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WO2008101414A1 - Procédé permettant d'extraire des métaux à partir de latérite - Google Patents

Procédé permettant d'extraire des métaux à partir de latérite Download PDF

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Publication number
WO2008101414A1
WO2008101414A1 PCT/CN2008/000355 CN2008000355W WO2008101414A1 WO 2008101414 A1 WO2008101414 A1 WO 2008101414A1 CN 2008000355 W CN2008000355 W CN 2008000355W WO 2008101414 A1 WO2008101414 A1 WO 2008101414A1
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WO
WIPO (PCT)
Prior art keywords
sulfur
cobalt
nickel
laterite ore
group
Prior art date
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Ceased
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PCT/CN2008/000355
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English (en)
Chinese (zh)
Inventor
Tong Deng
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Individual
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Individual
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Application filed by Individual filed Critical Individual
Priority to AU2008217468A priority Critical patent/AU2008217468B2/en
Publication of WO2008101414A1 publication Critical patent/WO2008101414A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • 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
    • C22B1/02—Roasting processes
    • C22B1/06—Sulfating roasting
    • 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof

Definitions

  • the present invention generally relates to a method of extracting metals from ore. More specifically, the present invention relates to a method of extracting nickel, cobalt and other metals from laterites.
  • Laterite ore is a mixture of hydrated iron oxide and hydrated magnesium silicate formed by long-term large-scale weathering leaching and alteration of basic rocks such as olivine or serpentine. It is a loose clay-like nickel oxide containing a large amount of water. Mineral resources, easy to mine, difficult to process. At present, the available parts of laterite ore are generally divided into three layers: the limonite layer, the saprolite layer and the transition layer between the two. The chemical composition of laterite ore varies not only from mineral deposit, but even the same deposit, its content of nickel, cobalt, iron, magnesium, etc. varies with the depth of the deposit, which increases the difficulty and cost of processing the laterite ore.
  • laterite ore can be treated by pyrometallurgical or hydrometallurgical methods.
  • leaching which not only requires the full dissolution of valuable metals such as nickel and cobalt, but also avoids impurities, especially iron, and enters the solution in large quantities.
  • the hydrometallurgical methods currently used in the industry to treat laterite ore are only the Caron method (reduction roasting-ammonia leaching method) and the HPAL method (high-pressure acid leaching method), which both better control the iron in the leaching of nickel and cobalt. Dissolved.
  • the Caron method combines pyrometallurgy with hydrometallurgy to first calcine the ore in a reducing atmosphere to selectively reduce nickel in the ore to metallic nickel and iron to Fe 3 0 4 as much as possible.
  • the baking is leached by ammonia medium. , to avoid the entry of iron and magnesium into the solution.
  • the nickel and cobalt in the Caron leaching solution are greatly lost due to the adsorption of the leaching residue, and the metal recovery rate is not high.
  • the nickel recovery rate is only 70% - 80%, and the cobalt recovery rate is even below 40%.
  • the Caron method needs to dry the ore before calcination. Since the laterite ore usually contains 30% - 50% of adsorbed water, the drying operation can be high. Therefore, although the Caron method is the earliest industrial application of the laterite hydrometallurgical method, it is now losing its competitiveness.
  • Sulfuric acid can effectively leaching nickel and cobalt directly from laterite ore, avoiding high-energy drying and reduction roasting operations, and the sulfuric acid is cheaper, but direct leaching with sulfuric acid under normal pressure Without selectivity, the iron in the ore is also almost all 3 ⁇ 4 V solution.
  • the dissolution of iron is controlled, and the high pressure acid leaching method is at 250.
  • the temperature of C (the vapor pressure is about 50 atmospheres) leaches the laterite ore with dilute sulfuric acid, and uses the hydrolysis reaction of iron at high temperature to precipitate iron into hematite and release sulfuric acid, which solves the problem of iron removal in solution and also reduces Acid consumption.
  • the high-pressure acid leaching method was once the preferred technology for the treatment of laterite ore.
  • the high investment and high energy consumption of the method requires that the material of the reactor can withstand corrosion, pressure and sealing at high temperatures, and the manufacturing process and operation technology requirements.
  • Sulfation roasting or selective oxidative roasting is an effective method for pretreating refractory ore in hydrometallurgy by controlling the temperature of roasting ore in an oxidizing atmosphere to bury copper, cobalt and nickel in the ore.
  • the non-ferrous metal compound is converted into a water-soluble sulfate, and the iron is converted into iron-insoluble iron oxide, so that it is easy to dissolve the nickel, cobalt, copper and the like sulfate by water in the subsequent leaching operation.
  • To the leachate iron remains in the leach residue. This method has been successfully used to treat sulfide ore, but oxidized ore cannot be directly subjected to sulphation roasting due to the lack of sulfur in its composition.
  • JH Canterford JH Canterford, The sulphation of oxidized nickel ores, Paper presented at the International Laterite Symposium, New Orleans, Louisiana, Feb. 19 - 21, 1979
  • the sulphuric acid roasting or the sulphur dioxide-air roasting laterite ore can achieve sulphation roasting, achieving the purpose of selectively leaching nickel, cobalt and controlling iron dissolution.
  • both methods require external fueling to heat the entire material, typically to 600. Above C, energy consumption is high, which is in energy shortage. The period of rising fuel prices is particularly undesirable.
  • the sulfuric acid needs to be supplied with sulfuric acid on-site or self-built sulfuric acid plant.
  • the use of sulfur dioxide needs to be close to the sulfide ore fire smelter produced by sulfur dioxide flue gas, which is inconvenient to operate and difficult to implement.
  • both roasting methods require a flue gas collection and absorption device to treat the sulfur oxides emitted from the flue gas of the roaster.
  • the present invention provides a method for extracting metals from a laterite ore containing nickel and cobalt, comprising:
  • the invention further relates to a method of calcining a laterite ore containing nickel and cobalt comprising mixing a laterite ore with a sulfur-containing material selected from the group consisting of elemental sulfur and a metal sulfide, and the resulting mixture is calcined in an oxidizing atmosphere.
  • the laterite ore is first mixed with a sulfur-containing substance selected from the group consisting of elemental sulfur and a metal sulfide, and the resulting mixture is calcined in an oxidizing atmosphere to obtain a result.
  • the metal in the calcine is converted to the respective sulfate and the iron is converted to an oxide.
  • the laterite ore may be limonite, sulphate or a mixture of the two.
  • the sulfur-containing material selected from the group consisting of elemental sulfur and metal sulfide is selected from the group consisting of sulfur and ores, concentrates or the like containing nickel, cobalt or other iron and non-ferrous metal sulfide minerals.
  • Materials such as nickel, cobalt sulfide precipitated from ore processing, antimony, etc.
  • Sulfide minerals containing nickel, cobalt or other metals such as chalcopyrite, chalcopyrite, copper blue, pyrrhotite, cobalt pyrite, pentlandite, pyrite and sphalerite.
  • the elemental sulfur and the metal sulfide may be used in combination or may be used singly.
  • the mixture of laterite ore and a sulfur-containing substance selected from the group consisting of elemental sulfur and metal sulfide is further added with a substance selected from the group consisting of alkali metal and alkaline earth metal sulfates, in particular sodium sulfate and One of magnesium sulfate, especially sodium sulfate.
  • the laterite ore is further added with sulfuric acid in a mixture of sulfur-containing materials selected from the group consisting of elemental sulfur and metal sulfides.
  • the total amount of sulfur contained in the sulfur-containing material selected from the group consisting of elemental sulfur and metal sulfide is the dry basis of all the to-be-calcined mixture (including laterite ore, selected from elemental sulfur and metal sulfide). 5 to 35 wt%, preferably less than 30 wt%, particularly preferably between 10 and 20 wt%, of the sulfur-containing material of the substance, and possibly the alkali metal and alkaline earth metal sulfates and sulfuric acid, etc. .
  • the calcination temperature is from 400 Torr to 850, preferably from 450 to 750*, especially from 600 C to 700* Torr.
  • a sulfur-containing substance selected from the group consisting of elemental sulfur and metal sulfide is mixed into the laterite ore, and when calcined, they are both a sulfating agent and a fuel.
  • the sulfur-containing material provides sulfur required to convert nickel and cobalt oxides in the laterite ore to sulfate, and excess sulfur can also be formed in situ from the flue gas.
  • the sulfur-containing substance can be used as a fuel, and a large amount of heat energy generated by oxidation of sulfur or sulfide is supplied to the ore for roasting without additional fuel.
  • the heat of oxidation of pyrite can be up to 12884 kJ/kg. It can not only realize the self-heating of the roasting operation, but also use the waste heat boiler to generate waste heat. Therefore, a method of separately calcining a sulfur-containing substance selected from elemental sulfur and metal sulfide to produce sulfur dioxide or sulfuric acid, and then calcining the laterite ore to convert nickel and cobalt therein to sulfate and iron to oxide In comparison, the method of the invention is clearly more economical and simple.
  • the calcination of the laterite ore and a mixture of sulfur-containing substances selected from elemental sulfur and metal sulfides is carried out in an oxidizing atmosphere.
  • the oxidizing atmosphere may be a mixed gas containing oxygen, particularly air, or an oxygen-enriched air mixture.
  • the proportion of oxygen is 20 - 35 vol%, preferably 20 - 30 vol%, particularly preferably 20 - 25 vol%, especially 20 vol% (i.e., directly using air) of the gas mixture.
  • the calcination time is from 0.5 to 5 hours, preferably from 1 to 3 hours.
  • the specific time varies depending on the specific conditions of the mixture of laterite ore and a sulfur-containing substance selected from the group consisting of elemental sulfur and metal sulfide, and it is easy for a person of ordinary skill to determine the time required by the present disclosure.
  • the laterite ore and the baking auxiliary can be uniformly mixed and directly fed into the baking furnace without prior drying.
  • this feature of the present invention is greatly reduced compared to methods requiring pre-drying, such as various pyrometallurgical methods for laterite ore and Caron for hydrometallurgy. Energy consumption.
  • non-ferrous metals such as nickel, cobalt, copper and the like are mainly present in the form of sulfate, iron. It mainly exists in the form of oxide, which is beneficial to the dissolution of nickel, cobalt and copper in the subsequent leaching operation and the control of iron in the leaching solution.
  • the extraction rate of nickel and cobalt can exceed 90%, and the dissolution of iron can be controlled below 3%.
  • nickel, cobalt and copper contained in the sulfur-containing substance are also converted into respective sulfates, and the sand is leached.
  • the nickel and cobalt contained in the laterite ore are leached together and subsequently recovered from the leachate.
  • the calcination obtained by the calcination step of the process of the present invention is leached with water, and nickel and cobalt and other non-ferrous metals such as copper are extracted into the leachate.
  • the leaching temperature is from 30 ° C to 95 ° C for 0.5 - 3 h.
  • the leaching water is added with or without an acid such as sulfuric acid, hydrochloric acid or the like, but sulfuric acid is preferably added. When sulfuric acid is added, it is preferred that the free sulfuric acid remaining in the leachate is less than 30 g/L.
  • nickel and cobalt, and other non-ferrous metals such as copper are recovered from the leaching solution which is separated from the obtained leached ore slurry.
  • the recovery of nickel, cobalt and copper from the leachate is carried out by a method selected from the group consisting of a precipitation method, a solvent extraction method or an ion exchange method, which are themselves well known to those skilled in the art.
  • the present invention also provides a method of calcining a laterite ore containing nickel and cobalt, comprising mixing a laterite ore with a sulfur-containing substance selected from the group consisting of elemental sulfur and a metal sulfide, and the resulting mixture is calcined in an oxidizing atmosphere.
  • a sulfur-containing substance selected from the group consisting of elemental sulfur and a metal sulfide
  • the sulfur-containing substance, the calcination conditions and the like are described in the calcination step in the above-described method of the present invention, and will not be described herein.
  • the product of the baking method of the present invention i.e., calcine, can be used for further processing, extraction of metal materials therefrom, etc. or for other uses.
  • the laterite ore containing (dry basis) 1.43% Ni, 0.041% Co, 21.43% Fe, 9.06% Mg and 35.43% moisture is finely ground to 90% over 74 ⁇ m sieve and divided into two parts, one part by weight with sulfur: 1 After mixing evenly, directly into the roaster (Test I); the other is mixed with 5 wt% (on a mineral weight basis) of concentrated sulfuric acid while mixing with sulfur at a weight ratio of 4:1, and then fed to the roaster. (Test 11). Both Test I and Test II were fired at 500 ° C for 1 h in an air atmosphere. The calcine was directly discharged from the furnace into the stirring leaching tank and leached for 2 hours.
  • the leaching temperature in the tank can reach 80. Above C.
  • the leached slurry was separated into solid and liquid.
  • the leaching rates of the two tests of nickel and cobalt were respectively calculated as Ni 90.32%, Co 93.33%, Fe 3.13% (test I); Ni 90.48% Co 93.60%, Fe 2.99% (Test 11). It can be seen that the present invention can effectively extract nickel and cobalt in laterite ore and control the dissolution of iron, and also reflects whether or not sulfuric acid is mixed in the laterite ore, and has no significant effect on the leaching result.
  • Example 1 The laterite ore of Example 1 was uniformly mixed with a cobalt-copper concentrate containing 1.62% Cu, 0.58% Co > 0.36% Ni and 28.55% S, and a weight ratio of 4:1:1.
  • the main useful minerals of the cobalt-copper concentrate are chalcopyrite, pyrite and cobalt pyrite.
  • the obtained mixture was calcined at 650 ° C for 2 h in an air atmosphere, and the calcination was carried out in the same manner as in Example 1 to obtain nickel, cobalt and copper leaching rates of Ni 89.95%, Co 94.02% and Cu 95.67%, respectively.
  • the laterite ore containing 1.85% Ni, 0.053% Co and 48.2% moisture is finely ground to 90% over 74 ⁇ sieve and divided into two parts, each containing 1.26% Ni, 0.50% Cu, 0.033% Co, 22.76% S and 46.68%.
  • the pyrrhotite concentrate of Fe is uniformly mixed in a weight ratio of 1:1, one part is directly fed into the roaster (test I); the other part is further added with 5 wt% (based on the weight of the aforementioned mixture) of sodium sulfate and then fed to the roasting Furnace (test 11).
  • the minerals contained in the pyrrhotite concentrate include pyrrhotite, pentlandite, chalcopyrite and pyrite.

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

Abstract

L'invention concerne un procédé permettant d'extraire des métaux à partir de latérite contenant du Ni et du Co. Ce procédé consiste à : (1) mélanger la latérite avec une matière contenant du soufre sélectionnée parmi du soufre élémentaire et du sulfure métallique; calciner le mélange obtenu dans une atmosphère oxydante de sorte à convertir les métaux non ferreux du mélange en sulfates de ceux-ci et à convertir le fer en oxyde; (2) lixivier les matières calcinées avec de l'eau, de sorte à extraire le Ni et le Co de ces matières pour obtenir une liqueur lixiviante. Un procédé de l'invention permettant de calciner de la latérite contenant Ni et du Co consiste à : mélanger la latérite avec une matière contenant du soufre sélectionnée parmi du soufre élémentaire et du sulfure métallique; et calciner le mélange obtenu dans une atmosphère oxydante.
PCT/CN2008/000355 2007-02-15 2008-02-15 Procédé permettant d'extraire des métaux à partir de latérite Ceased WO2008101414A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2008217468A AU2008217468B2 (en) 2007-02-15 2008-02-15 A process for extracting metals from laterite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200710079305.6 2007-02-15
CN2007100793056A CN101245414B (zh) 2007-02-15 2007-02-15 从红土矿提取金属的方法

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CN (1) CN101245414B (fr)
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CN101787439B (zh) * 2010-03-02 2011-12-14 邓彤 一种从冶金废料中回收有价金属的方法
CN102154545B (zh) * 2011-05-26 2012-11-28 中国地质科学院矿产综合利用研究所 一种低冰镍高温氧压水浸工艺
US8597601B2 (en) * 2011-06-03 2013-12-03 Vale S.A. Selective base metals leaching from laterite ores
CN102220483B (zh) * 2011-06-08 2013-03-06 广西银亿科技矿冶有限公司 一种二段焙烧处理红土镍矿的方法
CN103937963B (zh) * 2014-04-24 2016-08-24 中国恩菲工程技术有限公司 红土矿焙烧方法
CN103952539B (zh) * 2014-04-24 2016-08-17 中国恩菲工程技术有限公司 红土矿焙烧系统
CN104164557B (zh) * 2014-09-05 2016-05-11 合肥工业大学 一种黄铁矿和褐铁矿混合焙烧制备以磁黄铁矿为主要物相的多孔结构材料的方法
CN105112676B (zh) * 2015-09-09 2018-03-30 中南大学 一种黄铁矿焙烧铁橄榄石类冶金废渣回收铁的方法
CN105907949A (zh) * 2016-05-14 2016-08-31 北京矿冶研究总院 一种从红土镍矿中低温酸化酸解综合回收镍钴铁的新工艺
CN106086467B (zh) * 2016-08-09 2018-08-28 江苏省冶金设计院有限公司 一种利用红土镍矿提取氧化镍的方法及系统
CN106119573B (zh) * 2016-08-09 2018-08-28 江苏省冶金设计院有限公司 一种利用红土镍矿提取氧化镍的方法及系统
CN106086469B (zh) * 2016-08-09 2018-08-28 江苏省冶金设计院有限公司 一种利用红土镍矿提取氧化镍的方法及系统
CN106086468B (zh) * 2016-08-09 2018-08-28 江苏省冶金设计院有限公司 一种利用镍铁粉提取氧化镍的方法与系统
CN107236867A (zh) * 2017-05-15 2017-10-10 中国恩菲工程技术有限公司 从铁质红土矿浸出镍、钴元素的方法
EP3587599A1 (fr) * 2018-06-29 2020-01-01 Vito NV Procédé de récupération de métaux non ferreux à partir de résidus minéraux industriels
AU2019222783B2 (en) * 2018-09-04 2021-05-13 Linico Pty Ltd A metallurgical extraction method for co-processing laterite ores and sulphide concentrates
CN109609754B (zh) * 2019-01-10 2021-03-30 江西新金叶实业有限公司 一种贵金属提取过程产生的废物回收工艺
CN110255630B (zh) * 2019-07-24 2021-10-08 东北大学秦皇岛分校 一种多金属盐溶液制备金属氧化物复合材料的方法
CN112095004A (zh) * 2020-11-09 2020-12-18 矿冶科技集团有限公司 铁锰多金属氧化矿中提取有价金属的方法和有价金属溶液

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GB101285A (en) * 1915-08-24 1917-05-10 Frederic Augustus Eustis Improvements in the Treatment of Nickel Ores.
JPS4913129B1 (fr) * 1970-06-26 1974-03-29
US4328192A (en) * 1980-04-14 1982-05-04 Uop Inc. Ammoniacal nickel leach of laterites
US4594102A (en) * 1983-03-29 1986-06-10 Sherritt Gordon Mines Limited Recovery of cobalt and nickel from sulphidic material
RU2267547C1 (ru) * 2004-11-16 2006-01-10 Дмитрий Борисович Басков Способ извлечения никеля и кобальта из никелевых руд
RU2285732C1 (ru) * 2005-04-25 2006-10-20 Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный горный институт имени Г.В. Плеханова (технический университет)" Способ сульфатизации кобальта
CN1676634A (zh) * 2005-06-03 2005-10-05 北京矿冶研究总院 一种镍钴氧化矿加压氧化浸出法

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CN101245414B (zh) 2011-12-21
CN101245414A (zh) 2008-08-20
AU2008217468A1 (en) 2008-08-28
AU2008217468B2 (en) 2011-02-03

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