WO2023191737A1 - A method for obtaining zn and pb metals from zn-pb ore - Google Patents
A method for obtaining zn and pb metals from zn-pb ore Download PDFInfo
- Publication number
- WO2023191737A1 WO2023191737A1 PCT/TR2022/050487 TR2022050487W WO2023191737A1 WO 2023191737 A1 WO2023191737 A1 WO 2023191737A1 TR 2022050487 W TR2022050487 W TR 2022050487W WO 2023191737 A1 WO2023191737 A1 WO 2023191737A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metals
- deep eutectic
- obtaining
- ore
- leaching
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 96
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 150000002739 metals Chemical class 0.000 title claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 230000005496 eutectics Effects 0.000 claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 33
- 229910052745 lead Inorganic materials 0.000 claims abstract description 25
- 230000008901 benefit Effects 0.000 claims abstract description 10
- 238000005265 energy consumption Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000002608 ionic liquid Substances 0.000 claims abstract description 5
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 4
- 238000009853 pyrometallurgy Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 37
- 238000002386 leaching Methods 0.000 claims description 29
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 25
- 235000019743 Choline chloride Nutrition 0.000 claims description 25
- 229960003178 choline chloride Drugs 0.000 claims description 25
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 21
- 239000004202 carbamide Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 11
- 238000005363 electrowinning Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000011133 lead Substances 0.000 description 41
- 239000011701 zinc Substances 0.000 description 26
- 238000005188 flotation Methods 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000003839 salts Chemical group 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- -1 zinc metals Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229930003776 Vitamin B4 Natural products 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000009852 extractive metallurgy Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 150000007527 lewis bases Chemical group 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Chemical group 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 235000008979 vitamin B4 Nutrition 0.000 description 1
- 239000011579 vitamin B4 Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- 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
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with 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
- 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
Definitions
- the invention relates to a method for obtaining Zn and Pb metals from Zn-Pb ores.
- the invention relates to a new method for obtaining Zn and Pb metals from Zn-Pb ores which is using non-aqueous solvents such as molecular organic solvents, ionic liquids, and deep eutectic solvents instead of aqueous solutions and which provides less energy consumption advantages compared to the pyrometallurgy method and higher selectivity advantages compared to the hydrometallurgy method.
- non-aqueous solvents such as molecular organic solvents, ionic liquids, and deep eutectic solvents
- Zn-Pb ores are found in nature in oxidized, sulphurous and oxidized+sulphurous mineral forms.
- the production of zinc and lead metals is carried out using pyrometallurgical, hydrometallurgical and pyrometallurgical+hydrometallurgical methods that differ according to the grade values of the ore.
- Flotation process is an enrichment method that uses the water-loving and waterhating properties of the ore to be produced, creating bubbles in the liquid, and separating it from other materials by floating or sinking in water. It is generally used in the separation of sulfide ores. Flotation is one of the enrichment methods of copper, lead and zinc ores in the world.
- the calcination process is the process of breaking down carbonates and hydrates with the effect of heat in order to obtain oxide components. It is a method in which a solid chemical compound is raised to a high temperature without melting under a limited supply of ambient oxygen, generally to remove impurities or volatiles and/or to cause thermal degradation.
- Zn-Pb ores are fine-grained by nature and additionally grinding the ores to obtain ultra-fine grains in order to liberate the minerals sufficiently makes the flotation process difficult.
- complex flotation circuits are required from production facilities.
- Heavy metal-containing wastes released in the smelting process known as the process of separating the metal content of the ore from the rest of the ore with the help of a high-temperature reduction reaction, and SO2/CO2 gases released in the roasting/calcination processes harm the environment.
- the ore concentration process begins with reducing the size of the ore extracted from the mine.
- the ore passes through primary crushing and secondary crushing, continuing with a step of grinding in which fine particles are obtained. This step also generates overgrinding of the material.
- the invention is also aimed at solving a problem inherent in the conventional flotation process, as the fraction of ultra fine particles accumulates as slime at the bottom of the flotation system tanks and becomes a major consumers of reagents, owing to the large surface area thereof. A large part of the ultra fine ore fraction results in tailings.
- These ores demonstrate greater liberation (they are presented as individual particles of a single mineral per particle) at a lower particle size, meaning that a significant quantity of valuable mineral is lost in the process.” statements are included.
- a foam flotation system for the physical chemical separation of ultrafine ore particles.
- the subject of the invention is a method for the production of Zn-Pb collective concentrate with an increased silver content in the process of zinc sludge flotation.
- the method is carried out in such a way that the sludge from the zinc hydrometallurgy process is flotated in a flotation machine in order to produce a Zn-Pb flotation collective concentrate with an increased Ag content, and in order to filter the electrolyte residues, they are dewatered on a filter to the content of about 20% H2O and obtain a pH of 5 , 0-5.5. So cleaned, it is pumped to a flotation machine with four working sections.
- the sludge is introduced through the mixing chamber to the second section of the machine by preflotation at a pH value of 7.0 - 7.5, and the froth product of the second section is directed to the first concentrate chamber of the machine, from which the Zn-Pb-Ag collective concentrate is withdrawn.
- Sludges from the second section of the flotation machine after adding a foaming agent to them. (CuSO4 solution) and milk of lime until pH 9.5-11 .0 is fed into the third section of the machine.
- Foam products from the third and fourth section of the machine are fed into the mixing chamber, while the final waste from the fourth section of the machine is directed to the waste collection or settling ponds.” statements are included.
- the present invention contains at least one phosphonium salt (I) with the formula R1 R2R3R4P+X- and (b) at least one compound (II) with the formula MYn or MYn. It is related to a deep eutectic solvent.
- R1 , R2, R3 and R4 are independently selected from H, substituted or unsubstituted, linear or branched alkyl, alkoxy, cycloalkyl, aryl or alkaryl, or where two of R1, R2, R3 and R4 are optionally substituted are alkylene groups, preferably a C4-C10 alkylene groups;
- X is halogen;
- M is selected from the group consisting of Li, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Sn, Pb, Bi, La or Ce;
- Y is selected from halide, nitrate, phosphate and/or acetate; n is from 1 to 5; m is from 1 to 10; and the molar ratio of phosphonium salt (I) to compound (II) is in the range of 2:1 to 1 :10.
- a method for its preparation is also provided.” statements are included.
- the aim of the invention is to introduce a new method for the extraction of Zn and Pb metals from Zn-Pb ores, which eliminates the existing disadvantages.
- Another aim of the invention is to present a method in which the volume of water to be used is always lower compared to the volumes of organic solvents, and no or very little water consumption is realized.
- Another aim of the invention is to present a method that eliminates the problems related to wastewater generation and wastewater treatment.
- Another aim of the invention is to present a method where metal recovery from ore deposits in arid regions where sufficient water supply cannot be provided is easier.
- Another aim of the invention is to present a method that allows to reduce energy consumption by providing the opportunity to work at room temperature or at low temperatures ( ⁇ 100), unlike melting systems with very high energy consumption.
- Another aim of the invention is to present a method in which the leaching process is carried out with much lower acid consumption compared to the leaching process performed in traditional hydrometallurgical methods.
- Another aim of the invention is to present a method that makes it possible to leave the carbonate structured gangue minerals in the ore in the waste at a high rate.
- Another aim of the invention is to provide a method that does not require an extra process step to remove unwanted metals from leaching solutions by preventing the dissolution of unwanted metals such as iron with the leaching process.
- a method for direct obtaining Zn and Pb metals from Zn-Pb ores which is using nonaqueous solvents such as molecular organic solvents, ionic liquids, and deep eutectic solvents instead of aqueous solutions and which provides less energy consumption advantages compared to the pyrometallurgy method and higher selectivity advantages compared to the hydrometallurgy method characterized in that; includes method steps of; preparation of deep eutectic solvent with the help of a controlled mixer until a homogeneous and clear solution is obtained from 1 :2 mole ratio Choline Chloride (ChCI) - urea and 1 :0.5.1.5 mole ratio Choline Chloride (ChCI) - Urea- Ethylene or Choline Chloride (ChCI) - urea- organic acid or Choline Chloride (ChCI) - Organic acid, subjecting said Zn-Pb ore to deep eutectic solvent leaching under atmospheric conditions and the ore combined with the deep eutectic solvent
- Solvometallurgy is a new branch of extractive metallurgy that uses non-aqueous solvents such as molecular organic solvents, ionic liquids and deep eutectic solvents instead of aqueous solutions. Solvometallurgical methods provide advantages such as less energy consumption compared to the pyrometallurgical method and higher selectivity compared to the hydrometallurgical method.
- Said deep eutectic solvents are commonly defined as systems consisting of a mixture of at least two components, a hydrogen bond acceptor and a hydrogen bond donor. Deep eutectic solvents are systems formed from a eutectic mixture of Lewis or Bronsted acids and bases that may contain various anionic and/or cationic species.
- Deep eutectic solvents are usually a hydrogen bond acceptor such as a quaternary salt; It is a mixture of amines, carboxylic acids, alcohol and a hydrogen bond donor such as carbohydrates.
- Deep eutectic solvents can basically be classified into four types (Table 1): Type I (quaternary salt and metal salt), Type II (quaternary salt and hydrated metal salt), Type III (quaternary salt and hydrogen bond donor) and Type IV (hydrated metal salt), salt and hydrogen bond donor).
- Deep eutectic solvents are expressed by the general formula Cat + " zX Y.
- Cat + is any ammonium, phosphonium, or sulfonium cation
- X is a Lewis base, usually a halide anion.
- Complex anionic species are formed between X- and Y, a Lewis or Brbnsted acid (z refers to the number of Y molecules interacting with the anion).
- Deep eutectic solvents are used in many areas due to their low vapor pressure, non-flammability, and easy recyclability compared to other organic solvents, as well as their biodegradability.
- the low cost of deep eutectic solvents unlike ionic solvents and mineral acids used in hydrometallurgical processes, provides a great economic advantage for their use on a larger scale.
- expensive and complex devices are not needed for their synthesis. For example, a controlled heater or a lyophilizer may be sufficient for the synthesis of these compounds.
- ChCI choline chloride
- vitamin B4 with a melting point of 302°C, with the formula [(CH3)3N(CI)CH2- CH2OH], which consists of two functional groups containing a quaternary ammonium salt and alcohol.
- They are organics with the formula (CH 2 OH) 2 , such as ethylene glycol (EG) with a diol structure.
- Commonly used deep eutectic solvents are ChCl-urea in 1 :2 mole ratio, ChCl-EG in 1 :2 mole ratio, and ChCl-urea-ethylene glycol and ChCl-urea-organic acid and ChCl- organic acid in 1 :0.5.1.5 mole ratio.
- the combined organics are prepared by mixing at temperatures below their melting point ( ⁇ 100 °C).
- Ch+ and Cl-/urea and Cl-/urea/ ethylene glycol and organic acid ions in the solution prepared by hydrogen bonding of the Cl- ion in ChCI, which is used as a hydrogen bond acceptor, to the organics used as the hydrogen bond donor.
- Zn and Pb are obtained in metallic form by applying electrolysis to the solution of charged deep eutectic solvents by utilizing the high electrical conductivity of deep eutectic solvents after the leaching process, and the uncharged deep eutectic solvents from which the metals are removed can be reused in the leaching system.
- the process steps of the production method of the invention are basically as follows;
- Zn-Pb ore is subjected to atmospheric deep eutectic solvent leaching at a temperature range of 50-100 °C, solid/liquid ratios of 1/5-1/25, 12-72 hours, and at a stirring rate where all solids can be mixed in suspension.
- the Zn and Pb loaded solution is subjected to electrowinning in the range of 0-10 V, in the range of 1 hour -infinite hour.
- the physical water of the ore and the organics used is removed at 105 °C for 24 hours and stored in vacuum containers.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a new method for obtaining Zn and Pb metals from Zn-Pb ores which is using non-aqueous solvents such as molecular organic solvents, ionic liquids, and deep eutectic solvents instead of aqueous solutions and which provides less energy consumption advantages compared to the pyrometallurgy method and higher selectivity advantages compared to the hydrometallurgy method.
Description
A METHOD FOR OBTAINING Zn AND Pb METALS FROM Zn-Pb ORE
Technical Field
The invention relates to a method for obtaining Zn and Pb metals from Zn-Pb ores.
In particular the invention relates to a new method for obtaining Zn and Pb metals from Zn-Pb ores which is using non-aqueous solvents such as molecular organic solvents, ionic liquids, and deep eutectic solvents instead of aqueous solutions and which provides less energy consumption advantages compared to the pyrometallurgy method and higher selectivity advantages compared to the hydrometallurgy method.
Background of the Invention
Zn-Pb ores are found in nature in oxidized, sulphurous and oxidized+sulphurous mineral forms. The production of zinc and lead metals is carried out using pyrometallurgical, hydrometallurgical and pyrometallurgical+hydrometallurgical methods that differ according to the grade values of the ore.
Current applications for the obtaining Zn and Pb metals from Zn-Pb ores are generally using techniques that include metallurgical pretreatments such as roasting, known as calcination followed by flotation and heating the ore in the presence of excess air or oxygen, high temperature melting processes, leaching using hydrometallurgical methods, and electrowinning processes, being carried out.
Flotation process is an enrichment method that uses the water-loving and waterhating properties of the ore to be produced, creating bubbles in the liquid, and separating it from other materials by floating or sinking in water. It is generally used in the separation of sulfide ores. Flotation is one of the enrichment methods of copper, lead and zinc ores in the world.
The calcination process is the process of breaking down carbonates and hydrates with the effect of heat in order to obtain oxide components. It is a method in which a solid chemical compound is raised to a high temperature without melting under a limited supply of ambient oxygen, generally to remove impurities or volatiles and/or to cause thermal degradation.
The fact that Zn-Pb ores are fine-grained by nature and additionally grinding the ores to obtain ultra-fine grains in order to liberate the minerals sufficiently makes the flotation process difficult. In addition, complex flotation circuits are required from production facilities.
Another problem experienced is that the use of high amounts of reagents in the flotation method increases the production cost. The separate acquisition of metals by different production techniques sends zinc during lead production and lead to waste during zinc production.
For the reasons mentioned, most of the existing techniques have low lead and zinc recoveries, high capital investment, and it is very difficult for small enterprises to use all of these techniques to produce lead and zinc metals.
Heavy metal-containing wastes released in the smelting process known as the process of separating the metal content of the ore from the rest of the ore with the help of a high-temperature reduction reaction, and SO2/CO2 gases released in the roasting/calcination processes harm the environment.
Considering the environmental and economic disadvantages of the extraction of zinc and lead metal from these ores by existing methods, it is very important to eliminate the flotation, roasting/calcination and smelting processes in such systems.
In the PCT application numbered WO2019153098A1 in the literature, “he invention, corresponding to IPC symbol B03D1/02, relates to the design of a flotation system for ultra fine particles, with a system for dissolving air in water to generate micro bubbles with a surface area greater than that obtained in conventional aeration systems for ore flotation. The increased surface area increases the probability of collision
between ultra fine particles and micro bubbles, generating a particle-bubble aggregate able to rise to the surface of the liquid and be removed as a concentrate. The main field of application is flotation in metallurgical processes for the extraction of valuable minerals. In general, the majority of the industries focus on copper extraction. However, internationally, processes for the flotation of Zn, Ni, Pb and Mo, inter alia, have been developed, which all have problems with the presence of ultra fine material. The ore concentration process begins with reducing the size of the ore extracted from the mine. The ore passes through primary crushing and secondary crushing, continuing with a step of grinding in which fine particles are obtained. This step also generates overgrinding of the material. Thus, the invention is also aimed at solving a problem inherent in the conventional flotation process, as the fraction of ultra fine particles accumulates as slime at the bottom of the flotation system tanks and becomes a major consumers of reagents, owing to the large surface area thereof. A large part of the ultra fine ore fraction results in tailings. These ores demonstrate greater liberation (they are presented as individual particles of a single mineral per particle) at a lower particle size, meaning that a significant quantity of valuable mineral is lost in the process.” statements are included.
In said application, a foam flotation system is disclosed for the physical chemical separation of ultrafine ore particles.
Again, in the Polish patent application numbered PL399677A1 in the literature, " The subject of the invention is a method for the production of Zn-Pb collective concentrate with an increased silver content in the process of zinc sludge flotation. The method is carried out in such a way that the sludge from the zinc hydrometallurgy process is flotated in a flotation machine in order to produce a Zn-Pb flotation collective concentrate with an increased Ag content, and in order to filter the electrolyte residues, they are dewatered on a filter to the content of about 20% H2O and obtain a pH of 5 , 0-5.5. So cleaned, it is pumped to a flotation machine with four working sections. The sludge is introduced through the mixing chamber to the second section of the machine by preflotation at a pH value of 7.0 - 7.5, and the froth product of the second section is directed to the first concentrate chamber of the machine, from which the Zn-Pb-Ag collective concentrate is withdrawn. Sludges from the second section of the flotation machine after adding a foaming agent to them. (CuSO4
solution) and milk of lime until pH 9.5-11 .0 is fed into the third section of the machine. Foam products from the third and fourth section of the machine are fed into the mixing chamber, while the final waste from the fourth section of the machine is directed to the waste collection or settling ponds.” statements are included.
In the mentioned application, a method is described for the production of Zn-Pb bulk concentrate with higher silver content in zinc flotation sludge.
Again, in the European patent document numbered EP2597099A1 in the literature, “The present invention contains at least one phosphonium salt (I) with the formula R1 R2R3R4P+X- and (b) at least one compound (II) with the formula MYn or MYn. It is related to a deep eutectic solvent. m(H20) where R1 , R2, R3 and R4 are independently selected from H, substituted or unsubstituted, linear or branched alkyl, alkoxy, cycloalkyl, aryl or alkaryl, or where two of R1, R2, R3 and R4 are optionally substituted are alkylene groups, preferably a C4-C10 alkylene groups; X is halogen; M is selected from the group consisting of Li, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Sn, Pb, Bi, La or Ce; Y is selected from halide, nitrate, phosphate and/or acetate; n is from 1 to 5; m is from 1 to 10; and the molar ratio of phosphonium salt (I) to compound (II) is in the range of 2:1 to 1 :10. A method for its preparation is also provided.” statements are included.
In said patent, however, a deep eutectic solvent and a method for its preparation are disclosed.
For the reasons mentioned above, a new method was needed to obtain Zn and Pb metals from Zn-Pb ores.
Aim of the Invention
Starting from this position of the technique, the aim of the invention is to introduce a new method for the extraction of Zn and Pb metals from Zn-Pb ores, which eliminates the existing disadvantages.
Another aim of the invention is to present a method in which the volume of water to be used is always lower compared to the volumes of organic solvents, and no or very little water consumption is realized.
Another aim of the invention is to present a method that eliminates the problems related to wastewater generation and wastewater treatment.
Another aim of the invention is to present a method where metal recovery from ore deposits in arid regions where sufficient water supply cannot be provided is easier.
Another aim of the invention is to present a method that allows to reduce energy consumption by providing the opportunity to work at room temperature or at low temperatures (<100), unlike melting systems with very high energy consumption.
Another aim of the invention is to present a method in which the leaching process is carried out with much lower acid consumption compared to the leaching process performed in traditional hydrometallurgical methods.
Another aim of the invention is to present a method that makes it possible to leave the carbonate structured gangue minerals in the ore in the waste at a high rate.
Another aim of the invention is to provide a method that does not require an extra process step to remove unwanted metals from leaching solutions by preventing the dissolution of unwanted metals such as iron with the leaching process.
Detailed Description of the Invention
In this detailed explanation, the innovation that is the subject of the invention is only explained with examples that will not have any limiting effect for a better understanding of the subject.
A method for direct obtaining Zn and Pb metals from Zn-Pb ores which is using nonaqueous solvents such as molecular organic solvents, ionic liquids, and deep eutectic solvents instead of aqueous solutions and which provides less energy consumption
advantages compared to the pyrometallurgy method and higher selectivity advantages compared to the hydrometallurgy method characterized in that; includes method steps of; preparation of deep eutectic solvent with the help of a controlled mixer until a homogeneous and clear solution is obtained from 1 :2 mole ratio Choline Chloride (ChCI) - urea and 1 :0.5.1.5 mole ratio Choline Chloride (ChCI) - Urea- Ethylene or Choline Chloride (ChCI) - urea- organic acid or Choline Chloride (ChCI) - Organic acid, subjecting said Zn-Pb ore to deep eutectic solvent leaching under atmospheric conditions and the ore combined with the deep eutectic solvent during the leaching process becomes a slurry, obtaining solid waste and Zn-Pb loaded solution by making solid/liquid separation after the leaching process of said slurry, performing the electrowinning process by using different kinds of cathode anode from Zn-Pb loaded deep eutectic solvent obtained after the leaching process and obtaining metallic Zn/Pb or Zn and Pb metals as a result of electrowinning process.
Solvometallurgy is a new branch of extractive metallurgy that uses non-aqueous solvents such as molecular organic solvents, ionic liquids and deep eutectic solvents instead of aqueous solutions. Solvometallurgical methods provide advantages such as less energy consumption compared to the pyrometallurgical method and higher selectivity compared to the hydrometallurgical method.
Said deep eutectic solvents are commonly defined as systems consisting of a mixture of at least two components, a hydrogen bond acceptor and a hydrogen bond donor. Deep eutectic solvents are systems formed from a eutectic mixture of Lewis or Bronsted acids and bases that may contain various anionic and/or cationic species.
Deep eutectic solvents are usually a hydrogen bond acceptor such as a quaternary salt; It is a mixture of amines, carboxylic acids, alcohol and a hydrogen bond donor such as carbohydrates.
Deep eutectic solvents can basically be classified into four types (Table 1): Type I (quaternary salt and metal salt), Type II (quaternary salt and hydrated metal salt), Type III (quaternary salt and hydrogen bond donor) and Type IV (hydrated metal salt), salt and hydrogen bond donor). Deep eutectic solvents are expressed by the general formula Cat+ " zX Y.
Here Cat+ is any ammonium, phosphonium, or sulfonium cation and X is a Lewis base, usually a halide anion. Complex anionic species are formed between X- and Y, a Lewis or Brbnsted acid (z refers to the number of Y molecules interacting with the anion). Deep eutectic solvents are used in many areas due to their low vapor pressure, non-flammability, and easy recyclability compared to other organic solvents, as well as their biodegradability.
In addition, the low cost of deep eutectic solvents, unlike ionic solvents and mineral acids used in hydrometallurgical processes, provides a great economic advantage for their use on a larger scale. In addition, expensive and complex devices are not needed for their synthesis. For example, a controlled heater or a lyophilizer may be sufficient for the synthesis of these compounds.
Most of the deep eutectic solvents used are Type III. Here, eutectic formation is due to strong hydrogen bond interactions between hydrogen bond acceptor and hydrogen bond donor. One of the most common Cat+ X's is choline chloride (ChCI), also known as vitamin B4 with a melting point of 302°C, with the formula [(CH3)3N(CI)CH2- CH2OH], which consists of two functional groups containing a quaternary ammonium salt and alcohol. Common examples of Type III HBD are urea with the formula NH2CONH2, which is formed as a result of two -NH2 combined with a carbonyl (C=O) functional group with a melting temperature of 133 °C, which provides the formation of deep eutectic solvents, and b with a boiling temperature of 197 °C and a melting temperature of -12.9 °C. They are organics with the formula (CH2OH)2, such as ethylene glycol (EG) with a diol structure.
Commonly used deep eutectic solvents are ChCl-urea in 1 :2 mole ratio, ChCl-EG in 1 :2 mole ratio, and ChCl-urea-ethylene glycol and ChCl-urea-organic acid and ChCl- organic acid in 1 :0.5.1.5 mole ratio. The combined organics are prepared by mixing at temperatures below their melting point (<100 °C). There are Ch+ and Cl-/urea and Cl-/urea/ ethylene glycol and organic acid ions in the solution prepared by hydrogen bonding of the Cl- ion in ChCI, which is used as a hydrogen bond acceptor, to the organics used as the hydrogen bond donor.
These solvents, which are used in many fields, will be used in the technique of the invention to dissolve metals in the leaching of Zn-Pb ores. While Cl- ions in the content of deep eutectic solvents prepared with ChCl/urea or ChCl/Ure/ ethylene glycol or ChCl/Urea/organic acid or ChCl/organic acid are effective in the metal dissolution mechanism, Ch+ ion does not participate in the dissolution mechanism. During the leaching process, Cl- ions weaken the oxygen bond in metal oxide structures, causing the metal to bind to the oxygen of urea. In this case, Cl-/urea or CI-/urea/EG or Cl-/urea/organic acid or Cl-/organic acid compound bonded by hydrogen bonding takes the metal into its body and dissolution takes place (Reaction 1)-
MO + Ch+ + Cl-/urea — [MCIO. urea]- + Ch+ (M: Cu, Zn etc.)
In this method, which is the subject of the invention, Zn and Pb are obtained in metallic form by applying electrolysis to the solution of charged deep eutectic solvents by utilizing the high electrical conductivity of deep eutectic solvents after the leaching process, and the uncharged deep eutectic solvents from which the metals are removed can be reused in the leaching system.
The process steps of the production method of the invention are basically as follows;
- Choline Chloride (ChCI) in 1 :2 mol ratio - urea and Choline Chloride (ChCI)- Urea- Ethylene Glycol or Chloride (ChCI)- Urea - organic acid or Chloride (ChCI)- organic in 1 :0.5.1.5 mol ratio Preparation of deep eutectic solvent with the help of a controlled mixer until a homogeneous and clear solution is obtained from the acid,
- Subjecting the Zn-Pb ore to deep eutectic solvent leaching under atmospheric conditions and turning the ore into a slurry combined with the deep eutectic solvent during the leaching process,
- Obtaining solid waste and Zn-Pb loaded solution by making solid/liquid separation after leaching of the slurry,
- Electrowinning process using copper cathode and graphite anode from deep eutectic solvent with Zn-Pb load obtained after leaching,
- It is in the form of obtaining metallic Zn/Pb or Zn and Pb metals as a result of electrowinning process.
It is very important to prepare the aforementioned deep eutectic solvents with the help of a controlled mixer in the temperature range of 50-100 °C between 1 hour and infinite hours.
Zn-Pb ore is subjected to atmospheric deep eutectic solvent leaching at a temperature range of 50-100 °C, solid/liquid ratios of 1/5-1/25, 12-72 hours, and at a stirring rate where all solids can be mixed in suspension. In addition, the Zn and Pb loaded solution is subjected to electrowinning in the range of 0-10 V, in the range of 1 hour -infinite hour.
Before starting the leaching of the mentioned deep eutectic solvents, all equipment is cleaned in accordance with the experimental material cleaning procedure and contamination is prevented.
In order not to reduce the leaching efficiency of the organics and the physical water contained in the ore by being used in the leaching process, the physical water of the ore and the organics used is removed at 105 °C for 24 hours and stored in vacuum containers.
It is done at the voltage value at which Ch output will not occur during the electrowinning process.
Claims
CLAIMS A method for direct obtaining Zn and Pb metals from Zn-Pb ores which is using non-aqueous solvents such as molecular organic solvents, ionic liquids, and deep eutectic solvents instead of aqueous solutions and which provides less energy consumption advantages compared to the pyrometallurgy method and higher selectivity advantages compared to the hydrometallurgy method characterized in that; includes method steps of; preparation of deep eutectic solvent with the help of a controlled mixer until a homogeneous and clear solution is obtained from 1 :2 mole ratio Choline Chloride (ChCI) - urea and 1 :0.5.1.5 mole ratio Choline Chloride (ChCI) - Urea-Ethylene or Choline Chloride (ChCI) - urea- organic acid or Choline Chloride (ChCI) - Organic acid, subjecting said Zn-Pb ore to deep eutectic solvent leaching under atmospheric conditions and the ore combined with the deep eutectic solvent during the leaching process becomes a slurry, obtaining solid waste and Zn-Pb loaded solution by making solid/liquid separation after the leaching process of said slurry, performing the electrowinning process by using different kinds of cathode anode from Zn-Pb loaded deep eutectic solvent obtained after the leaching process and obtaining metallic Zn/Pb or Zn and Pb metals as a result of electrowinning process. A method for direct obtaining Zn and Pb metals from Zn-Pb ores in accordance with Claim 1 ; its feature is; preparation of said deep eutectic solvent at a temperature range of 50-100 °C for at least 1 hour with the help of a controlled mixer. A method for obtaining Zn and Pb metals from Zn-Pb ores according to any one of the above claims, it includes the method step of subjecting the Zn-Pb ore to atmospheric deep eutectic solvent leaching at a temperature range of 50-100 °C, in the range of solids/liquid ratios of 1/5-1/25, in the range of 12-72 hours and at a mixing speed where all the solids can be mixed in suspension.
A method for obtaining Zn and Pb metals from Zn-Pb ores according to any one of the above claims; it includes the method step of subjecting the Zn and Pb loaded solution to the electrowinning process in the 0-10 V range for at least 1 hour. A method for obtaining Zn and Pb metals from Zn-Pb ores according to any one of the above claims; it includes the method step of cleaning all equipment in accordance with the experimental material cleaning procedure before starting the deep eutectic solvent leaching in order to prevent contamination. A method for obtaining Zn and Pb metals from Zn-Pb ores according to any one of the above claims; it includes the method step of cleaning the ore and the organics used in the leaching process by removing the physical water at 105 °C for 24 hours and storing them in vacuum containers in order not to reduce the leaching efficiency of the organics and the physical water in the ore.
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CN112111655A (en) * | 2020-08-31 | 2020-12-22 | 江苏科技大学 | Method for deleading and purifying zinc-containing dust |
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CN108754137A (en) * | 2018-08-02 | 2018-11-06 | 桐乡市思远环保科技有限公司 | The method that metallic lead is produced using solvent extraction electrodeposition process |
CN112111655A (en) * | 2020-08-31 | 2020-12-22 | 江苏科技大学 | Method for deleading and purifying zinc-containing dust |
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