• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    9COMMUNICATIONS Calcium (Ca), manganese (Mn) and magnesium (Mg) carbonate plus lead (Pb) and Zinc (Zn) sulphide minerals in a permeable host, crushed ore, concentrates as slag are selectively extracted by solution (in situ or ex situ) with a selected acid, e.g. acetic acid, to extract Ca, Mn and Mg followed by oxidizing salts with several valencies, e.g. ferric salts, to extract Pb and Zn sequentially. For in situ leaching, a relationship has been identified between pressure, temperature, target depth and leachate concentration, so that carbonate leaching is carried out in a manner that prevents the escape of carbon dioxide gas (CO 2) which clogs the permeability pathways of the resilient stone and prevents further leaching. This requires control of leaching rate with acetic acid in steps with the presence of solution to dissolve the emitting CO 2. Thereafter, sulphide leaching is performed on the carbonate depleted values. The two resulting leachates are chemically treated to selectively extract extracted minerals in the form of products with added value that are ready for industrial use. The in situ method is particularly advantageous for the preparation of manganese products with a high degree of purity required for lithium ion batteries, since they prevent the presence of small metal particles in the products which may be the case in conventional recovery. Alternatively, the in situ carbonate recovery steps can be used independently, all in an environmentally friendly manner.
    公开号:SE536155C2
    申请号:SE1250178
    申请日:2010-08-17
    公开日:2013-06-04
    发明作者:Robert A Geisler；Madhav P Dahal
    申请人:Yava Technologies Inc；
    IPC主号:
    专利说明:

    535 155 2 particles during the nanometer range to achieve improved properties of its host products due to the reduced size of the calcium material. In some cases, the improvements in the host product have been clear enough to justify a dramatic increase in the price of calcium material. For use as a filler, the main characteristic for the buyer is particle size, uniformity and packing density, which mainly governs functionality.
    Calcium is also used as a soil supplement or fertilizer and, to a lesser extent, in medicines.
    Calcium occurs mainly as calcium carbonate, which is called limestone, or in the form of calcium magnesium carbonate, which is called dolomite.
    Both are marine deposits, usually of considerable size. They are usually mined on a large scale in open pits and the individual components are selectively extracted by mechanical or chemical means.
    The main form of manganese is in the form of manganese oxide (brown stone), MnO 2. Deposits are usually in the form of veins that are extracted by underground mining. Manganese is mainly used as a substation alloy. It is extracted in large pieces, crushed to a usable size and fed together with iron ore into blast furnaces for the manufacture of steel. In this way, it does not require a particularly high price. It is also used in chemistry. However, manganese has recently become increasingly important as the main component in rechargeable batteries used for a growing number of types of industrial, electrical and motor equipment, which extends to car batteries, and has led to a price increase. The desired shape for batteries is in the form of lithium-treated manganese oxide (Li Mn2O4), called LMD.
    The rut can be used and used for this purpose. It is broken down, crushed and dissolved in a solution and extracted electrochemically as electrolytic manganese oxide (EMD). This must then be crushed again and treated with a lithium compound at high temperature to form LMD. This process is complicated and costly. In addition, it has been found that the resulting LMD often contains small metal particles which could obviously short-circuit batteries made therefrom. The particles cannot be removed electromagnetically, nor can their presence be fully identified by means of a scanning electron microscope (SEM). The solution to the problem so far has been to test all 535 'H55 3 new batteries with LMD and discard those found to be unsuitable. Alternatively, your treatment steps can be performed to purify MnO 2 as a precursor material.
    We have to our surprise found that manganese in the form of carbonate veins, which cannot be normally mined economically but which exists geologically, with sufficient permeability can advantageously be extracted by in situ leaching (ISLM) as leachate produces LMD with high purity . Such a solution is free of metal particles, as it does not involve conventional mining or crushing and thus can cause problems with electrical short circuits in batteries in which it is used. In addition, the presence of calcium carbonate with the manganese that normally occurs in such contexts allows for its and manganese extraction, which thus further improves the economy of the process.
    A patent search resulted in two methods, one proposed by Geisleri US5523066 and the other by Turner in US6726828, which describes the use of ISLM where a mixture of acetic acid and hydrogen peroxide (for sulfide oxidation) is used to recover Ca, Mn, Pb and Zn as a combined leachate from a permeable geological host material. Both methods are dependent on a separate oxidant (ie peroxide) and do not take any precautions against the increasing blockage of fl channels of destiny below the surface which prevents further leaching. None of these methods indicate what is proposed herein.
    Another observed patent (US4500398) treats sulphide ore with silicic acid and an oxidizing agent to release the metals.
    SUMMARY OF THE INVENTION The invention comprises a process for leaching minerals from ore with metal carbonate and metal sulphide components, comprising: leaching the carbonates with an acidic leaching agent selected to dissolve the carbonates but not the sulphides at a rate to avoid the release of CO2 gas in situ, and then leach the sulphides with an oxidizing leaching agent to dissolve the sulphides, followed by selective recovery of desired metals from the individual leachates.
    The particles from the ore may include crushed ore, ore concentrate and slag products. 535 155 4 Different acids can be selected for step a) Detergents, e.g. acetic acid, formic acid, nitric acid, sulfuric acid, hydrochloric acid, fluorosilicic acid and fluoroboric acid.
    For step b), the oxidizing leaching agent comprises a selected salt of a metal having fl your valence states and which is in the highest valence state.
    Preferred salts for step b) are oxidizing Iakmede | which includes iron (III) fluorosilicon, iron (III) fluoroborate, iron (|) sulphate and iron (III) nitrate.
    Leaching step b) has been found to be more effective if a rinsing step is inserted between steps a) and b).
    In general, the invention comprises the carbonate leaching from an ore body by means of acid (independent of the sulphide leaching), which is controlled to a leaching rate which avoids the release of CO 2 gas in the ore body and maintains the permeability of the ore. The leaching rate is controlled by regulating the pressure, temperature and acid concentration of the leaching agent to achieve a leaching rate during which CO 2 gas begins to be released. This has been shown to maintain the permeability of the ore body. The limit value for the release of CO 2 gas can be obtained by comparing the gas dissolved in the leachate with the maximum solubility at temperatures and pressures occurring below the ground surface.
    DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS In one embodiment, Ca, Mn and Pb (in sulfide form) are recovered from a carbonate host containing the same using two-step ISL mining techniques well known to one skilled in the art. Ca and Mn are initially extracted by means of leaching with dilute acetic acid. After completion of this step, the source area leached with water is rinsed to remove all traces of acetic acid and the deposit is leached again with iron (III) fl uorkise | solution to recover the remaining Pb. The chemical reactions of two successive leaching steps are hereinafter referred to as (A) and (B). 535 155 INITIAL Leaching (A) (A) Carbonate leaching reactions Calcium and manganese carbonates react with the acetic acid lacquer to form soluble calcium and manganese acetate.
    CaCO 3 + 2CH 3 COOH = (CH 3 COO) 2 Ca + CO 2 + H 2 O MFICO 3 + 2CH 3 COOH = (CH 3 COO) QMH + CQQ + H 2 O (A) Calcium recovery reactions Calcium is selectively precipitated from the leachate, which consists of a mixture of manganese and calcium acid . This is possible because calcium sulphate is insoluble while manganese sulphate is a soluble compound.
    This step also regenerates the Iakmedlet (acetic acid). Calcium sulphate is then converted to precipitated calcium carbonate by reacting it with ammonium carbonate. Ammonium sulphate is produced as a by-product with a high degree of purity during this process.
    (CH3COO) 2Ca + H2SO4 = CaSO4 + 2CH3COOH C8SO4 + (NH4) 2CÛ3 = C8CO3 + (NH4) SO4 (A) Manganese recovery reactions Leachate where calcium has been removed and which consists mainly of manganese acetate is treated with potassium manganese manganese oxides for attan manganese permanganate. The manganese dioxide thus obtained can be used as a precursor material for the production of lithium-treated manganese dioxide by heating it together with lithium carbonate at elevated temperature. Manganese can also be extracted selectively by liquid extraction. sivln ”+ zkivlno., + 2H2o _» 5Mno2 + 4H * + zk * The regenerated lacquer is injected underground and forms a closed process.
    Subsequent leaching (B) (B) Lead leaching reaction using iron (III) fluorosilicate leaching agent Fe2 (SlF6) 3 + PbS -> 2FeSiF6 + PbSiF fi + S 536 155 6 In a preferred embodiment, lead is recovered as a lead metal with a high degree of purity by electroconvulsive the resulting leachate. The electro-extraction process regenerates the original leaching agent by oxidizing ferrous orsorosilicate to iron (lll) flsorilicate at the anode and the iron (| il) floorsilicate is recovered for recycling.
    权利要求:
    Claims (13)
    [1]
    A process for leaching minerals from a permeable ore body or from particles from ore, wherein the ore has metal carbonate and metal sulphide components, comprising: a) first leaching the carbonates with an aqueous leaching agent comprising an acid selected to dissolve the carbonates but not the sulphides , while the leaching rate, for in situ ore, is controlled to avoid the release of CO 2 gas in the ore body; b) leaching the sulphides with an aqueous leaching agent comprising a metal salt having several valencies and ability to oxidize the salts to soluble oxidation products; and c) recovering desired metals from separate leachate.
    [2]
    A method according to claim 1, wherein the leaching steps are performed in situ in a permeable ore body.
    [3]
    A method according to claim 2, wherein the leaching rate in step a) is controlled by controlling the pressure, temperature and concentration of the leaching agent to avoid the release of CO 2 gas in situ.
    [4]
    The method of claim 3, wherein the in situ leached layer is rinsed between steps a) and b) to remove residual acid lacquer agent from step a).
    [5]
    A method according to claim 1, wherein the leaching steps are performed on particles from ore of the types: crushed ore, ore concentrate and slag.
    [6]
    A process according to any one of claims 1 to 5, wherein the acid component of the leaching in step a) is selected from acetic acid, formic acid, nitric acid, sulfuric acid, hydrochloric acid, flboronic acid and florsilicic acid. 10 15 20 25 30 536 155 8
    [7]
    A process according to claim 6, wherein the acid in step a) is acetic acid and the metals recovered by the leaching in step a) comprise manganese, calcium and magnesium.
    [8]
    A process according to any one of claims 1 to 7, wherein the saline leaching agent in step b) is an aqueous solution of a salt of a metal having fl your valence states and which is in the highest valence state.
    [9]
    A method according to claim 8, wherein the metal is primarily selected from Fe-containing compounds.
    [10]
    The method of claim 8, wherein the solvent in step b) comprises a ferric salt selected to oxidize any salts present.
    [11]
    A process according to claim 10, wherein the ferric salt is at least one of orssorilicate, fluoroborate, sulphate and nitrate, and the metals recovered mainly comprise lead and zinc.
    [12]
    A process for leaching permeable ore bodies containing metal carbonate with acidic leaching agent, the method comprising: controlling the pressure, temperature and acid concentration of the leaching agent to control the leaching rate to a rate that avoids the release of CO 2 gas in the ore body, and maintains the ore body permeability. .
    [13]
    A method according to claim 12, wherein the limit value for the release of CO 2 gas is determined by the maximum solubility of the gas in the leachate at the temperature corresponding to the ground and the pressure and leaching rate are controlled so that dissolved CO 2 is below this limit value.
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    同族专利:
    公开号 | 公开日
    US20120177551A1|2012-07-12|
    SE1250178A1|2012-02-28|
    RU2553106C2|2015-06-10|
    MX2012001928A|2012-05-08|
    RU2012110295A|2013-09-27|
    CA2676273A1|2011-02-19|
    CN102597278A|2012-07-18|
    WO2011020181A1|2011-02-24|
    PL218920B1|2015-02-27|
    PL399142A1|2012-11-19|
    AU2010283920A1|2012-04-05|
    CN102597278B|2014-08-20|
    PE20121371A1|2012-10-07|
    CA2770367A1|2011-02-24|
    AU2010283920B2|2014-10-30|
    US8454915B2|2013-06-04|
    引用文献:
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    CN108842066A|2018-08-24|2018-11-20|淄博淦达环保科技有限公司|A kind of leaching liquid and extract technology of lead|
    WO2021116742A1|2019-12-13|2021-06-17|Scarab Chile Spa|Method for obtaining an alkaline earth metal compound|
    法律状态:
    2016-03-29| NUG| Patent has lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    CA2676273A|CA2676273A1|2009-08-19|2009-08-19|Leach recovery of minerals from composite carbonate/sulfide ores|
    PCT/CA2010/001263|WO2011020181A1|2009-08-19|2010-08-17|Selective leach recovery of minerals from composite ores|
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