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WO2018161652A1 - Procédé de recyclage combinant valorisation et métallurgie et destiné à un minerai d'oxyde de cuivre à inclusions solides - Google Patents

Procédé de recyclage combinant valorisation et métallurgie et destiné à un minerai d'oxyde de cuivre à inclusions solides Download PDF

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Publication number
WO2018161652A1
WO2018161652A1 PCT/CN2017/114278 CN2017114278W WO2018161652A1 WO 2018161652 A1 WO2018161652 A1 WO 2018161652A1 CN 2017114278 W CN2017114278 W CN 2017114278W WO 2018161652 A1 WO2018161652 A1 WO 2018161652A1
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WIPO (PCT)
Prior art keywords
copper
copper oxide
magnetic separation
heating
leaching
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.)
Ceased
Application number
PCT/CN2017/114278
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English (en)
Chinese (zh)
Inventor
文书明
朱景和
刘媛媛
黄草明
邓久帅
刘建
沈海英
王伊杰
陈瑜
张谦
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.)
Kunming University of Science and Technology
China Nonferrous Metal Mining Group Co Ltd
Original Assignee
Kunming University of Science and Technology
China Nonferrous Metal Mining Group Co Ltd
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Publication date
Application filed by Kunming University of Science and Technology, China Nonferrous Metal Mining Group Co Ltd filed Critical Kunming University of Science and Technology
Publication of WO2018161652A1 publication Critical patent/WO2018161652A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • 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
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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 invention relates to a method for the combined recycling and utilization of solid inclusion copper oxide ore, belonging to the technical field of mineral processing metallurgy.
  • Copper oxide minerals mainly include malachite, chrysocolla, azurite, cuprite, chert, garnet malachite, copper, etc., mainly with gangue minerals such as silicate, carbonate and iron oxide.
  • the independently present oxidized copper ore such as malachite, chrysocolla, azurite, cuprite, and epochrite can be recovered by the fluorinated yellow medicine flotation method, and the binding rate is high, and the silicic acid is used.
  • the copper oxide ore which is densely symbiotic with salt minerals can be recycled by means of sulfuric acid leaching, solid-liquid separation and extraction electrowinning.
  • ammonia leaching and solidification can be used. The liquid is separated and extracted by electrowinning.
  • part of the copper oxide ore is closely symbiotic with limonite, hematite and biotite.
  • the copper ore is mostly oxidized by iron oxidized minerals and biotite. The method utilized makes this part of the copper oxide ore resources not effectively recycled.
  • vulcanization-xanthate flotation method is difficult to recover such copper oxide minerals because part of the copper oxide ore is encapsulated by hematite, limonite, biotite, and copper oxide minerals cannot be dissociated by monomers, vulcanizing agents and The collector xanthate is difficult to contact with the surface of the copper oxide mineral and cannot be floated to recover this part of the copper oxide mineral.
  • Conventional ammonia leaching-extraction-electrowinning technology cannot effectively recover this part of copper oxide ore because ammonia cannot damage the structure of iron oxide ore and biotite, and it is difficult to contact with copper oxide minerals in inclusions, and this part cannot be effectively leached. Copper oxide ore.
  • Ke Shengnan et al. used hydrochloric acid as the leaching agent to investigate the effects of leaching temperature, leaching time, hydrochloric acid volume and red mud mass ratio and hydrochloric acid concentration on the leaching rate of hydrazine during the recovery of sputum from hydrochloric acid by conventional and microwave strengthening. Studies have shown that microwaves have a certain strengthening effect on the leaching of bismuth [rare metals and hard alloys, 2016 (5): 26-31]. Gong Mingming analyzed the current status of aluminum leaching process of fly ash, aimed at reducing energy consumption and improving utilization of fly ash. Microwave heating technology was introduced to promote the rapid dissolution of aluminum in fly ash, and mechanical activation-hydrochloric acid leaching powder was explored.
  • a polymer bridge flotation method combining copper impregnation body is a combined copper impregnation body which cannot be recovered by conventional flotation, and adopts polymer bridging agent, copper ion bridge ion and xanthate bridge.
  • the collector is adsorbed by the polymer bridge ion on the surface of the copper-impregnated body, and the copper ion is adsorbed on the bridged adsorbent on the surface, and the collector xanthate anion is adsorbed on the bridged copper ion.
  • the surface of the copper-impregnated body is made hydrophobic to achieve effective flotation. The method can not be effectively used for the recovery and utilization of the solid inclusion copper oxide ore.
  • the reason is that the polymer of the compound of the overseas Chinese cannot be combined with the copper oxide ore which is surrounded by gangue minerals such as hematite, limonite and biotite.
  • the copper oxide mineral is recovered by means of Float flotation.
  • the method is for the oxygen-sulfur mixed copper ore with high combination rate and high calcium-magnesium carbonate gangue mineral content, firstly recovering the copper sulfide mineral and free copper oxide mineral by flotation, and the flotation tailings with fatty acid anti- Flotation of calcium-magnesium carbonate minerals, obtaining calcium-magnesium carbonate minerals low, containing copper in the middle ore, adding sulfuric acid, stirring and leaching combined with copper, solid-liquid separation of copper-containing solution to obtain copper products by metallurgical methods .
  • the method cannot be used for treating such solid inclusion copper oxide ore because the free copper oxide mineral in the solid inclusion copper oxide ore is less, the flotation of the yellow drug has no good effect, and the calcium and magnesium are floating.
  • the selection will cause some of the iron-containing minerals to enter the carbonate minerals, resulting in the loss of copper minerals.
  • the object of the present invention is to provide a method for solid-encapsulated copper oxide ore separation and utilization for a copper oxide ore which is difficult to recover by flotation and has a low direct acid leaching rate, and is obtained by strong magnetic separation.
  • the magnetic product of copper oxide is coated, the magnetic product is filtered, microwave drying and heating are used, and the selectivity of heating of different minerals in the solid inclusion by microwave is utilized, so that the temperature rises between the minerals and the volume expansion is different, and the crack is generated, which is the later sulfuric acid.
  • Leaching provides diffusion channels, increases leaching rates and leaching rates, and efficiently recovers this refractory copper ore resource.
  • a method for solid-packaged copper oxide ore separation and utilization comprising the following steps:
  • the copper content is 0.8% to 1.5%, the oxidation rate is greater than 95%, the copper distribution rate in the free copper oxide ore is less than 40%, and the distribution rate of copper wrapped in limonite, hematite and biotite is 50%.
  • the magnetic separation concentrate obtained in the step (1) is dried and heated by a continuous industrial microwave oven, and the heating temperature is heated.
  • the degree reaches 400 degrees Celsius to 450 degrees Celsius the temperature is kept for 10 minutes to 15 minutes, and the copper-containing inclusion material is obtained by microwave heating, and the steam generated by the magnetic separation concentrate is used to supplement the heated magnetic separation tailings slurry;
  • step (3) mixing the microwave-heated copper-containing inclusion material obtained in the step (2) with the normal-temperature magnetic separation tailings slurry obtained in the step (1) to cause water quenching of the inclusion mineral particles, and heating the slurry to be mixed.
  • the slurry is introduced into the mixing tank, sulfuric acid is added to the pH value of 1 to 1.5, and the steam is further introduced to continue heating, and the leaching is carried out for 90 minutes to 120 minutes under the condition of 50 to 60 degrees Celsius;
  • step (3) Performing solid-liquid separation of the leached pulp in step (3), extracting electrowinning to obtain electrowinning copper, and separating solid and liquid leaching slag into tailings.
  • the microwave is directly heated to the slurry. Because of the good absorbing properties of the water, the water is preferentially heated, the temperature of the ore is slow, and the temperature rise is less than 100 degrees Celsius.
  • the selective heating of the microwave causes cracks in the ore. Can not be used, the effect of microwave enhanced leaching is not obvious.
  • the invention directly heats the ore, has a fast heating rate, a high temperature, and has obvious cracks in the ore. Later, the leaching effect is obvious, and the amount of ore heated by the microwave is reduced, and the cost is also greatly reduced.
  • Figure 1 is a flow chart of the principles of the present invention.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Raw materials 1.5% copper grade, oxidation rate greater than 95%, copper distribution in free copper oxide ore is less than 40%, solid inclusion oxidation of 60% copper distribution in limonite, hematite and biotite Copper ore.
  • the magnetic separation concentrate is dried and heated by a continuous industrial microwave oven. When the heating temperature reaches 450 degrees Celsius, the temperature is kept for 15 minutes, and the copper-containing inclusion material is obtained by microwave heating, and the steam generated by the magnetic separation concentrate is used for replenishing. Heating magnetic separation tailings slurry;
  • the overall recovery rate of copper is 90%.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Raw materials 1.0% copper grade, oxidation rate greater than 95%, copper distribution in free copper oxide ore is less than 40%, and the distribution of copper encapsulated by limonite, hematite and biotite is 53% solid inclusion oxidation. Copper ore.
  • the magnetic separation concentrate is dried and heated by a continuous industrial microwave oven. When the heating temperature reaches 450 degrees Celsius, the temperature is kept for 15 minutes, and the copper-containing inclusion material is obtained by microwave heating, and the steam generated by the magnetic separation concentrate is used for replenishing. Heating magnetic separation tailings slurry;
  • the overall recovery rate of copper is 84%.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • Raw materials 0.8% copper content, oxidation rate greater than 95%, copper distribution rate in free copper oxide ore is less than 40%, solid inclusion oxidation of 50% copper distribution in limonite, hematite and biotite Copper ore.
  • the magnetic separation concentrate is dried and heated by a continuous industrial microwave oven, and when the heating temperature reaches 400 degrees Celsius, the temperature is kept for 10 minutes, and the copper-containing inclusion material is obtained by microwave heating;
  • the overall recovery rate of copper is 82%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de recyclage combinant valorisation et métallurgie et destiné à un minerai d'oxyde de cuivre à inclusions solides. Dans cette perspective, ledit procédé comprend les étapes consistant à : effectuer une séparation magnétique à haute intensité sur un minerai d'oxyde de cuivre enveloppé d'un minerai faiblement magnétique qui est difficile à recycler par flottation et qui a un taux de lixiviation directe à l'acide de façon à obtenir un produit magnétique enveloppé d'oxyde de cuivre ; filtrer le produit magnétique ; procéder à un séchage et à un chauffage par micro-ondes ; et utiliser la sélectivité du chauffage par micro-ondes sur différents minerais dans une inclusion solide. Les augmentations de température des minerais sont différentes, les dilatations volumiques sont différentes, ce qui génère des fissures. Un canal de diffusion est prévu pour une lixiviation ultérieure à l'acide sulfurique. La vitesse du taux de lixiviation et le taux de lixiviation sont augmentés. De plus, des ressources en minerai de cuivre difficiles à traiter sont efficacement recyclées.
PCT/CN2017/114278 2017-03-09 2017-12-01 Procédé de recyclage combinant valorisation et métallurgie et destiné à un minerai d'oxyde de cuivre à inclusions solides Ceased WO2018161652A1 (fr)

Applications Claiming Priority (2)

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CN201710139134.5 2017-03-09
CN201710139134.5A CN106916944B (zh) 2017-03-09 2017-03-09 一种固体包裹体氧化铜矿选冶联合回收利用的方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114112720A (zh) * 2022-01-11 2022-03-01 合肥工业大学 一种纳米材料辅助微波岩石致裂的室内试验方法
CN117225585A (zh) * 2023-11-13 2023-12-15 昆明理工大学 一种微细粒嵌布硫氧混合铜铅锌矿选矿方法
CN120400553A (zh) * 2025-06-30 2025-08-01 矿冶科技集团有限公司 一种冶炼富铂冰镍的方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106916944B (zh) * 2017-03-09 2018-01-12 昆明理工大学 一种固体包裹体氧化铜矿选冶联合回收利用的方法
CN107971123B (zh) * 2017-11-17 2020-01-10 昆明理工大学 一种铁质包裹型混合铜矿的选冶方法
CN108160311B (zh) * 2017-11-24 2020-01-10 昆明理工大学 一种弱磁性矿物包裹型硫氧混合锌矿的选冶方法
CN109261347B (zh) * 2018-09-05 2020-04-21 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) 一种铅锌冶炼废渣资源化利用的方法
CN109632976B (zh) * 2018-12-29 2021-08-24 紫金矿业集团股份有限公司 金矿加压预氧化氰化渣中金的诊断方法
CN110079680B (zh) * 2019-06-03 2021-07-27 东北大学 一种多种铜赋存状态的复杂氧化铜矿的提铜方法
CN113499855B (zh) * 2021-05-27 2024-05-17 中国地质科学院郑州矿产综合利用研究所 采用微波预处理提高玻璃相煤系废弃物除铁效果的方法

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US8173086B2 (en) * 2009-07-14 2012-05-08 Vale S.A. Process of recovery of base metals from oxide ores
CN104815746A (zh) * 2015-04-09 2015-08-05 湖南有色金属研究院 一种高铁高泥质碱性脉石难处理氧化铜矿的回收方法
CN104988333B (zh) * 2015-08-01 2017-04-05 新兴发展集团有限公司 一种从结合氧化铜矿中回收铜的选冶方法

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CN1668769A (zh) * 2002-05-31 2005-09-14 技术资源有限公司 矿石的微波处理
WO2014074985A1 (fr) * 2012-11-12 2014-05-15 Flsmidth A/S Procédé et traitement pour la lixiviation améliorée de minéraux sulfureux de cuivre contenant de la chalcopyrite
CN103725889A (zh) * 2013-12-16 2014-04-16 金川集团股份有限公司 一种微波辅助浸出冰铜/冰镍浸出渣中铜镍的方法
CN106916944A (zh) * 2017-03-09 2017-07-04 昆明理工大学 一种固体包裹体氧化铜矿选冶联合回收利用的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114112720A (zh) * 2022-01-11 2022-03-01 合肥工业大学 一种纳米材料辅助微波岩石致裂的室内试验方法
CN117225585A (zh) * 2023-11-13 2023-12-15 昆明理工大学 一种微细粒嵌布硫氧混合铜铅锌矿选矿方法
CN120400553A (zh) * 2025-06-30 2025-08-01 矿冶科技集团有限公司 一种冶炼富铂冰镍的方法

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