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WO2025107216A1 - Procédé de recyclage complet pour scories hydrométallurgiques de minerai de nickel latéritique - Google Patents

Procédé de recyclage complet pour scories hydrométallurgiques de minerai de nickel latéritique Download PDF

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Publication number
WO2025107216A1
WO2025107216A1 PCT/CN2023/133546 CN2023133546W WO2025107216A1 WO 2025107216 A1 WO2025107216 A1 WO 2025107216A1 CN 2023133546 W CN2023133546 W CN 2023133546W WO 2025107216 A1 WO2025107216 A1 WO 2025107216A1
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WIPO (PCT)
Prior art keywords
leaching
optionally
iron
selective
solution
Prior art date
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Application number
PCT/CN2023/133546
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English (en)
Chinese (zh)
Inventor
许开华
智文科
张坤
彭亚光
金国泉
刘文泽
许鹏云
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Pt Gem Indonesia New Energy Materials
Pt Qmb New Energy Materials
GEM Co Ltd Korea
Original Assignee
Pt Gem Indonesia New Energy Materials
Pt Qmb New Energy Materials
GEM Co Ltd Korea
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Priority to PCT/CN2023/133546 priority Critical patent/WO2025107216A1/fr
Publication of WO2025107216A1 publication Critical patent/WO2025107216A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C22B21/00—Obtaining aluminium
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • 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
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • 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
    • 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 application relates to the field of mineral metallurgy technology, specifically to the field of nickel hydrometallurgy technology, and in particular to a comprehensive recycling method for laterite nickel ore hydrometallurgical slag.
  • Nickel sulfide deposits and nickel oxide deposits are the main nickel deposits in the world.
  • the nickel reserves in nickel oxide deposits account for 70% of the total nickel reserves on land.
  • laterite nickel ore Because the surface of the ore is red due to iron oxidation, it is called laterite nickel ore.
  • laterite nickel ore is divided into silico-magnesia laterite nickel ore and limonite laterite nickel ore.
  • the content of nickel, silicon and magnesium in silico-magnesia laterite nickel ore is high, and the content of iron and cobalt is low.
  • Nickel iron or nickel pig iron is mainly obtained by pyrometallurgical process; while the content of iron and cobalt in limonite laterite nickel ore is high, and the content of nickel and magnesium is low.
  • the main hydrometallurgical process is used to obtain nickel cobalt sulfide or nickel cobalt hydroxide intermediates.
  • the nickel reserves of limonite laterite nickel ore account for 70% of the total resource reserves of laterite nickel ore, so its development and utilization are increasingly valued.
  • limonite laterite nickel ore is treated by acid leaching wet metallurgy, a lot of metallurgical slag is produced, of which the iron content is close to 50%, mainly in the form of hematite.
  • the grade of such slag iron does not meet the metallurgical raw material standards of steel mills, and conventional processing methods make it difficult to utilize it as a resource.
  • the metallurgical slag produced by acid-leaching wet metallurgical treatment of limonitic laterite nickel ore is currently stored in dams or discharged into the deep sea, which not only wastes resources but also easily pollutes the environment.
  • researchers have conducted some research so far, but the recycling is often single and the effect is not good.
  • CN109467101A discloses a process for preparing aluminum silicon solution by dissolving laterite nickel ore smelting slag, wherein the aluminum silicon solution is prepared by alkali melting laterite nickel ore slag, ultrasonically strengthening the water leaching process, and adding Al(OH) 3 as an aluminum source to adjust the silicon-aluminum molar ratio, thereby obtaining a water-slag mixed crude aluminum silicon solution, and filtering and liquid-solid separation to obtain the aluminum silicon solution.
  • Aluminum-silicon solution and solid filter residue with a certain molar ratio are obtained.
  • the above technical solution does not recycle iron resources.
  • CN108910909A discloses a method for preparing ZSM-5 molecular sieve using laterite nickel ore smelting waste residue, based on laterite nickel ore smelting waste residue, through crushing and screening, alkali boiling extraction, centrifugal separation, hydrothermal crystallization, centrifugal washing, powder drying, demolding and roasting, etc. to prepare ZSM-5 molecular sieve.
  • the above technical scheme adopts alkali boiling extraction method for nickel ore smelting waste residue, realizes effective extraction of Si-Al, avoids multi-step impurity removal, and greatly simplifies the process, but the above technical scheme does not recycle iron resources.
  • CN114774685A discloses a method for treating limonitic laterite-nickel ore hydrometallurgical slag, wherein the limonitic laterite-nickel ore hydrometallurgical slag is dried, crushed, moist-grinded and pelletized, and then high-volatile lignite is used as a source of reducing agent and heating fuel, and magnetized roasting is performed in a rotary kiln, and the discharged roasted ore is subjected to wet weak magnetic separation after indirect air cooling, and the iron concentrate after magnetic separation can be used as a sintering ironmaking raw material, thereby realizing the resource utilization of a large amount of limonitic laterite-nickel ore hydrometallurgical slag, and reducing the storage and discharge costs of metallurgical slag and the pressure on the environment.
  • the above technical scheme recycles iron resources, it does not recycle resources such as silicon, aluminum, calcium, and magnesium, and does not realize the comprehensive recycling of laterite-nickel or
  • the present application provides a comprehensive recycling method for laterite nickel ore hydrometallurgical slag, which mainly performs acid leaching, alkali leaching, calcination and other operations on the laterite nickel ore hydrometallurgical slag.
  • sodium silicate, calcium sulfate, magnesium oxide and aluminum oxide products can also be recovered, thereby maximizing the realization of laterite nickel ore hydrometallurgical slag.
  • the comprehensive recycling and utilization of slag can realize the comprehensive development and utilization of laterite nickel ore resources; the comprehensive recycling and utilization method described in this application has no discharge of three wastes during the process, the process is green and environmentally friendly, the method is simple and feasible, and is conducive to promotion and application.
  • the purpose of the present application is to provide a comprehensive recycling method for laterite nickel ore hydrometallurgical slag, the comprehensive recycling method comprising the following steps:
  • step (1) uniformly mixing the first leaching residue in step (1) with the second leaching agent to perform a second selective leaching, and obtaining a calcium sulfate product and a sodium silicate solution through a second solid-liquid separation;
  • step (3) uniformly mixing the first leachate obtained in step (1) with a third leachant to perform a third selective leaching, and obtaining a metal hydroxide and a third leachate through a third solid-liquid separation;
  • step (3) uniformly mixing the metal hydroxide of step (3) with a fourth leaching agent to perform a fourth selective leaching, and obtaining iron magnesium hydroxide and a sodium aluminate solution through a fourth solid-liquid separation, wherein the sodium aluminate solution is used to recover aluminum;
  • step (4) uniformly mixing the iron-magnesium hydroxide of step (4) with the fifth leaching agent to perform a fifth selective leaching, and obtaining magnesium hydroxide leaching residue and an iron-containing leaching liquid through a fifth solid-liquid separation; cooling the iron-containing leaching liquid and diluting it with water to obtain an iron hydroxide precipitate;
  • step (6) subjecting the magnesium hydroxide leaching residue of step (5) to a first calcination to obtain a magnesium oxide product
  • step (5) subjecting the iron hydroxide precipitate of step (5) to a second calcination to obtain iron oxide, and then recovering the elemental iron product, and/or subjecting the iron hydroxide precipitate of step (5) to acid leaching to obtain an iron-containing acid leaching solution, and then recovering the iron phosphate product;
  • step (2) There is no order between step (2) and step (3), and there is no order between step (6) and step (7). Order of precedence.
  • Fe, Mg, Al, and P can be introduced into the first leachate by performing a first selective leaching on the laterite nickel ore hydrometallurgical slag, and the first leaching slag is calcium sulfate and silicon dioxide.
  • the first leaching slag is subjected to a second selective leaching to obtain a calcium sulfate product and a sodium silicate solution.
  • the first leachate containing sulfate and phosphoric acid is subjected to a third selective leaching to obtain a metal hydroxide and a third leachate.
  • the comprehensive recycling and utilization method described in the present application mainly performs acid leaching, alkali leaching, calcination and other operations on the laterite nickel ore hydrometallurgical slag.
  • sodium silicate, calcium sulfate, magnesium oxide and aluminum oxide products can also be recovered, thereby maximizing the comprehensive recycling and utilization of the laterite nickel ore hydrometallurgical slag, thereby realizing the comprehensive development and utilization of laterite nickel ore resources;
  • the comprehensive recycling and utilization method described in the present application has no three wastes discharged during the process, the process is green and environmentally friendly, the method is simple and feasible, and is conducive to promotion and application.
  • the laterite nickel ore hydrometallurgical slag in step (1) is the metallurgical slag after high-pressure acid leaching of laterite nickel ore.
  • the laterite nickel ore hydrometallurgical slag in step (1) is limonitic laterite nickel ore hydrometallurgical slag, that is, limonitic laterite nickel ore hydrometallurgical slag is limonitic laterite nickel ore treated with high sulfuric acid Metallurgical slag obtained after acid leaching.
  • the dry basis composition of the laterite nickel ore hydrometallurgical slag in step (1) satisfies: TFe 46-58wt%, SiO 2 1.4-10.4wt%, MgO 1.2-11.2wt%, Al 2 O 3 5.9-10.9wt%, and CaO 1.1-9.5wt%.
  • TFe in laterite nickel ore hydrometallurgical slag refers to the total iron oxide content, that is, all contents including FeO, Fe 2 O 3 and Fe 3 O 4 ; moreover, those skilled in the art are well aware that the sum of the dry basis composition measured in laterite nickel ore hydrometallurgical slag is not 100%, because this is the normal loss rate caused by instrument detection, which is a normal situation caused by unified processing.
  • the laterite nickel ore hydrometallurgical slag is pre-treated before the first selective leaching in step (1).
  • the pretreatment includes drying, crushing and grinding performed in sequence to obtain laterite nickel ore hydrometallurgical fine powder slag.
  • the first leaching agent is a sulfuric acid solution, which can be selected from a sulfuric acid solution with a concentration of 100-200 g/L, such as a sulfuric acid solution with a concentration of 100 g/L, a sulfuric acid solution with a concentration of 110 g/L, a sulfuric acid solution with a concentration of 120 g/L, a sulfuric acid solution with a concentration of 140 g/L, a sulfuric acid solution with a concentration of 150 g/L, a sulfuric acid solution with a concentration of 180 g/L or a sulfuric acid solution with a concentration of 200 g/L, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • a sulfuric acid solution with a concentration of 100-200 g/L such as a sulfuric acid solution with a concentration of 100 g/L, a sulfuric acid solution with a concentration of 110 g/L, a sulfuric acid solution with a concentration of 120 g
  • the oxidant in step (1) is hydrogen peroxide, which can be selected from hydrogen peroxide with a concentration of 20-100 g/L, such as 20 g/L hydrogen peroxide, 30 g/L hydrogen peroxide, 40 g/L hydrogen peroxide, 50 g/L hydrogen peroxide, 60 g/L hydrogen peroxide, 70 g/L hydrogen peroxide, 80 g/L hydrogen peroxide, 90 g/L hydrogen peroxide or 100 g/L hydrogen peroxide, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the volume ratio of the first leaching agent to the oxidant in step (1) is 0.9-1.1, such as 0.9, 0.95, 1, 1.05 or 1.1, etc., but are not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the solid-to-liquid ratio of the first selective leaching in step (1) is 1g:(0.5-2.0)mL, for example 1g:0.5mL, 1g:0.7mL, 1g:0.8mL, 1g:1.0mL, 1g:1.1mL, 1g:1.3mL, 1g:1.5mL, 1g:1.8mL or 1g:2.0mL, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the solid-to-liquid ratio of the first selective leaching in step (1) of the present application refers to the ratio of the laterite nickel ore hydrometallurgical slag to the sum of the sulfuric acid solution and the hydrogen peroxide liquid.
  • the temperature of the first selective leaching in step (1) is 100-300°C, for example, 100°C, 130°C, 150°C, 180°C, 200°C, 230°C, 250°C, 280°C or 300°C, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the insulation time of the first selective leaching in step (1) is 0.5-4h, for example 0.5h, 0.8h, 1h, 1.3h, 1.5h, 1.8h, 2h, 2.3h, 2.5h, 2.8h, 3h, 3.3h, 3.5h, 3.8h or 4h, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the stirring rate of the first selective leaching in step (1) is 100-300 rpm, for example, 100 rpm, 120 rpm, 140 rpm, 150 rpm, 180 rpm, 200 rpm, 230 rpm, 250 rpm, 270 rpm, 280 rpm or 300 rpm, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the second leaching agent is a sodium hydroxide solution, which can be a sodium hydroxide solution with a concentration of 100-200 g/L, such as 100 g/L sodium hydroxide solution, 110 g/L sodium hydroxide solution, 120 g/L sodium hydroxide solution, 130 g/L sodium hydroxide solution, 150 g/L sodium hydroxide solution, 160 g/L sodium hydroxide solution, 180 g/L sodium hydroxide solution or 200 g/L sodium hydroxide solution.
  • Sodium oxide solution, etc. but are not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the solid-to-liquid ratio of the second selective leaching in step (2) is 1g:(0.9-1.9)mL, for example 1g:0.9mL, 1g:1mL, 1g:1.1mL, 1g:1.2mL, 1g:1.3mL, 1g:1.4mL, 1g:1.5mL, 1g:1.6mL, 1g:1.7mL, 1g:1.8mL or 1g:1.9mL, etc., but is not limited to the listed values, and other values not listed within the above numerical range are equally applicable.
  • the temperature of the second selective leaching in step (2) is 70-150°C, for example, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the insulation time of the second selective leaching in step (2) is 0.5-2h, for example 0.5h, 0.7h, 0.8h, 1h, 1.1h, 1.3h, 1.5h, 1.7h, 1.8h or 2h, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the stirring rate of the second selective leaching in step (2) is 150-350 rpm, for example, 150 rpm, 160 rpm, 180 rpm, 200 rpm, 210 rpm, 230 rpm, 250 rpm, 270 rpm, 280 rpm, 300 rpm, 310 rpm, 330 rpm or 350 rpm, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the third leaching agent in step (3) is a sodium hydroxide solution, which can be selected from a sodium hydroxide solution with a concentration of 100-200 g/L, such as 100 g/L sodium hydroxide solution, 110 g/L sodium hydroxide solution, 120 g/L sodium hydroxide solution, 130 g/L sodium hydroxide solution, 150 g/L sodium hydroxide solution, 160 g/L sodium hydroxide solution, 180 g/L sodium hydroxide solution or 200 g/L sodium hydroxide solution, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the volume ratio of the third selective leaching in step (3) is 1ml:(0.5-1.5)mL, for example, 1ml:0.5mL, 1ml:0.6mL, 1ml:0.7mL, 1ml:0.8mL, 1ml:0.9mL, 1ml:1.0mL, 1ml:1.1mL, 1ml:1.2mL, 1ml:1.3mL, 1ml:1.4mL or 1ml:1.5mL, etc., but is not limited to the listed values, other values not listed within the above numerical range are also applicable.
  • the temperature of the third selective leaching in step (3) is 80-150°C, for example 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the insulation time of the third selective leaching in step (3) is 0.5-2h, for example 0.5h, 0.7h, 0.8h, 1h, 1.1h, 1.3h, 1.5h, 1.7h, 1.8h or 2h, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the stirring rate of the third selective leaching in step (3) is 150-350 rpm, for example, 150 rpm, 160 rpm, 180 rpm, 200 rpm, 210 rpm, 230 rpm, 250 rpm, 270 rpm, 280 rpm, 300 rpm, 310 rpm, 330 rpm or 350 rpm, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the fourth leaching agent in step (4) is a sodium hydroxide solution, which can be selected from a sodium hydroxide solution with a concentration of 100-200 g/L, such as 100 g/L sodium hydroxide solution, 110 g/L sodium hydroxide solution, 120 g/L sodium hydroxide solution, 130 g/L sodium hydroxide solution, 150 g/L sodium hydroxide solution, 160 g/L sodium hydroxide solution, 180 g/L sodium hydroxide solution or 200 g/L sodium hydroxide solution, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the solid-liquid ratio of the fourth selective leaching in step (4) is 1g: (1-3) mL, for example, 1g: 1mL, 1g: 1.3mL, 1g: 1.5mL, 1g: 1.8mL, 1g: 2mL, 1g: 2.3mL, 1g: 2.5mL, 1g: 2.8mL or 1g: 3mL, but is not limited to the values listed above. Other values not listed in the above numerical ranges are The same applies to the values given above.
  • the insulation time of the fourth selective leaching in step (4) is 0.5-2h, for example 0.5h, 0.7h, 0.8h, 1h, 1.1h, 1.3h, 1.5h, 1.7h, 1.8h or 2h, etc., but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the stirring rate of the fourth selective leaching in step (4) is 150-350rpm, for example, 150rpm, 160rpm, 180rpm, 200rpm, 210rpm, 230rpm, 250rpm, 270rpm, 280rpm, 300rpm, 310rpm, 330rpm or 350rpm, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the fifth leaching agent in step (5) is a hot sodium hydroxide solution, which can be a sodium hydroxide solution with a concentration of 200-400 g/L, such as 200 g/L, 202 g/L, 240 g/L, 260 g/L, 280 g/L, 300 g/L, 320 g/L, 340 g/L, 360 g/L, 380 g/L or 400 g/L, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • 200-400 g/L such as 200 g/L, 202 g/L, 240 g/L, 260 g/L, 280 g/L, 300 g/L, 320 g/L, 340 g/L, 360 g/L, 380 g/L or 400 g/L, etc.
  • the fifth leaching agent in step (5) of the present application is a hot sodium hydroxide solution, and the temperature of the corresponding sodium hydroxide solution is 80-160°C, that is, consistent with the temperature of the fifth selective leaching.
  • the solid-to-liquid ratio of the fifth selective leaching in step (5) is 1g:(1-3)mL, for example, 1g:1mL, 1g:1.3mL, 1g:1.5mL, 1g:1.8mL, 1g:2mL, 1g:2.3mL, 1g:2.5mL, 1g:2.8mL or 1g:3mL, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the temperature of the fifth selective leaching in step (5) is 80-160°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C or 160°C, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the insulation time of the fifth selective leaching in step (5) is 0.5-2h, for example 0.5h, 0.7h, 0.8h, 1h, 1.1h, 1.3h, 1.5h, 1.7h, 1.8h or 2h, etc., but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the stirring rate of the fifth selective leaching in step (5) is 150-350 rpm, for example, 150 rpm, 160 rpm, 180 rpm, 200 rpm, 210 rpm, 230 rpm, 250 rpm, 270 rpm, 280 rpm, 300 rpm, 310 rpm, 330 rpm or 350 rpm, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the temperature of the first calcination in step (6) is 350-600°C, for example, 350°C, 380°C, 400°C, 430°C, 450°C, 480°C, 500°C, 530°C, 550°C, 580°C or 600°C, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the temperature of the second calcination in step (7) is 500-800°C, for example, 500°C, 530°C, 550°C, 580°C, 600°C, 620°C, 650°C, 670°C, 700°C, 730°C, 750°C, 780°C or 800°C, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the method for recovering aluminum using the sodium aluminate solution in step (4) comprises: adding Al(OH) 3 seed crystals to the sodium aluminate solution, filtering after precipitation of Al(OH) 3 crystals to obtain a metallurgical grade Al(OH) 3 product, and then calcining to obtain an Al2O3 product.
  • the method for recovering an elemental iron product using the iron oxide obtained in step (7) comprises: reducing the obtained iron oxide under a reducing atmosphere to obtain an elemental iron product, which is generally in the form of iron concentrate.
  • the reducing atmosphere is H2 and/or CO.
  • the acid solution used for acid leaching in step (7) is a hydrochloric acid solution.
  • the step (7) of recovering the iron phosphate product comprises: adding phosphoric acid and ammonia water to the iron-containing acid leaching solution for co-precipitation to obtain the iron phosphate product.
  • solutions described in this application refer to aqueous solutions, for example, a sulfuric acid solution refers to an aqueous sulfuric acid solution.
  • the comprehensive recycling method described in the present application mainly performs acid leaching, alkali leaching, calcination and other operations on the laterite nickel ore hydrometallurgical slag.
  • sodium silicate, calcium sulfate, magnesium oxide and aluminum oxide products can also be recovered, thereby maximizing the comprehensive recycling of laterite nickel ore hydrometallurgical slag, thereby realizing the comprehensive development and utilization of laterite nickel ore resources;
  • FIG1 is a process flow chart of the comprehensive recycling method of laterite nickel ore hydrometallurgical slag described in the present application.
  • the present application provides a comprehensive recycling method for laterite nickel ore hydrometallurgical slag, the process flow chart of which is shown in FIG1 , and the comprehensive recycling method comprises the following steps:
  • step (1) uniformly mixing the first leaching residue (mainly containing CaSO 4 +SiO 2 ) in step (1) with a second leaching agent to perform a second selective leaching, and obtaining a calcium sulfate product and a sodium silicate solution through a second solid-liquid separation;
  • step (3) uniformly mixing the first leachate obtained in step (1) with a third leachant to perform a third selective leaching, and obtaining a metal hydroxide and a third leachate through a third solid-liquid separation;
  • step (3) (4) uniformly mixing the metal hydroxide of step (3) with a fourth leaching agent to perform a fourth selective leaching, and obtaining iron magnesium hydroxide and a sodium aluminate solution through a fourth solid-liquid separation, wherein the sodium aluminate solution is used to recover aluminum; wherein the method for using the sodium aluminate solution to recover aluminum comprises: Add Al(OH) 3 seed crystals to the sodium hydroxide solution, precipitate Al(OH) 3 crystals, filter to obtain metallurgical grade Al(OH) 3 products, and then calcine to obtain Al 2 O 3 products;
  • step (4) uniformly mixing the iron-magnesium hydroxide of step (4) with the fifth leaching agent to perform a fifth selective leaching, and obtaining magnesium hydroxide leaching residue and an iron-containing leaching liquid through a fifth solid-liquid separation; cooling the iron-containing leaching liquid and diluting it with water to obtain an iron hydroxide precipitate;
  • step (6) subjecting the magnesium hydroxide leaching residue of step (5) to a first calcination to obtain a magnesium oxide product
  • step (5) subjecting the iron hydroxide precipitate of step (5) to a second calcination to obtain iron oxide, and then calcining it in a reducing atmosphere of H 2 and CO to obtain an elemental iron product, mainly iron concentrate;
  • the iron hydroxide precipitate in step (5) is acid-leached with a hydrochloric acid solution to obtain an acid leaching solution containing FeCl 3 , phosphoric acid and ammonia water are added for co-precipitation to obtain an iron phosphate product;
  • step (2) There is no order of precedence between step (2) and step (3), and there is no order of precedence between step (6) and step (7).
  • This embodiment provides a comprehensive recycling method for laterite nickel ore hydrometallurgical slag, and the comprehensive recycling method comprises the following steps:
  • the laterite nickel ore hydrometallurgical slag is limonite type laterite nickel ore hydrometallurgical slag, and the dry basis composition satisfies: TFe 46-58wt%, SiO 2 1.4-10.4wt%, MgO 1.2-11.2wt%, Al 2 O 3 5.9-10.9wt%, CaO 1.1-9.5wt%;
  • the first leached residue in step (1) is mixed evenly with a sodium hydroxide solution having a concentration of 100 g/L.
  • a second selective leaching was performed with a solid-liquid ratio of 1 g:0.9 mL, a temperature of 70° C., a holding time of 0.5 h, and a stirring rate of 150 rpm, and a calcium sulfate product and a sodium silicate solution were obtained through the second solid-liquid separation;
  • step (3) the first leachate of step (1) was mixed evenly with a sodium hydroxide solution having a concentration of 100 g/L to perform a third selective leaching, the volume ratio being 1 mL:0.5 mL, the temperature being 80° C., the insulation time being 0.5 h, the stirring rate being 150 rpm, and the metal hydroxide and the third leachate being obtained by a third solid-liquid separation;
  • step (3) The metal hydroxide of step (3) is mixed evenly with a sodium hydroxide solution having a concentration of 100 g/L to perform a fourth selective leaching, with a solid-liquid ratio of 1 g:1 mL, a temperature of 80° C., a holding time of 0.5 h, and a stirring rate of 150 rpm, and iron magnesium hydroxide and sodium aluminate solution are obtained through a fourth solid-liquid separation; Al(OH) 3 seed crystals are added to the sodium aluminate solution, and Al(OH) 3 crystals are precipitated and filtered to obtain a metallurgical grade Al(OH) 3 product, which is then calcined to obtain an Al 2 O 3 product;
  • the iron-magnesium hydroxide of step (4) is mixed evenly with the fifth leaching agent (hot sodium hydroxide solution) to perform the fifth selective leaching, the solid-liquid ratio is 1g:1mL, the temperature is 80°C, the insulation time is 0.5h, the stirring rate is 150rpm, and the magnesium hydroxide leaching residue and the iron-containing leaching liquid are obtained by the fifth solid-liquid separation; the iron-containing leaching liquid is cooled and diluted with water to obtain iron hydroxide precipitate;
  • the fifth leaching agent hot sodium hydroxide solution
  • step (5) subjecting the iron hydroxide precipitate of step (5) to a second calcination at 500° C., and reducing the obtained iron oxide in a CO reducing atmosphere to obtain an elemental iron product;
  • step (2) There is no order of precedence between step (2) and step (3), and there is no order of precedence between step (6) and step (7).
  • This embodiment provides a comprehensive recycling method for laterite nickel ore hydrometallurgical slag, the comprehensive recycling method comprising the following steps:
  • the laterite nickel ore hydrometallurgical slag is limonite type laterite nickel ore hydrometallurgical slag, and the dry basis composition satisfies: TFe 46-58wt%, SiO 2 1.4-5.4wt%, MgO 1.2-5.2wt%, Al 2 O 3 5.9-9.9wt%, CaO 1.1-4.1wt%;
  • step (2) the first leaching residue of step (1) was mixed evenly with a sodium hydroxide solution having a concentration of 150 g/L to perform a second selective leaching, with a solid-liquid ratio of 1 g:1.3 mL, a temperature of 110° C., a holding time of 1 h, a stirring rate of 250 rpm, and a calcium sulfate product and a sodium silicate solution were obtained by a second solid-liquid separation;
  • step (1) the first leachate of step (1) was mixed evenly with a sodium hydroxide solution having a concentration of 150 g/L to perform a third selective leaching, with a volume ratio of 1 mL:1 mL, a temperature of 110° C., a holding time of 1 h, a stirring rate of 250 rpm, and a third solid-liquid separation to obtain a metal hydroxide and a third leachate;
  • step (3) The metal hydroxide of step (3) is mixed evenly with a sodium hydroxide solution having a concentration of 150 g/L to perform a fourth selective leaching, with a solid-liquid ratio of 1 g:2 mL, a temperature of 120° C., a holding time of 1 h, and a stirring rate of 250 rpm, and iron magnesium hydroxide and sodium aluminate solution are obtained through a fourth solid-liquid separation; Al(OH) 3 seed crystals are added to the sodium aluminate solution, and Al(OH) 3 crystals are precipitated and filtered to obtain a metallurgical grade Al(OH) 3 product, which is then calcined to obtain an Al 2 O 3 product;
  • the iron-magnesium hydroxide of step (4) is mixed evenly with the fifth leaching agent (hot sodium hydroxide solution) to perform the fifth selective leaching, the solid-liquid ratio is 1g:2mL, the temperature is 120°C, the insulation time is 1h, the stirring rate is 250rpm, and the magnesium hydroxide leaching residue and the iron-containing leaching liquid are obtained by the fifth solid-liquid separation; the iron-containing leaching liquid is cooled and diluted with water to obtain iron hydroxide precipitate;
  • the fifth leaching agent hot sodium hydroxide solution
  • step (5) The magnesium hydroxide leached residue of step (5) is first calcined at 450° C. to obtain an oxide Magnesium products;
  • step (5) subjecting the iron hydroxide precipitate of step (5) to a second calcination at 650° C., and reducing the obtained iron oxide in a CO reducing atmosphere to obtain an elemental iron product;
  • step (2) There is no order of precedence between step (2) and step (3), and there is no order of precedence between step (6) and step (7).
  • This embodiment provides a comprehensive recycling method for laterite nickel ore hydrometallurgical slag, and the comprehensive recycling method comprises the following steps:
  • the laterite nickel ore hydrometallurgical slag is limonite type laterite nickel ore hydrometallurgical slag, and the dry basis composition satisfies: TFe 46-58wt%, SiO 2 1.4-5.4wt%, MgO 1.2-5.2wt%, Al 2 O 3 5.9-9.9wt%, CaO 1.1-4.1wt%;
  • step (2) mixing the first leached residue of step (1) with a sodium hydroxide solution having a concentration of 200 g/L and performing a second selective leaching, the solid-liquid ratio being 1 g:1.9 mL, the temperature being 150° C., the insulation time being 2 h, the stirring rate being 350 rpm, and obtaining a calcium sulfate product and a sodium silicate solution through a second solid-liquid separation;
  • step (3) the first leachate of step (1) was mixed evenly with a sodium hydroxide solution having a concentration of 200 g/L to perform a third selective leaching, the volume ratio being 1 mL:1.5 mL, the temperature being 150° C., the insulation time being 2 h, the stirring rate being 350 rpm, and the metal hydroxide and the third leachate being obtained by a third solid-liquid separation;
  • step (3) The metal hydroxide described in step (3) was mixed evenly with a sodium hydroxide solution having a concentration of 200 g/L for a fourth selective leaching, with a solid-liquid ratio of 1 g:3 mL, a temperature of 160° C., a holding time of 2 h, and stirring.
  • the stirring rate is 350 rpm, and iron magnesium hydroxide and sodium aluminate solution are obtained through the fourth solid-liquid separation;
  • Al(OH) 3 seed crystals are added to the sodium aluminate solution, and Al(OH) 3 crystals are precipitated and filtered to obtain metallurgical grade Al(OH) 3 products, which are then calcined to obtain Al 2 O 3 products;
  • the iron-magnesium hydroxide of step (4) is mixed evenly with the fifth leaching agent (hot sodium hydroxide solution) to perform the fifth selective leaching, the solid-liquid ratio is 1 g:3 mL, the temperature is 160° C., the insulation time is 2 h, the stirring rate is 350 rpm, and the magnesium hydroxide leaching residue and the iron-containing leaching liquid are obtained by the fifth solid-liquid separation; the iron-containing leaching liquid is cooled and diluted with water to obtain an iron hydroxide precipitate;
  • the fifth leaching agent hot sodium hydroxide solution
  • step (5) calcining the iron hydroxide precipitate in step (5) at 800° C. for a second time, leaching the obtained iron oxide with a hydrochloric acid solution to obtain a ferric chloride solution, adding phosphoric acid and ammonia water as precipitants to co-precipitate, and obtaining an iron phosphate product;
  • step (2) There is no order of precedence between step (2) and step (3), and there is no order of precedence between step (6) and step (7).
  • the comprehensive recycling method described in this application mainly performs acid leaching, alkali leaching, calcination and other operations on the laterite nickel ore hydrometallurgical slag.
  • sodium silicate, calcium sulfate, magnesium oxide and aluminum oxide products can also be recovered, thereby maximizing the recovery of laterite nickel ore hydrometallurgical slag.
  • the comprehensive recycling and utilization of metallurgical slag can realize the comprehensive development and utilization of laterite nickel ore resources.
  • the comprehensive recycling and utilization method described in this application has no discharge of three wastes during the process, the process is green and environmentally friendly, the method is simple and feasible, and is conducive to promotion and application.

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Abstract

Procédé de recyclage complet pour scories hydrométallurgiques de minerai de nickel latéritique. Le procédé est principalement destiné à effectuer des opérations telles que la lixiviation acide, la lixiviation alcaline et la calcination sur des scories hydrométallurgiques de minerai de nickel latéritique, et dans le procédé de récupération de concentrés de fer et/ou de produits de phosphate de fer, le silicate de sodium, le sulfate de calcium, l'oxyde de magnésium et les produits d'oxyde d'aluminium peuvent également être récupérés, de telle sorte qu'un recyclage complet des scories hydrométallurgiques de minerai de nickel latéritique est obtenu au maximum, ce qui permet d'obtenir une utilisation et un développement complets de ressources de minerai de nickel latéritique ; le procédé ne produit aucune émissions de trois types de déchets, le procédé est écologique et respectueux de l'environnement, et le procédé est simple et réalisable, et est propice à la popularisation et à l'application.
PCT/CN2023/133546 2023-11-23 2023-11-23 Procédé de recyclage complet pour scories hydrométallurgiques de minerai de nickel latéritique Pending WO2025107216A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101525143A (zh) * 2009-01-09 2009-09-09 东北大学 一种由红土镍矿制备氧化镁、二氧化硅及氧化镍产品的方法
WO2010094161A1 (fr) * 2009-02-18 2010-08-26 中南大学 Procédé d'extraction de métaux de valeur à partir de minerai de nickel latéritique avec circulation d'acide chlorhydrique entièrement en boucle fermée
CN102115816A (zh) * 2011-01-07 2011-07-06 东北大学 一种综合利用红土镍矿的方法
CN107739829A (zh) * 2017-09-29 2018-02-27 中国恩菲工程技术有限公司 红土镍矿冶炼中和渣中镍元素、钴元素、铜元素及锌元素的回收方法
CN108328659A (zh) * 2018-02-23 2018-07-27 北京科技大学 一种综合处理利用高镁镍铁渣的方法
CN112520766A (zh) * 2020-09-21 2021-03-19 河南省睿博环境工程技术有限公司 一种石棉尾矿低成本综合利用方法
WO2022126761A2 (fr) * 2020-12-14 2022-06-23 荆门市格林美新材料有限公司 Procédé d'extraction complète de métaux de valeur à partir de minerai de nickel latéritique
CN115747516A (zh) * 2022-11-21 2023-03-07 昆明理工大学 一种高镁硅红土镍矿回收镍、钴、镁和铁的方法
CN116770065A (zh) * 2023-06-25 2023-09-19 四川顺应动力电池材料有限公司 一种红土镍矿酸浸渣资源化利用的方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101525143A (zh) * 2009-01-09 2009-09-09 东北大学 一种由红土镍矿制备氧化镁、二氧化硅及氧化镍产品的方法
WO2010094161A1 (fr) * 2009-02-18 2010-08-26 中南大学 Procédé d'extraction de métaux de valeur à partir de minerai de nickel latéritique avec circulation d'acide chlorhydrique entièrement en boucle fermée
CN102115816A (zh) * 2011-01-07 2011-07-06 东北大学 一种综合利用红土镍矿的方法
CN107739829A (zh) * 2017-09-29 2018-02-27 中国恩菲工程技术有限公司 红土镍矿冶炼中和渣中镍元素、钴元素、铜元素及锌元素的回收方法
CN108328659A (zh) * 2018-02-23 2018-07-27 北京科技大学 一种综合处理利用高镁镍铁渣的方法
CN112520766A (zh) * 2020-09-21 2021-03-19 河南省睿博环境工程技术有限公司 一种石棉尾矿低成本综合利用方法
WO2022126761A2 (fr) * 2020-12-14 2022-06-23 荆门市格林美新材料有限公司 Procédé d'extraction complète de métaux de valeur à partir de minerai de nickel latéritique
CN115747516A (zh) * 2022-11-21 2023-03-07 昆明理工大学 一种高镁硅红土镍矿回收镍、钴、镁和铁的方法
CN116770065A (zh) * 2023-06-25 2023-09-19 四川顺应动力电池材料有限公司 一种红土镍矿酸浸渣资源化利用的方法

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