WO2008003160A1 - Système de récupération de métaux pour lixiviation haute pression de latérites de nickel limoniteuses - Google Patents

Système de récupération de métaux pour lixiviation haute pression de latérites de nickel limoniteuses Download PDF

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Publication number
WO2008003160A1
WO2008003160A1 PCT/CA2007/000916 CA2007000916W WO2008003160A1 WO 2008003160 A1 WO2008003160 A1 WO 2008003160A1 CA 2007000916 W CA2007000916 W CA 2007000916W WO 2008003160 A1 WO2008003160 A1 WO 2008003160A1
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Prior art keywords
nickel
pulp
cobalt
solution
produce
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PCT/CA2007/000916
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English (en)
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WO2008003160A9 (fr
Inventor
Walter Curlook
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Curlook Enterprises Inc.
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Publication date
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Priority to AU2007271672A priority Critical patent/AU2007271672A1/en
Publication of WO2008003160A1 publication Critical patent/WO2008003160A1/fr
Publication of WO2008003160A9 publication Critical patent/WO2008003160A9/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043Sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention is directed at a unique non-conventional method of recovering nickel and cobalt from leach solutions produced by pressure acid leaching limonitic nickel laterite ores in a manner such that the amount of "fresh" water required is minimized and virtually no used process waste waters are discharged to the external environment thereby protecting the external environment from intrusion of extraneous chemical elements and compounds.
  • the conventional acid pressure leaching circuits rely on the use of large quantities of fresh water for make-up water in the preparation of the feed pulp; and of necessity have correspondingly large quantities of so-called barren solutions that need to be disposed of.
  • barren solutions There is a growing objection in many jurisdictions to the disposal of such solutions to the external environment.
  • the practitioner In certain cases where the hydrometallurgical process is being carried out in proximity of the sea, the practitioner has been permitted by the host country to dispose of its process waste waters by discharging into the sea; however, in today's strong focus on protecting the external environment, such practice is not permitted by many jurisdictions.
  • Another disadvantage of the conventional CCD circuit is that barren solution used for washing out of the nickel-cobalt values, must be acidified with acid to maintain a pH low enough so that nickel and cobalt do not precipitate out of solution and be lost to the solid tailings. This excess acid must eventually be neutralized with further limestone additions.
  • the conventional CCD circuit employs at least seven thickener separators to maximize the recovery of nickel and cobalt pregnant solutions at levels of at least 98%. Furthermore, the number of thickeners (solid-liquid separators) required is more or less independent of the throughput rate if one strives for the same degree of nickel and cobalt recovery. Higher throughput rates require either larger thickeners or additional parallel lines.
  • the final tailings and barren solutions need to be neutralized first with limestone followed by treatment with lime to insure low levels of base metal traces in these waters going firstly to a tailings disposal pond, and subsequently the excess process waste waters need to be discharged to the external environment.
  • the present invention relies on the "free" moisture that is inherent in the wet raw limonitic nickel laterite ores which usually contain between about 35% and about 45% H 2 O by weight of the wet ore, and on the use of recycled "mother” liquor emanating from the autoclaves to provide the total make-up water required for pulping the laterite ores.
  • the mother liquor is produced in a dedicated first thickener that separates out a portion of the mother liquor for recycle, while the remainder of the mother liquor and the leached tailings, (together with reverted filtrate and a portion of thickener unflow recycle discussed hereunder), pass onto primary partial neutralization with limestone pulp to pH of about 4.
  • the excess acid in the leach solution is reacted with the limestone to produce gypsum, the iron is precipitated as ferric hydroxide and the aluminum and chromium are also precipitated as hydroxides.
  • a portion of the thickener underflow is recycled to the partial neutralization reactors to provide "seed" materials for the freshly formed precipitates, in order to improve settling and densification of the solids and to enhance subsequent filtration rates.
  • the present invention by employing single-stage filtration instead of a multi-stage CCD circuit, yields a washed tailings filter cake containing all the solid waste compounds, i.e., the leached ore, the iron hydroxide precipitate, the gypsum precipitate and other hydroxide wastes.
  • This composite tailings can be placed in impoundment areas but preferably in mined out areas, with the only outflows of waters being the normal rainfall which can be collected/captured and returned to processing as wash water.
  • the pregnant solutions with their nickel and cobalt values can be recovered by this single-stage filtration at levels equivalent to those achieved by the conventional seven-stage CCD circuits.
  • process of leaching a nickel and cobalt containing predominantly limonitic portion of a laterite ore profile comprising the steps of: a) preparing a feedstock of a predominantly limonitic portion of a laterite ore containing nickel and cobalt; b) pulping said feedstock with a liquid to produce a pulped ore; c) adding an effective amount of sulphuric acid to the pulped ore to produce a sulphuric acid solution, agitating and leaching said feedstock in said sulphuric acid solution at an elevated temperature under pressure for a selected period of time whereby metal oxides are leached from said ore to produce a leach pulp; d) separating said leach pulp into a mother liquor solution and a first thickened leach pulp, wherein said liquid includes a selected amount of said mother liquor solution; e) partially neutralizing said first thickened leach pulp by mixing it with a limestone (calcium carbonate) pulp and
  • FIG. 1 is a block flow diagram of the overall process in accordance with the present invention.
  • Figure 2 is a more detailed mechanical flow diagram showing the steps of the present method
  • Figure 3 is a plot of % nickel recovery versus the number of displacements of cake water (gypsum + iron hydroxide cake) demonstrating the efficacy of the vacuum filtratration mode of recovering nickel values as virtually iron-free pregnant solutions, wherein wash water in amounts of 2 displacements of the liquid in the filter cake, is used.
  • the raw run-of-mine ore is typically passed over a grizzly to reject +25 cm and greater rock boulders, the less than -25 cm ore is then crushed to about -10 cm size and screened at about 6 cm to reject further low-nickel rock material and ore less than 6 cm is passed as feed to the processing plant.
  • This less than 6 cm ore can be trucked, sluiced or pumped to the processing plant site. In the latter two cases a dewatering system would need to be provided with the drained water recycled to the mine site for reuse.
  • the feed preparation in step [2] of Figure 1 could include a further crushing stage ahead of the pulping, screening, grinding and pumping to feed storage tanks ahead of the autoclaves.
  • a feature at this stage is the addition of the recycled mother liquor to make-up the liquid necessary for pulping of the screened and ground ore.
  • This mother liquor is produced in step [4] of the process It is desirable to maintain a pulp density as high as is practical, preferably over 35% and at around 40% but below about 45% solids, in order that the pulp density through the autoclave is maximized for maximum ore throughput rates, recognizing that further dilution will be effected before the ore pulp reaches the autoclave due to water pick up in the direct heat exchange with steam in the feed preheaters.
  • the amount of mother liquor solution used for pulping said feedstock should be sufficient to give the pulped ore a pulp density in a range from about 35% to about 45%.
  • the pulper could effectively be a rubber lined mill, while the following equipment in the feed preparation could be of stainless steel construction.
  • the multi deck screen should pass all minus 48 mesh material onwards to the feed storage tank, the +1 cm coarse could be discarded if it analyzes below about 0.9%Ni, and the minus 1 cm plus 48 mesh intermediate fraction would pass through a hammer mill on the way to the feed storage tank. If the +1 cm fraction assays l% or higher in nickel then it too could be passed through the hammer mill and accepted as feed. (These cut-off levels of 0.9% and 1.0% could vary depending on detailed economic evaluations.) A small quantity of fresh water could be effectively employed to wash the oversized rock fraction on the screen.
  • the resulting feed should be, largely, -100 mesh size and essentially all -48 mesh size. It is self evident to those skilled in the art, that some leaching, particularly of the minor portion of magnesium silicate minerals present in the predominantly limonitic ores, will take place in the pulping stage; and it is further self evident to those skilled in the art that other devices other than a mill can be employed for pugging and pulping of the ore.
  • the acid pressure leaching step in step [3] of Figure 1 may be achieved using the autoclave depicted in Figure 2, which may be a conventional six compartment unit designed to operate at temperatures between 250 0 C and 27O 0 C.
  • the pressure letdown at the discharge end of the autoclave is effected in flash tanks, in three stages shown, although two stages may be adequate, and that the steam thereby produced at three (or two) different temperatures is returned to the feed end of the autoclave for preheating the feed pulp by direct contact and heat exchange with the three (or two) steam streams, in three (or two) separate preheat tanks.
  • the major limonite components are dissolved and reconstituted as hematite, while the minor saprolite components are largely decomposed by the dissolution of the magnesia and liberation of free silica, and in both cases the water of crystallization present in the natural unreacted minerals, which could vary between about 10% and as much as 15%, is also liberated causing further dilution of the pulp in the autoclave.
  • Other solid minerals hosting the nickel, cobalt and manganese are also dissolved along with a high proportion of the alumina and a smaller proportion of the chromite.
  • the acid pressure leaching step involves adding an effective amount of sulphuric acid to the pulped ore to produce a sulphuric acid solution, agitating and leaching the feedstock in the sulphuric acid solution at an elevated temperature under pressure for a selected period of time whereby metal oxides are leached from said ore to produce a leach pulp.
  • the "mother" thickener receives the incoming reacted leach pulp at about 30% solids; but after the decanting of a fraction of the mother liquor for recycle back to step [2] for feed preparation, the remaining portion of mother liquor along with the leached tailings pass as thickener underflow at a pulp density preferably between about 35% to about 40% solids, depending on the amount of mother liquor that is required for pulping of the feed, directly to partial neutralization.
  • this step involves separating the leach pulp into the mother liquor solution and a first thickened leach pulp, wherein the first thickened leach pulp will still include some of the mother liquor solution.
  • the first thickened leach pulp arriving from the mother thickener in step [4] is too dense to accommodate the extra solid products such as gypsum, ferric hydroxide and alumina and chromium hydroxides to be produced upon neutralization. Accordingly, a very significant dilution of the pulp must be effected, and this is accomplished in a number of ways.
  • the neutralizing reagent limestone (calcium carbonate)
  • limestone calcium carbonate
  • a large volume of filtrate containing diluted quantities of nickel and cobalt is reverted from the tailings vacuum filters back to the neutralization reactors for recovery of their metal values shown by the dotted line 20 (from step [7] to back to step [5] in Figure 1)
  • a significant proportion of the tailings thickener underflow is also recycled back to the neutralizing reactors used in step [5] as "seed" material for the fresh precipitates being formed during the partial neutralization, as indicated by solid line 22 on Figure 1.
  • this step involves separating the partially neutralized first leach pulp into a pregnant solution containing sulphates of all extracted metal values and a second thickened pulp in which the second thickened pulp includes a tailings fraction which includes leached ore, precipitated gypsum and precipitated hydroxides of iron and other impurity elements present and pregnant solution, some of which is recycled back as mentioned above (line 22) to be mixed with the first thickened leach pulp limestone pulp and liquid filtrate from step [7] in the partial neutralization step [5].
  • Embodiments of the present process involve using some of the barren solutions of pH of around 8.5 produced in steps [9] and [10] discussed below for producing the limestone (calcium carbonate) pulp for use in this partial neutralization step.
  • the number of neutralizing reactors employed preferably will usually be four (4) in series, to insure efficient consumption of the limestone reagent and to control the pH within narrow limits, of around pH 4.0, so as to insure maximum precipitation of the undesirable dissolved iron while suppressing the precipitation and loss of any nickel and cobalt values to tailings.
  • the solids in the tailings fraction of the second thickened leach pulp are comprised of the leached ore residues, the gypsum, the ferric hydroxide, as well as the hydroxides of aluminium and chromium and the second thickened leach pulp also includes some residual pregnant solution.
  • the present process includes washing the tailings filter cake with the barren solutions produced in steps [9] and [10] (see broken lines 24 and 26 in Figure 1) to produce the liquid filtrate containing residual nickel and cobalt values and separating the washed tailings filter cake from the liquid filtrate which is then recycled back and mixed with the first thickened leach pulp and the limestone (calcium carbonate) pulp in partial neutralization step [5] (indicated by the broken line 20 in Figure 1), thereby virtually obviating the need to dispose of any excess barren solution to the external environment.
  • the liquid phase in the washed tailings filter cake contains dissolved magnesium sulphate and only trace amounts of the base metals such a nickel and cobalt but a significant proportion of the manganese that arrived with the raw ore. Based on laboratory drying tests the solids/liquid contents of the filter cakes usually hover around 50%/50%.
  • the tailings filter cake is a permanent host for the other leached components that had been leached and precipitated.
  • a drum vacuum filter is depicted in Figure 2, other filters such as a pan filter may prove to be more efficient particularly with the washing.
  • step [6] Figure 1
  • steps [6] involve treating the pregnant solution from step [6] ( Figure 1) with precipitating agents to yield barren solution and a third thickened pulp containing precipitated metal values and residual barren solution, followed by separating the third thickened pulp from the barren solution.
  • the metal recovery circuit while receiving and treating large volumes of clear pregnant liquid with precipitating agents, yields but a small amount of solid precipitates. This results in dilute feed to the product thickener usually of less than about 5% solids, and a thickened underflow pulp usually containing around 10% or less of solids. In order to enhance subsequent filtration rates, a portion of the thickener underflow is recycled back to the product precipitation reactors to serve as "seed" materials for the fresh precipitates, see solid line 28 in Figure 1.
  • the number of precipitating reactors is usually greater than two (2), with normally four (4) employed in series.
  • the addition of a flocculent to the product thickener dilute pulp feed, is extremely useful at this stage, to flocculate the relatively small amount of suspended and dispersed solids.
  • several different precipitating agents may be used for recovering the nickel and cobalt values from the pregnant solutions, each being discussed herebelow.
  • the pregnant solution streams pass onto nickel-cobalt precipitation which can render final neutralization of the leach solutions in the cases wherein lime or soda ash are employed as the reagents.
  • magnesia as the precipitating reagent
  • NaHS sodium sulphide
  • further neutralization needs to be carried out on the treated feed liquor, after separation of the nickel-cobalt sulphides as a pulp from the treated feed liquor, to neutralize its acid content and to remove any last traces of nickel and cobalt.
  • Use of sodium sulphide (Na 2 S) would require a minimal amount of further scavenging neutralizing.
  • the scavanged solids containing residual nickel and cobalt values would normally be recycled to the front end of the partial neutralization reactors in step [5].
  • Embodiments of the present process involve using some of the barren solutions of pH of around 8.5 for producing the lime pulp for use in this partial neutralization step.
  • a magnesia pulp as the neutralizing/precipitation agent
  • the reaction is much slower and pH's of 8 and higher are difficult to achieve efficiently.
  • the magnesium sulphate stays largely in solution, and nickel assays of around 35% or slightly higher can be achieved.
  • nickel assays of around 35% or slightly higher can be achieved.
  • after the separation and recovery of the nickel cobalt hydroxides as a pulp from the treated pregnant feed liquor it is generally desirable and may be preferable to subject the treated feed liquor to a final scavenging neutralization step with lime to remove the last traces of nickel and cobalt.
  • the final neutralized barren solution of pH 8.5 or higher could proceed to a clarifier for recovery of the scavenged nickel cobalt hydroxides for recycle to step [5], producing a clarified barren solution for wash water at step [7].
  • the auxiliary equipment for this scavenging step is not shown in Figure 2).
  • Embodiments of the present process involve using some of the barren solutions of pH of around 8.5 for producing the magnesia pulp for use in this partial neutralization step. With a soda ash (NaCO 3 ) pulp being used as the neutralization/precipitating agent, similar higher grades of precipitates of 35%Ni or higher, can be produced, as the sodium sulphate produced stays largely in solution.
  • Embodiments of the present process involve using some of the barren solutions of pH of around 8.5 for producing soda ash (NaCO 3 ) pulp for use in this partial neutralization step.
  • the acid must first be neutralized; and a final scavenging neutralization step must be carried out to raise the pH high enough to remove the last traces of nickel and cobalt from the barren solution, as in the case of precipitation with magnesia.
  • Sodium sulphide reagent would require the simplest circuit, and the higher grade sulphide precipitates could be produced without concomitant production of acid; and final neutralization of the filtrate from the sulphiding circuit, to achieve a pH of 8.5 (or higher) in final barren solutions, can readily be produced with a small addition of lime.
  • the big difference between the three sulphiding techniques are technology/equipment and costs.
  • the pregnant solutions contained between 5 and 6 gpl of Ni, between 0.1 and 0.6 gpl of Co, between 0.3 and 0.5 gpl of Mn, and between 15 and 20 gpl of Fe before partial neutralization, and the iron levels were lowered to between about 1 and 0.1 gpl after the partial neutralization.
  • Figure 3 is a plot of % nickel recovery versus the number of displacements of cake water (gypsum + iron hydroxide cake) demonstrating the efficacy of the vacuum filtratration mode of recovering the soluble nickel values as virtually iron-free pregnant solutions, wherein wash water in amounts of two (2) displacements of the liquid in the filter cake, is used.
  • the present method disclosed herein solves a major problem in this type of metal value recovery in that it greatly reduces the amount of "fresh" water required in preparing the feed pulp from which the metal values are extracted, and obviates the need to dispose of process waste waters to the external environment.
  • the terms “comprises”, “comprising”, “includes” and “including” are to be construed as being inclusive and open ended, and not exclusive. Specifically, when used in this specification including claims, the terms “comprises”, “comprising”, “includes” and “including” and variations thereof mean the specified features, steps or components are included. These terms are not to be interpreted to exclude the presence of other features, steps or components.
  • the foregoing description of the preferred embodiments of the invention has been presented to illustrate the principles of the invention and not to limit the invention to the particular embodiment illustrated. It is intended that the scope of the invention be defined by all of the embodiments encompassed within the following claims and their equivalents.

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Abstract

L'invention concerne un procédé de lixiviation acide sous pression appliqué aux latérites Ni limoniteuses. Une partie de la liqueur mère résultant de la lixiviation acide sous pression est recyclée aux fins d'obtention d'une préparation de pulpes de minerais. La pulpe de lixiviation épaissie est mélangée au filtrat recyclé issu de la filtration des résidus, puis elle est partiellement neutralisée pour être transformée en pulpe partiellement neutralisée, cette dernière étant alors soumise à une opération de filtration en une étape pour obtenir une liqueur mère renfermant des métaux précieux. La liqueur mère est traitée avec un agent de précipitation pour obtenir soit des hydroxydes Ni et Co soit des précipités sulfuriques qui forment un produit intermédiaire Ni/Co ainsi qu'une solution stérile. La solution stérile est recyclée comme eau de rinçage utilisée dans la filtration des résidus après ajustement de son pH autour de 8,5 minimum. Le procédé de l'invention permet d'éviter le circuit classique CCD à opérations multiples, de réduire la quantité d'eau fraîche nécessaire au prétraitement ainsi que la quantité d'eaux usées évacuées, et enfin, de réduire de manière significative la consommation totale d'acide ainsi que la quantité d'agents de neutralisation et de récupération de métaux.
PCT/CA2007/000916 2006-07-03 2007-05-24 Système de récupération de métaux pour lixiviation haute pression de latérites de nickel limoniteuses WO2008003160A1 (fr)

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AU2007271672A AU2007271672A1 (en) 2006-07-03 2007-05-24 Metal recovery system as applied to the high pressure leaching of limonitic nickel laterite ores

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US81770706P 2006-07-03 2006-07-03
US60/817,707 2006-07-03

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WO2009155652A1 (fr) * 2008-06-27 2009-12-30 Bhp Billiton Ssm Development Pty Ltd Procédé de formation de sulfures à haute densité
CN102974455A (zh) * 2012-12-04 2013-03-20 江西稀有稀土金属钨业集团有限公司 浓密逆流洗涤矿浸出渣洗水量的调节系统与方法
EP2924133A4 (fr) * 2012-11-20 2016-08-17 Sumitomo Metal Mining Co Procédé de séparation par décantation de boue neutralisée et procédé de fusion à l'état humide de minerai d'oxyde de nickel
CN109338122A (zh) * 2018-11-06 2019-02-15 广东佳纳能源科技有限公司 一种水钴矿的浸出方法
WO2019049593A1 (fr) * 2017-09-11 2019-03-14 住友金属鉱山株式会社 Procédé de métallurgie par voie humide pour du minerai d'oxyde de nickel
JP2019077928A (ja) * 2017-10-26 2019-05-23 住友金属鉱山株式会社 中和処理方法およびニッケル酸化鉱石の湿式製錬方法
CN110699557A (zh) * 2019-10-23 2020-01-17 金川集团股份有限公司 一种氢氧化镍钴渣低成本处理装置及方法
CN112095005A (zh) * 2020-08-12 2020-12-18 矿冶科技集团有限公司 一种粗制氢氧化镍钴两段浸出镍钴的方法
CN112375916A (zh) * 2020-11-04 2021-02-19 昆明理工精诚技术开发有限公司 一种铜钴湿法冶炼过滤洗涤系统及其作业方式
CN113087430A (zh) * 2021-03-23 2021-07-09 中国葛洲坝集团水泥有限公司 一种提氨脱硫石膏及其处置利用方法

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CN109306403B (zh) * 2018-10-27 2020-05-12 湖南懋天世纪新材料有限公司 金属钨湿法冶炼中季铵盐碱性萃取三相絮凝物的处理方法
CN113528857A (zh) * 2021-06-16 2021-10-22 福建常青新能源科技有限公司 一种从含钴废渣中回收钴的连续化生产方法

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