or epimerization procedures known to those skilled in the art, the products of such procedures can be a mixture of stereoisomers.
  • references to a chemical compound refers to one or more molecules of the chemical compound rather than being limited to a single molecule of the chemical compound. Furthermore, the one or more molecules may or may not be identical, so long as they fall under the category of the chemical compound described. Thus, for example, "a" chemical compound such as a polymer is interpreted to include one or more polymer molecules of the polymer, where the polymer molecules may or may not be identical (e.g., different one or more molecular weights consistent with the molecular weight defined for the polymer such as a weight average molecular).
  • ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect.
  • a further aspect includes from the one particular value and/or to the other particular value.
  • ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’.
  • the range can also be expressed as an upper limit, e.g.
  • ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of Tess than x’, less than y’, and Tess than z’.
  • the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y’, and ‘greater than z’.
  • the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values includes “about ‘x’ to about ‘y’”.
  • a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible subranges) within the indicated range.
  • the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined.
  • contacting refers to bringing a disclosed analyte, compound, solvent, composition, chemical, or material in proximity to another disclosed analyte, compound, solvent, composition, chemical, or material as indicated by the context.
  • a solvent leach composition contacting a high value metal-containing material refers to the solvent leach composition being in proximity to the high value metal-containing material by the high value metalcontaining material interacting and binding to the high value metal-containing material via ionic, dipolar and/or van der Waals interactions.
  • contacting can comprise both physical and chemical interactions between the indicated components.
  • chemical interactions can comprise a combination of covalent and non-covalent interactions, including one or more of ionic, dipolar, van der Waals interactions, and the like.
  • a solvent leach composition contacting a high value metal-containing material is understood to mean that the solvent leach composition is in physical and chemical contact with the high value metal-containing material and can comprise covalent, ionic, and non-covalent interactions.
  • an "effective amount” of a solvent leach composition refers to an amount that is sufficient to achieve the desired leaching of high value metals from a high value metal-containing material.
  • the specific level in terms of wt%, vol% and/or ratio (either weight or volume ratio) in a composition required as an effective amount will depend upon a variety of factors including the amount and type of high value metal-containing material, amount and type of solvent leach composition, and economic considerations.
  • Certain materials, compounds, compositions, and components disclosed herein can be obtained commercially or readily synthesized using techniques generally known to those of skill in the art.
  • the starting materials and reagents used in preparing the disclosed compounds and compositions are either available from commercial suppliers such as Aldrich Chemical Co., (Milwaukee, Wis.), Acros Organics (Morris Plains, N. J.), Fisher Scientific (Pittsburgh, Pa.), or Sigma (St.
  • compositions of the disclosure Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
  • compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
  • temperatures referred to herein are based on atmospheric pressure (i.e., one atmosphere).
  • PGM Platinum Group Metals i.e., Pd, Pt, Ir, Rh, Ru, and Os
  • a method of extracting a high-value metal from a high-value metal source material comprising: contacting the high-value metal source material with a leach composition described herein for a first period of time to form a high-value metal slurry;filtering the high-value metal slurry to remove impurities from the high- value metal slurry that are insoluble in the leach composition to form a pregnant solution; and extracting the high value metal from the pregnant solution, thereby forming a spent leach composition.
  • Aspect 2 The method according to any one of Aspects 1-91, wherein the solvent in the leach composition is selected from the group consisting of water, a polyethylene glycol, an alcohol, an ether, a ketone, and combinations thereof; wherein the oxidizing agent in the leach composition is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof; andwherein the halogen salt in the leach composition is present in in a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof.
  • the solvent in the leach composition is selected from the group consisting of water, a polyethylene glycol, an alcohol, an ether, a ketone, and combinations thereof; wherein the oxidizing agent in the leach composition is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof
  • Aspect 3 The method according to any one of Aspects 1-91, wherein the method comprises a batch leaching method, and wherein the contacting step comprises applying the leach composition to the high-value metal source material in a batch reactor.
  • Aspect 4 The method according to any one of Aspects 1-91, wherein the method comprises a batch leaching method, and wherein the contacting step comprises applying the leach composition to the high-value metal source material in a batch reactor.
  • Aspect 5 The method according to any one of Aspects 1-91, wherine the method comprises a continuous leaching method, and wherein the contacting step comprises continuously contacting the leach composition to the high-value metal source material as it passes through one or more reactors.
  • Aspect 6 The method according to any one of Aspects 1-91, wherine the method comprises a continuous leaching method, and wherein the contacting step comprises continuously contacting the leach composition to the high-value metal source material as it passes through one or more reactors.
  • Aspect 7 The method according to any one of Aspects 1-91, wherein the method comprises a heap leach method, and wherein the contacting step comprises applying the leach composition to a heap comprising the high-value metal source material.
  • Aspect 8 The method according to any one of Aspects 1-91, wherein the method comprises a heap leach method, and wherein the contacting step comprises applying the leach composition to a heap comprising the high-value metal source material.
  • Aspect 9 The method according to any one of Aspects 1-91, further comprising prior to step (a) one or both of: commution of the high-value metal source material; and agglomeration of the high-value metal source material.
  • Aspect 10 The method according to any one of Aspects 1-91, wherein the method comprises step (i) and wherein the commution is selected from the group consisting of griding, crushing, milling, and combinations thereof.
  • Aspect 11 The method according to any one of Aspects 1-91, wherein the method comprises step (ii) and wherein the agglomeration step is selected from the group consisting of drum agglomeration, pan agglomeration, pugmill agglomeration, and combinations thereof.
  • Aspect 12 The method according to any one of Aspects 1-91, wherein the first period of time is from about 0.5 hours to about 48 hours.
  • Aspect 13 The method according to any one of Aspects 1-91, wherein the first period of time is from about 8 hours to about 24 hours.
  • Aspect 14 The method according to any one of Aspects 1-91, wherein the first period of time is from about one week to about 10 weeks.
  • Aspect 15 The method according to any one of Aspects 1-91, wherein the first period of time is from about 24 hours to about 96 hours.
  • Aspect 16 The method according to any one of Aspects 1-91, wherein the first period of time is from about 30 days to about 1 year.
  • Aspect 17 The method according to any one of Aspects 1-91, wherein the high-value metal source is selected from the group consisting of a mining extract, a recycled material, and combinations thereof.
  • Aspect 18 The method according to any one of Aspects 1-91, wherein the high-value metal source material is selected from the group consisting of ore deposits, electronic waste (E-Waste), industrial waste, catalytic converters, battery waste, waste from photovoltaic solar panels, printed circuit boards (PCBs), mining concentrates, and mining tailings.
  • Aspect 19 The method according to any one of Aspects 1-91, wherein the high-value metal source material is a mining extract selected from the group consisting of a mining concentrate, an ore, a mining tailing, and combinations thereof.
  • the high-value metal source material is a mining extract selected from the group consisting of a mining concentrate, an ore, a mining tailing, and combinations thereof.
  • Aspect 20 The method according to any one of Aspects 1-91, wherein the high-value metal source material is a low-grade ore.
  • Aspect 21 The method according to any one of Aspects 1-91, wherein the high-value metal source material is not a high-grade ore.
  • Aspect 22 The method according to any one of Aspects 1-91, wherein the high-value metal source material is electronic waste.
  • Aspect 23 The method according to any one of Aspects 1-91, wherein the ore is selected from a sulfide ore, an oxide ore, and combinations thereof.
  • Aspect 24 The method according to any one of Aspects 1-91, wherein the high-value metal source material is a recycled material selected from the group consisting of a spent catalyst, a hydrogen membrane fuel cell, a high value metal-bearing electrode, electronic waste, a spark plug, a high value metal-bearing sensor, an alloy, recycled dental equipment, and combinations thereof.
  • the high-value metal source material is a recycled material selected from the group consisting of a spent catalyst, a hydrogen membrane fuel cell, a high value metal-bearing electrode, electronic waste, a spark plug, a high value metal-bearing sensor, an alloy, recycled dental equipment, and combinations thereof.
  • Aspect 25 The method according to any one of Aspects 1-91, wherein the high-value metal source material comprises a metal-bearing electrode comprising a metal selected from the group consisting of Au, Ag, Pd, Pt, Ir, Rh, Ru, Os, and combinations thereof.
  • Aspect 26 The method according to any one of Aspects 1-91, wherein the high-value metal source material comprises a spent catalyst that an automotive spent catalyst such as a catalytic converter.
  • Aspect 27 The method according to any one of Aspects 1-91, wherein the high-value metal source material comprises a metal-bearing electrode that is a mixed-metal-oxide (MMO) electrode.
  • MMO mixed-metal-oxide
  • Aspect 28 The method according to any one of Aspects 1-91, wherein the high-value metal is gold, wherein the high-value metal source material is selected from the group consisting of a low-grade oxide ore containing gold, a low-grade sulfide ore containing gold, an electronic waste containing from about 0.1 g/t to about 1.5 g/t gold, an industrial waste containing from about 0.1 g/t to about 1 g/t gold, a mining tailing containg about 2 g/t to about 10 g/t gold, and a combination thereof; and wherein a recovery percentage of the gold from the high-value metal source is about 90% or greater.
  • the high-value metal source material is selected from the group consisting of a low-grade oxide ore containing gold, a low-grade sulfide ore containing gold, an electronic waste containing from about 0.1 g/t to about 1.5 g/t gold, an industrial waste containing from about 0.1 g/t to about 1 g/t gold
  • Aspect 29 The method according to any one of Aspects 1-91, wherein the high-value metal is silver, wherein the high-value metal source material is selected from the group consisting of a low-grade oxide ore containing silver, a low-grade sulfide ore containing silver, an electronic waste containing from about 5 g/t to about 100 g/t silver, an industrial waste containing from about 1 g/t to about 10 g/t silver, a mining tailing containg about 2 g/t to about 10 g/t silver, and a combination thereof; and wherein a recovery percentage of the silver from the high-value metal source is about 90% or greater.
  • the high-value metal source material is selected from the group consisting of a low-grade oxide ore containing silver, a low-grade sulfide ore containing silver, an electronic waste containing from about 5 g/t to about 100 g/t silver, an industrial waste containing from about 1 g/t to about 10 g/t silver, a mining
  • Aspect 30 The method according to any one of Aspects 1-91, wherein the high-value metal is copper, wherein the high-value metal source material is selected from the group consisting of a low-grade oxide ore containing copper, a low-grade sulfide ore containing copper, a low-grade carbonate ore containing copper, an electronic waste containing from about 10% to about 30% copper, a mining tailing containg about 0.5% to about 10 % copper, and a combination thereof; and wherein a recovery percentage of the copper from the high-value metal source is about 90% or greater.
  • the high-value metal is copper
  • the high-value metal source material is selected from the group consisting of a low-grade oxide ore containing copper, a low-grade sulfide ore containing copper, a low-grade carbonate ore containing copper, an electronic waste containing from about 10% to about 30% copper, a mining tailing containg about 0.5% to about 10 % copper, and a combination thereof; and wherein a recovery percentage of
  • Aspect 31 The method according to any one of Aspects 1 -91 , wherein the high-value metal is a platinum group metal, wherein the high-value metal source material is selected from the group consisting of a sulfide ore containing the platinum group metal, a chromite ore containing the platinum group metal, a silicate ore containing the platinum group metal, an electronic waste containing from about 1 g/t to about 5 g/t palladium, an industrial waste containing about 5 ppb to about 5 ppm a platinum group metal, a mining tailing containg about 1 g/t to about 10 g/t of the platinum group metal, and a combination thereof; and wherein a recovery percentage of the platinum group metal from the high-value metal source is about 90% or greater.
  • the high-value metal source material is selected from the group consisting of a sulfide ore containing the platinum group metal, a chromite ore containing the platinum group metal, a silicate ore containing the platinum
  • Aspect 32 The method according to any one of Aspects 1-91, wherein the high-value metal slurry has a pH from about 0 to about 5.
  • Aspect 33 The method according to any one of Aspects 1-91, wherein the high value metal slurry has a pH from about 1.5 to about 3.5.
  • Aspect 34 The method according to any one of Aspects 1-91, wherein the high value metal slurry has a pH from about 2 to about 3.
  • Aspect 35 The method according to any one of Aspects 1-91, further comprising adding an effective amount of an acid to the slurry to adjust the pH to between about 0 and about 5, between about 1.5 and about 3.5, or between about 2 and about 3.
  • Aspect 36 The method according to any one of Aspects 1-91, wherein the acid is selected from hydrobromic acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, citric acid, and combinations thereof.
  • Aspect 37 The method according to any one of Aspects 1 -91 , wherein the high value metal slurry comprises from about 5 wt% to about 50 wt% high value metal material.
  • Aspect 38 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 10 wt% to about 50 wt% high value metal material.
  • Aspect 39 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 15 wt% to about 50 wt% high value metal material.
  • Aspect 40 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 20 wt% to about 50 wt% high value metal material.
  • Aspect 41 The method according to any one of Aspects 1 -91 , wherein the high value metal slurry comprises from about 5 wt% to about 40 wt% high value metal material.
  • Aspect 42 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 10 wt% to about 40 wt% high value metal material.
  • Aspect 43 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 15 wt% to about 40 wt% high value metal material.
  • Aspect 44 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 20 wt% to about 40 wt% high value metal material.
  • Aspect 45 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 5 wt% to about 30 wt% high value metal material.
  • Aspect 46 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 10 wt% to about 30 wt% high value metal material.
  • Aspect 47 The method according to any one of Aspects 1-91, The method according to any one of claims 1-16, about 30 wt% high value metal material.
  • Aspect 48 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 20 wt% to about 30 wt% high value metal material.
  • Aspect 49 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 5wt% to about 25 wt% high value metal material.
  • Aspect 50 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 10 wt% to about 25 wt% high value metal material.
  • Aspect 51 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 15 wt% to about 25 wt% high value metal material.
  • Aspect 52 The method according to any one of Aspects 1-91, wherein the high value metal slurry comprises from about 20 wt% to about 25 wt% high value metal material.
  • Aspect 53 The method according to any one of Aspects 1-91, wherein the contacting step further comprises agitating the slurry.
  • Aspect 54 The method according to any one of Aspects 1 -91 , wherein the contacting step further comprises heating the slurry to a temperature from about 40 °C to about 120 °C.
  • Aspect 55 The method according to any one of Aspects 1 -91 , wherein the contacting step further comprises wherein the heating the slurry is heating to a temperature from about 40 °C to about 115 °C.
  • Aspect 56 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 40 °C to about 110 °C.
  • Aspect 57 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 40 °C to about 100 °C.
  • Aspect 58 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 50 °C to about 120 °C.
  • Aspect 59 The method according to any one of Aspects l-89wherein the heating the slurry is heating to a temperature from about 50 °C to about 115 °C.
  • Aspect 60 The method according to any one of Aspects l-89wherein the heating the slurry is heating to a temperature from about 50 °C to about 110 °C.
  • Aspect 61 The method according to any one of Aspects l-89wherein the heating the slurry is heating to a temperature from about 50 °C to about 100 °C.
  • Aspect 62 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 60 °C to about 120 °C.
  • Aspect 63 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 60 °C to about 115 °C.
  • Aspect 64 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 60 °C to about 110 °C.
  • Aspect 65 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 60 °C to about 100 °C.
  • Aspect 66 The method according to any one of Aspects 1-91, wherein the heating the slurry is heating to a temperature from about 60 °C to about 90 °C.
  • Aspect 67 The method according to any one of Aspects 1 -91 , further comprising purifying the spent leach composition to form a purified leach composition.
  • Aspect 68 The method according to any one of Aspects 1-91, further comprising, repeating step (a) with the purified leach composition.
  • Aspect 69 The method according to any one of Aspects 1-91, wherein the method comprises a batch leaching method, and wherein the batch leaching method comprises prior to step (a) one or both of: commution of the high-value metal source material; and agglomeration of the high-value metal source material; wherein the contacting step (b) comprises combining the high-value metal source material with the leach composition in a batch reactor.
  • Aspect 70 The method according to any one of Aspects 1-91, wherein the method comprises a continuous leaching method, and wherein the continuous leaching method comprises prior to step (a) one or both of: commution of the high-value metal source material; and agglomeration of the high-value metal source material; wherein the contacting step (b) comprises feeding the high-value metal source material through a series of reactors where it is contacted with the leach composition.
  • Aspect 71 The method according to any one of Aspects 1-91, wherein wherein the method comprises a continuous leaching method, and wherein the continuous leaching method comprises prior to step (a) one or both of: commution of the high-value metal source material; and agglomeration of the high-value metal source material; wherein the method further comprises prior to step (a) forming a heap comprising the high- value metal source material; and wherein the contacting step (b) comprises applying the leach composition to the heap.
  • Aspect 72 The The method according to any one of Aspects 1-91, wherein the contacting step is performed at around room temperature.
  • Aspect 73 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 40 °C to about 120 °C.
  • Aspect 74 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 40 °C to about 115 °C.
  • Aspect 75 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 40 °C to about 110 °C.
  • Aspect 76 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 40 °C to about 100 °C.
  • Aspect 77 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 50 °C to about 120 °C.
  • Aspect 78 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 50 °C to about 115 °C.
  • Aspect 79 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 50 °C to about 110 °C.
  • Aspect 80 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 50 °C to about 100 °C.
  • Aspect 81 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 60 °C to about 120 °C.
  • Aspect 82 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 60 °C to about 115 °C.
  • Aspect 83 Th The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 60 °C to about 110 °C.
  • Aspect 84 T The method according to any one of Aspects 1 -91 ,, wherein the contacting step is performed at a temperature from about 60 °C to about 100 °C.
  • Aspect 85 The method according to any one of Aspects 1-91, wherein the contacting step is performed at a temperature from about 60 °C to about 90 °C.
  • Aspect 86 The method according to any one of Aspects 1-91, wherein a recovery percentage of the high-value metal is about 60% to about 99% or about 60% to about 80%.
  • Aspect 87 The method according to any one of Aspects 1-91, wherein a recovery percentage of the high-value metal is about 80% to about 99% or about 80% to about 90%.
  • Aspect 88 The method according to any one of Aspects 1-91, wherein a recovery percentage of the high-value metal is about 90% to about 99.9% or about 90% to about 98%.
  • Aspect 89 The method according to any one of Aspects 1-91, wherein a recovery percentage of the high-value metal is about 98%% to about 99.9%.
  • Aspect 90 The method according to anyone of Aspects 1-91, wherein the oxidizing agent comprises a halogen gas; and wherein the method comprises producing the halogen gas prior to or contemporaneous with the contacting step (a) and adding it to the leach composition.
  • Aspect 91 The method according to any one of Aspects 1-91, wherein prior to the contacting step the leach composition is stable and has a pH of about 5 to about 12 or about 5 to about 10; and wherein prior to or contemporaneous with the contacting step (a) the pH of the leach composition is adjusted to a pH of below about 4 e.g., about 1 to about 4.
  • a leach composition for leaching a high-value metal from a high-value metal source material comprising: a solvent; an oxidizing agent; and a halogen salt; wherein the solvent comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, a ketone, a carboxylic acid, an ester, a carbonate ester, and combinations thereof; and wherein the alcohol, the ether, the ketone, a carboxylic acid, an ester, a carbonate ester are optionally substituted with one or more group independently selected from a C1-C5 alkyl, a hydroxy group, and combinations thereof.
  • the solvent comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, a ketone, a carboxylic acid, an ester, a carbonate ester, and combinations thereof; and wherein the alcohol, the ether, the ketone, a carboxylic acid, an ester, a carbonate ester are optionally substituted
  • Aspect 93 The leach composition according to any one of Aspects 92-155, further comprising a ligand.
  • Aspect 94 The leach composition according to any one of Aspects 92-155, wherein the oxidizing agent is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof; and wherein the halogen salt is present at a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof.
  • Aspect 95 The leach composition according to any one of Aspects 92-155, wherein the oxidizing agent is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof; wherein the halogen salt is present at a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof; and wherein the ligand is selected from the group consisting of sodium acetate, sodium citrate, ethylenediaminetetraacetic acid (EDTA), and combinations thereof.
  • the oxidizing agent is selected from the group consisting of lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof
  • the halogen salt is present at a concentration of about 0.1 M to about 1 M and is selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, and combinations thereof
  • the ligand is
  • Aspect 96 The leach composition according to any one of Aspects 92-155, wherein the solvent is selected from water, a polyethylene glycol, an alcohol, an ether, a ketone, and combinations thereof.
  • Aspect 97 The leach composition according to any one of Aspects 92-155, , wherein the solvent comprises a solvent selected from water, a polyethylene glycol, an alcohol, an ether, and combinations thereof.
  • Aspect 98 The leach composition according to any one of Aspects 92-155, , wherein the solvent comprises a solvent selected from water, an alcohol, an ether, a ketone, and combinations thereof.
  • Aspect 99 The leach composition according to any one of Aspects 92-155, , wherein the solvent comprises a solvent selected from a polyethylene glycol, an alcohol, an ether, a ketone, and combinations thereof.
  • Aspect 100 The leach composition according to any one of Aspects 92-155, wherein the solvent does not comprise water.
  • Aspect 102 The leach composition according to any one of Aspects 92-155, wherein the solvent comprises a solvent selected from water, a CH3-(C1-C8 alkanediyl)m-O-(Cl- C10 alkanediyl)n-CH3, CH3-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-OH, HO- CH2-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-OH, and combinations thereof; wherein the solvent is optionally substituted with one or more group independently selected from hydroxyl and C1-C5 alkyl; wherein the total number carbon residues is ten or less; and wherein each of m and n is independently selected from 0 and 1.
  • the solvent comprises a solvent selected from water, a CH3-(C1-C8 alkanediyl)m-O
  • Aspect 103 The leach composition according to any one of Aspects 92-155, wherein the solvent comprises a solvent selected from a CH3-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-CH3, CH3-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-OH, HO- CH2-(C1-C8 alkanediyl)m-O-(Cl-C10 alkanediyl)n-OH, and combinations thereof; wherein the solvent is optionally substituted with one or more group independently selected from hydroxyl and C1-C5 alkyl; wherein the total number carbon residues is ten or less; and wherein each of m and n is independently selected from 0 and 1.
  • the solvent comprises a solvent selected from a CH3-(C1-C8 alkanediyl)m-O-(Cl
  • the solvent comprises a solvent selected from water, CH3-(C1-C8 alkane
  • the solvent comprises a solvent selected from a CH3-(C1-C8 alkane
  • the solvent comprises a solvent selected from water, CH3-(C
  • the solvent comprises a solvent selected from water, CH3
  • Aspect 114 The leach composition according to any one of Aspects 92-155, wherein the solvent comprises a compound selected from a structure represented by a formula:
  • Aspect 115 The leach composition according to any one of Aspects 92-155, wherein the solvent comprises a compound selected from a structure represented by a formula:
  • Aspect 116 The leach composition according to any one of Aspects 92-155, wherein the solvent comprises water.
  • Aspect 117 The leach composition according to any one of Aspects 92-155, wherein the water is present in an amount from about 35 wt% to about 65 wt%; and wherein the wt% is based on the total weight of the solvent.
  • Aspect 118 The leach composition according to any one of Aspects 92-155, wherein the water is present in an amount from about 40 wt% to about 60 wt%; and wherein the wt% is based on the total weight of the solvent.
  • Aspect 119 The leach composition according to any one of Aspects 92-155, wherein the water is present in an amount from about 45 wt% to about 55 wt%; and wherein the wt% is based on the total weight of the solvent.
  • Aspect 120 The leach composition according to any one of Aspects 92-155, wherein the solvent comprises polyethylene glycol.
  • Aspect 121 The leach composition according to any one of Aspects 92-155, wherein the polyethylene glycol has an average molecular weight from about 200 g/mol to about 20,000 g/mol.
  • Aspect 122 The leach composition according to any one of Aspects 92-155, wherein the polyethylene glycol has an average molecular weight from about 600 g/mol to about 4,000 g/mol.
  • Aspect 123 The leach composition according to any one of Aspects 92-155, wherein the polyethylene glycol has an average molecular weight from about 1,000 g/mol to about 3,000 g/mol.
  • Aspect 124 The leach composition according to any one of Aspects 92-155, wherein the polyethylene glycol has an average molecular weight from about 1,500 g/mol to about 2,500 g/mol.
  • Aspect 125 The leach composition according to any one of Aspects 92-155, wherein the polyethylene glycol has an average molecular weight from about 1,900 g/mol to about 2,100 g/mol.
  • Aspect 126 The leach composition according to any one of Aspects 92-155, wherein the oxidizing agent is selected from chlorine, bromine, a bromate salt, a perbromate salt, a chlorate salt, a chlorite salt, a perchlorate salt, hydrogen peroxide, ozone, an organic peroxyacid, a superoxide, a peroxide-superoxide, an organic peroxyacid (and a salt thereof), a peroxyhydrate, a water-soluble organic peroxide, a nitrosodisulfonate, a hypochlorite, a hypobromite, chlorine dioxide, a chloroamine, a chloroamide, a chlorosulfamide, a bromoamine, a bromoamide, a bromosulfamide, a chlorosulfonic acid, a bromosulfonic acid, an inorganic peroxide (or salt thereof), an inorganic peroxyacid (or salt thereof), and combinations thereof.
  • Aspect 127 The leach composition according to any one of Aspects 92-155, wherein the oxidizing agent is selected to oxidize bromide.
  • Aspect 128 The leach composition according to any one of Aspects 92-155, wherein the oxidizing agent is selected from a bromate salt, a perbromate salt, a chlorate salt, a chlorite salt, a perchlorate salt.
  • Aspect 129 The leach composition according to any one of Aspects 92-155, wherein the oxidizing agent is selected from lithium bromate, lithium perbromate, lithium chlorate, lithium perchlorate, lithium chlorite, and combinations thereof.
  • Aspect 130 The leach composition according to any one of Aspects 92-155, wherein the bromate salt, the perbromate salt, the chlorate salt, the chlorite salt, or the perchlorate salt do not comprise a calcium cation.
  • Aspect 131 The leach composition according to any one of Aspects 92-155, wherein the bromate salt, the perbromate salt, the chlorate salt, the chlorite salt, or the perchlorate salt comprise a calcium cation.
  • Aspect 132 The leach composition according to any one of Aspects 92-155, wherein the oxidizing agent has a concentration from about 0.1 to about 100 g/L based on the total volume of the solvent leach composition.
  • Aspect 133 The leach composition according to any one of Aspects 92-155, wherein the halogen salt is selected from an alkali metal bromide salt, an alkali chloride salt, an alkaline earth bromide salt, an alkaline earth chloride salt, and combinations thereof.
  • Aspect 134 The leach composition according to any one of Aspects 92-155, wherein the halogen salt is selected from sodium chloride, potassium chloride, sodium bromide, potassium bromide, lithium bromide, and combinations thereof.
  • Aspect 135. The leach composition according to any one of Aspects 92-155, wherein the halogen salt is selected from lithium bromide, sodium bromide, potassium bromide, and combinations thereof.
  • Aspect 136 The leach composition according to any one of Aspects 92-155, wherein the halogen salt is selected from lithium bromide, sodium bromide, potassium bromide, and combinations thereof.
  • Aspect 137 The leach composition according to any one of Aspects 92-155, wherein the halogen salt has a concentration from about 0.1 M to about 1.0 M based on based on the total volume of the solvent leach composition.
  • Aspect 138 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential that is greater than or equal to about 400 mV.
  • Aspect 139 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 400 mV to about 900 mV.
  • Aspect 140 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 500 mV to about 900 mV.
  • Aspect 141 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 600 mV to about 900 mV.
  • Aspect 142 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 700 mV to about 900 mV.
  • Aspect 143 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 400 mV to about 800 mV.
  • Aspect 144 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 500 mV to about 800 mV.
  • Aspect 145 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 600 mV to about 800 mV.
  • Aspect 146 The leach composition according to any one of Aspects 92-155, wherein the composition has an oxidization reduction potential from about 700 mV to about 800 mV.
  • Aspect 147 The leach composition according to any one of Aspects 92-155, wherein the composition has a pH from about 1 to about 4.
  • Aspect 148 The leach composition according to any one of Aspects 92-155, wherein the composition has a pH from about 1 to about 3.
  • Aspect 149 The leach composition according to any one of Aspects 92-155, wherein the leach composition has a pH greater than about 5.
  • Aspect 150 The leach composition according to any one of Aspects 92-155, wherein the leach composition has a pH from about 5 to about 12.
  • Aspect 151 The leach composition according to any one of Aspects 92- 155, wherein the leach composition has a pH from about 5 to about 10.
  • Aspect 152 The leach composition according to any one of Aspects 92-155, wherein the leach composition has a pH from about 5 to about 8.
  • Aspect 153 The leach composition according to any one of Aspects 92-155, wherein the leach composition has a pH from about 5 to about 7.
  • Aspect 154 The leach composition according to any one of Aspects 92-155, wherein the ligand is a compound according to the following formula or a sodium or calcium salt thereof where each occurrence of Ri, R2, and R3 is independently selected from the group consisting of H, alkyl, heteroalkyl, -R4CO(OH), and -RsN ⁇ RsXR?) so long as at least one of Ri, R2, or R3 is -R4CO(OH); where each occurrence of Re and R7 is independently selected from the group consisting of H, alkyl, heteroalkyl, -R4CO(OH), and -RsN(R9)(Rio) so long as at least one of R6 and R7 is -R4CO(OH); where each occurrent of R5 and Rs is independently a Cl- C12 substituted or unsubstituted alkyl, a Cl -Cl 2 substituted or unsubstituted heteroalkyl, or a a Cl -Cl 2
  • Aspect 155 The leach composition according to any one of Aspects 92-155, wherein the ligand is selected from the group consisting of sodium acetate, sodium citrate, oxalate, malonate, tartrate, gluconate, nitrilotriacetic acid, phthalate, citramalate, ethylenediaminetetraacetic acid (EDTA), diaminoethanetetraacetic acid (CDTA), trans- 1 ,2-Diaminocy cl ohexanetetraacetic acid (DCTA), nitrilotriacetic acid, N- hydroxyethylethylenediaminetriacetic acid (HEDTA), iminodiacetic acid (IDHA), propylenediaminetetraacetic acid (PDTA), sodium and calcium salts of any of the foregoing, and combinations thereof.
  • the ligand is selected from the group consisting of sodium acetate, sodium citrate, oxalate, malonate, tartrate,
  • Example 1 Referential Example - Leach Test
  • the test duration varied from a few hours to several days. There is no waste for reagents and solvent because the solution is continuously used (which makes the process unique and novel).
  • the high value metal pregnant leach solution and tailings i.e., the solid residues
  • ICP-MS inductively coupled plasma mass spectrometry
  • the head sample contains 100 grams of high value metals, and 99 grams are extracted with 99% recovery, it means 1 gram of high value metals is left in the solid residue. Completing the mass balance provided values of recovery and efficiency of the solvent, which is presented in the examples.
  • the produced bromine is a strong oxidizing agent which will be dissolved into the solvent.
  • bromine will be the predominant component.
  • acid can be added to the solvent.
  • the acid may be diluted or concentrated sulfuric acid, hydrochloric acid, acetic acid or citric acid.
  • an oxidant such as lithium chlorate
  • a chloride salt e.g., lithium chloride
  • the chloride can be oxidized to chlorine as shown below:
  • bromide salt e.g., lithium bromide
  • bromide can be oxidized to bromine as shown below:
  • the oxidizing strength of bromine is suitable for dissolution of high value metals, particularly PGMs.
  • the PGM halide salts such as PGMs bromide or PGM chloride salts will be produced, which can be highly soluble into the solvent leach composition.
  • the following reactions are such exemplary reactions, where X is a halogen such as Br or Cl:
  • a sample of a very high-grade spent catalyst substance containing PGMs was ground to a grind size of P100, 125 pm (meaning 80% of the particles are less than 75 pm in size and 100% of the particles are less than 125 pm in size) to increase the overall surface area of the PMG-containing substance to increase leaching reactions.
  • the sample was riffle split into two homogenous samples. Each sample was used for two leach tests as explained in the Referential Example above, with the same conditions, except the solution.
  • One sample was soaked in Aqua Regia (3: 1 hydrochloric acid and nitric acid), as one of the strongest lixiviants, and the other sample was leached in the solvent leach composition of the current disclosure.
  • a sample of a spent catalyst containing PGMs was pulverized to Pl 00, 125 pm.
  • the sample was leached as explained in the Referential Example above, using the disclosed solvent.
  • the sample was assayed using an XRF device.
  • the results showed that the sample contained 1850 ppm of palladium, 207 ppm of platinum and 350 ppm of Rh.
  • the leach test was performed with 10% w/w pulp density for 6 hours, one at room temperature and the other at 50 °C.
  • the recoveries for Pd, Pt and Rh are shown in Table 1 for both temperatures. There is a significant increase in the recovered Pt and Rh at 50 degrees compared to room temperature. There is a modest increase in the amount of Pd recovered at 50 degrees compared to room temperature, as Pd is generally easier to extract.
  • a refinery spent catalyst containing high-grade platinum levels was used as a sample.
  • the sample was pulverized to a grind size of Pl 00, 125 pm.
  • the effect of oxidizing agent levels in the solvent leach composition (by weight %) on solvent efficiency was studied. All the tests were performed as explained in the Referential Example and at 45 °C for 12 hours with 5% w/w pulp density.
  • FIG. 4 shows the results of this example. As it is shown in FIG. 4, higher oxidant levels in the solvent leach composition resulted in higher dissolved amounts of platinum.
  • a halogen gas as an oxidizing agent, to the solvent leach composition
  • one or more of the following processes can be used: direct halogen gas addition, onsite chemical halogen gas production, and electrochemical halogen gas production.
  • a halogen oxygen leaching procedure such as a chlorineoxygen or bromine-oxygen leaching procedure can be used, wherein halogen gas is combined with oxygen in an acidic environment to convert copper sulphides to soluble forms such as halides and sulphates.
  • the halogen and oxygen can be added in the form of pressurized gas dispensed from high-pressure cylinders at a controlled rate.
  • the leaching reactor can be sealed, and its temperature controlled to maximize leaching efficiency.
  • the following reactions provide an exemplary reaction for chlorine (Refs. 1-2):
  • halogen gas such as chlorine gas
  • halogen gas is produced on-site, directly (in-situ) in the leaching reactor from a halogen containing precursor.
  • halogen bleach such as chlorine bleach (NaOCl)
  • acid can be dosed in the reactor in a controlled manner.
  • the same halogen production reaction can take place in a secondary vessel (ex-situ), which contains a halogen gas permeable membrane, separating the halogen gas and the leaching products.
  • a secondary vessel ex-situ
  • On-site production of halogen gas has the advantage of not requiring more expensive high-pressure cylinders of halogens, such as chlorine gas cylinders, to be transported to remote sites such as copper mines, instead only needing commonly available acids and halogen bleach solutions.
  • other halogen-containing precursors to halogen gas such as trichloroisocyanuric acid (also referred to as Trichloro-S-Triazinetrione or Trichlor) can be used.
  • halogen gas can be also produced on-site electrochemically, for example from a chloralkali process in case of chlorine production.
  • Chloralkali process is an electrolysis reaction used to produce hydrogen gas, sodium hydroxide and chlorine gas from a brine (sodium chloride) solution as shown in formula (15) and in FIG. 5.
  • the chloralkali process is shown in FIG. 5 generally at 260.
  • the process starts at step 270 in which an amount of sodium chloride, from a salt storage tank 282, is mixed with water in a tank or any other container to form a brine solution.
  • the brine solution then goes through a membrane electrolysis process 274 in which chlorine gas, hydrogen gas, and sodium hydroxide being created.
  • the depleted brine can be recycled back into the brine tank 270 where sodium chloride is added for a new brine solution.
  • the chloralkali reaction can also produce hydrogen gas and sodium hydroxide (caustic soda), both of which have utility in some industries or can be used on-site directly.
  • Hydrogen gas especially when derived from electrolysis (green hydrogen), is a highly energy-dense, carbon-neutral fuel source.
  • Caustic soda is an industrially important material that could also be used on-site or sold as a commodity.
  • the resulting hydrogen sodium hydroxide gases can be stored in a hydrogen storage tank 286, and a sodium hydroxide storage tank respectively.
  • a similar electrochemical process as shown in FIG. 5 can be used for production of other halogens such as bromine.
  • Producing on-site chlorinehalogen gas for example from the chloralkali process, has several advantages such as simplifying the logistics and reducing the cost of the overall chlorine halogen gas acquisition by only requiring salt, water and electricity for the process.
  • a ligating group such as acetate (OAc) oxalate (ox 2- ) and citrate (Cit 3 ') is added to the solvent leach composition to stabilize the copper ions.
  • L a ligating group
  • OAc acetate
  • oxalate ox 2-
  • citrate Cit 3 '
  • L indicates a ligating group
  • (aq) indicates the chemical element being in an aqueous phase
  • (s) indicates the chemical element being in a solid phase
  • (g) indicates the chemical element being in a gaseous phase.
  • sodium acetate is used as the ligating group and the following reaction takes place in the solvent leach composition:
  • references cited in the disclosure are enumerated below. References may be cited herein using the format of reference number(s) enclosed by parentheses corresponding to one or more of the following numbered references. References may also be cited herein using a superscript format. For example, citation of references numbers 1 and 2 immediately herein below could be indicated in the disclosure as (Refs. 1 and 2) or as the superscript ii 1-2 ii

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Abstract

L'invention concerne des compositions de lixiviation recyclables, à base de solvants non toxiques et des procédés de lixiviation et d'extraction d'un métal de haute valeur, en particulier des métaux du groupe du platine (MGP), du cuivre, de l'or et de l'argent. La composition de lixiviation comprend : a. un solvant ; b. un agent oxydant ; et c. un sel d'halogène. Les procédés peuvent comprendre la préparation de la composition de lixiviation à base de solvant, l'ajout d'un matériau source en métal de haute valeur à la composition de lixiviation à base de solvant et l'agitation destinée à lixivier le métal de haute valeur à partir du matériau source. L'agitation peut être effectuée pendant plusieurs heures à des jours à une température relativement basse. Après la lixiviation, une filtration peut être effectuée pour séparer les métaux à haute valeur solubles dans un solvant des résidus insolubles. Le procédé peut en outre comprendre l'affinage du métal à haute valeur et la purification du solvant. Le solvant purifié peut être recyclé/réutilisé dans les procédés décrits dans la description.
EP23911135.4A 2022-12-29 2023-12-29 Compositions et procédés de lixiviation de métaux de haute valeur Pending EP4642935A1 (fr)

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US202263436102P 2022-12-29 2022-12-29
US202363462485P 2023-04-27 2023-04-27
PCT/IB2023/063396 WO2024142022A1 (fr) 2022-12-29 2023-12-29 Compositions et procédés de lixiviation de métaux de haute valeur

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US3709681A (en) * 1970-01-08 1973-01-09 Golden Cycle Corp Process for the recovery noble metals
US5401296A (en) * 1994-06-28 1995-03-28 Martenson; Irvin Precious metal extraction process
JP4524593B2 (ja) * 2003-10-27 2010-08-18 三菱化学株式会社 貴金属の溶解液及びこの溶解液を用いた貴金属の溶解・回収方法
EP2705168A4 (fr) * 2011-05-02 2015-04-29 Trimetals Mining Inc Procédé pour la récupération d'indium, d'argent, d'or et d'autres métaux rares, précieux et de base à partir de minerais d'oxydes et sulfures complexes
WO2015102867A1 (fr) * 2013-12-30 2015-07-09 Albemarle Corporation Procédé de dissolution ou d'extraction d'au moins un métal précieux à partir d'une matière source contenant celui-ci
CN111593199A (zh) * 2020-06-04 2020-08-28 杨炯 Boc体系溶液、其制备方法及浸金、冶金方法
US20240150867A1 (en) * 2020-08-07 2024-05-09 Excir Works Corp. Methods for leaching and recovery of platinum group metals in organic solvents

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