CN107475511A - It is a kind of by low nickel matte calcification baking acidleach high efficiency extraction nickel, copper, cobalt method - Google Patents

It is a kind of by low nickel matte calcification baking acidleach high efficiency extraction nickel, copper, cobalt method Download PDF

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Publication number
CN107475511A
CN107475511A CN201710574121.0A CN201710574121A CN107475511A CN 107475511 A CN107475511 A CN 107475511A CN 201710574121 A CN201710574121 A CN 201710574121A CN 107475511 A CN107475511 A CN 107475511A
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Prior art keywords
nickel
copper
cobalt
matte
roasting
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CN107475511B (en
Inventor
耿淑华
鲁雄刚
赵勇
程红伟
李光石
路长远
许茜
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B15/0002—Preliminary treatment
    • C22B15/001—Preliminary treatment with modification of the copper constituent
    • C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
    • C22B15/0015—Oxidizing 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
    • 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
    • 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
    • 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
    • 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
    • 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

Abstract

The present invention relates to it is a kind of by low nickel matte calcification baking acidleach high efficiency extraction nickel, copper, cobalt method, belong to green metallurgical technology field.It is a kind of by low nickel matte calcification baking acidleach high efficiency extraction nickel, copper, cobalt method, there are following steps：By lime powder and low nickel matte powder（Less than 200 mesh）It is in mass ratio（1~2）：1 is well mixed, and the material after mixing is placed in crucible, open, then in certain temperature 500 1100oIn 13 h of roasting in resistance furnace under C；After the corresponding time is calcined, room temperature is rapidly cooled to, calcining is placed in beaker, adds the mL of dilute sulfuric acid 100 that concentration is 2 mol/L, heating stirring leaches, and filters mixture after 1 h, that is, obtains rich in nickel, copper, the leachate of cobalt, can be used as extracting nickel, copper, cobalt；Can be as the raw material for producing gypsum after filter residue drying.Compared to traditional thermal process, simplification of flowsheet, reduce valuable metal（Especially cobalt）Loss, and due to the sulfur fixation of calcium oxide, SO can be reduced2Discharge, is advantageous to environmental protection.

Description

It is a kind of by low nickel matte calcification baking-acidleach high efficiency extraction nickel, copper, cobalt method
Technical field
The present invention relates to it is a kind of by low nickel matte calcification baking-acidleach high efficiency extraction nickel, copper, cobalt method, belong to greenization Learn technology field.
Background technology
Low nickel matte is intermediate product of traditional pyrometallurgy using valuable metals such as copper-nickel concentrate extraction nickel, copper, cobalts, high-precision The sulfide eutectic of ore deposit shape richness nickel, copper, cobalt after the techniques such as matte smelting, i.e. low nickel matte, low nickel matte is again after bessemerizing Converter mattes are obtained, converter mattes are obtaining the final products such as nickel, copper through techniques such as overground floating separation, and technical process is numerous and diverse, and valuable Metal loss is larger, especially bessemerizes to obtain high nickel matte process, can more lose substantial amounts of metallic cobalt, cause the wave of resource Take.Traditional pyrometallurgical processes can also produce a large amount of sulfur dioxide, pollute environment.
For low nickel matte relative to high concentrate, metal target enrichment of element is less relative to converter mattes valuable metal element loss, Therefore technological process can be shortened by metallic elements such as object extraction nickel, copper, cobalts of low nickel matte, save energy consumption, it is dirty to reduce environment Dye.
The A of Chinese patent CN 102206834 disclose a kind of method that electrolytic nickel is directly produced using low nickel matte, by low ice After nickel preimpregnation of pulp, autoclave pressure leaching is placed into, input can be reduced, is saved intensity and the time of work, but is reacted Process needs to pressurize and logical oxygen, to equipment requirement height.、
The A of Chinese patent CN 102154545 disclose a kind of low nickel matte high-temperature oxygen pressure water leaching process, by low nickel matte by ore grinding Reason, low nickel matte and water are then uniformly mixed into ore pulp, ore pulp is put into autoclave and carries out high temperature oxygen pressure water logging, leaching terminates Afterwards, separation of solid and liquid, and using conventional extraction separation method separation copper, cobalt and nickel.The technique carries relative to traditional pyrometallurgy The high rate of recovery of cobalt, at the same also solve in the prior art using the oxygen pressure acid-hatching of young eggs present in environmental pollution serious problems. But still belonging to needs high pressure, logical oxygen, and high to equipment requirement, recovery rate of valuable metals is not high.
The A of Chinese patent CN 105177307 disclose a kind of method of the floating separation and recovery Cu, Ni and Co of low nickel matte mill, including will Low nickel matte, which carries out grinding floating separating treatment, obtains copper-bearing mineral and nickeliferous iron-bearing mineral, the copper-bearing mineral is smelted copper production is made Product, cobalt product, the nickeliferous iron-bearing mineral is smelted iron product, nickel product and cobalt product is made.Although the technique can also be reduced The loss to valuable metal, but complex technical process are bessemerized in traditional pyrometallurgy, and course of reaction control requires high.
The content of the invention
The defects of existing for prior art, it is an object of the invention to provide a kind of low nickel matte calcification baking-acidleach is efficient Nickel, copper, the method for cobalt are extracted, energy simplification of flowsheet, the loss of valuable metal is reduced, efficiently using resource, and due to calcification Roasting has sulfur fixation, can reduce environmental pollution.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
The present invention it is a kind of by low nickel matte calcification baking-acidleach high efficiency extraction nickel, copper, cobalt method, it is characterised in that have it is as follows Process and step：
A. it is by certain mass ratio with low nickel matte by calcium oxide（1~2）：1 ratio is well mixed, low to make it fully react Ice nickel answers the levigate mesh of mistake 200；
B. mixed material is placed in crucible, it is open, then in certain temperature 500oC-1100 oUnder C, in resistance furnace It is calcined 1-3 h；
C. after the completion for the treatment of material roasting, sampling is cooled to room temperature；
D. the calcining after cooling being placed in beaker, the concentration for adding certain volume 50-150 ml is 2 mol/L dilute sulfuric acid, Beaker is placed on magnetic stirring apparatus and leached；Temperature is 90oC, extraction time 1-2 h；
E. after the completion of calcining leaches in beaker, mixture is filtered while hot, and beaker, filter residue is washed with deionized 3-4 times；
F. gained filtrate is rich in nickel, copper, the leachate of cobalt, can be used as extracting nickel, copper, cobalt；Leached mud is in drying in oven Afterwards, production gypsum raw material can be used as.
It is of the present invention it is a kind of by low nickel matte calcification baking-acidleach high efficiency extraction nickel, copper, cobalt method, it is most preferably Technological parameter be：Roasting additive is calcium oxide, and roasting time is 2 h, and the mass ratio of calcium oxide and low nickel matte is 1:1, roasting It is 1100 to burn temperatureoC；Product of roasting is leached with the dilute sulfuric acid that 100 mL concentration are 2 mol/L；After extract filtering, filtrate is made To extract the raw material of nickel, copper, cobalt.
The principle of the present invention is that at high temperature, calcium oxide can absorb sulfur dioxide caused by roasting process, and can press down completely The generation of ferrite processed, nickel, copper, cobalt are changed into oxide, leached completely in acid condition.
Compared with traditional thermal process, the present invention have substantive distinguishing features prominent as follows and it is notable the advantages of：
Simplify technological process, shorten the time, it is cost-effective, and greatly reduce bessemerize during valuable metal be particularly The loss of cobalt, and due to CaO sulfur fixation, prevent roasting process SO2Discharge, be advantageous to environmental protection.
Brief description of the drawings
Fig. 1 is under different temperatures, and CaO is 1 with low nickel matte mass ratio:Behind 1, with baking mixed 2 h of low nickel matte, nickel, copper, cobalt Leaching rate curve map.
Fig. 2 is 1100oUnder C, CaO and low nickel matte different material are calcined the nickel after 2 h, copper, the leaching rate of cobalt when matching bent Line chart.
Fig. 3 is 1100oUnder C, CaO is 1 with low nickel matte mass ratio:1, the CaO and baking mixed 1-3 h of low nickel matte nickel, copper With the leaching rate curve map of cobalt.
Embodiment
Below in conjunction with the accompanying drawings, the specific embodiment of the present invention is further described.
Embodiment 1
(1) low nickel matte after 1 g CaO powders and 1 g fine grindings is weighed first, then both are well mixed.
(2) after mixing, batch mixing is laid in crucible bottom, it is open, treat that resistance furnace rises to setting sintering temperature 1100 oC, It is incubated 2 h.
(3) material after being calcined takes out after being rapidly cooled to room temperature, is put into 250 ml beakers, and it is 2 to add concentration The mol/L ml of dilute sulfuric acid 100.
(4) beaker is placed on magnetic stirrer and stirs 1 h, temperature 90oC。
(5) leach after terminating, slurry is filtered while hot, that is, obtain rich in nickel, copper, the leachate of cobalt, can after filter residue drying Raw material as production gypsum.
Nickel, copper, cobalt leaching rate under different sintering temperatures are observed by leaching rate curve, as shown in Figure 1.Roasted by calcification Burning-sulfuric acid leaching, 1100oUnder the conditions of C, nickel, copper, the leaching rate of cobalt are attained by more than 90%, and the leaching rate of copper can reach 97 %。
Embodiment 2
(1) low nickel matte after lime powder and fine grinding is weighed first, and both are well mixed, calcium oxide and low nickel matte Mass ratio is（1~2）：1.
(2) after mixing, batch mixing is laid in crucible bottom, it is open, treat that resistance furnace rises to 1100oIt is put into during C, insulation 3 h。
(3) material after being calcined takes out after being rapidly cooled to room temperature, is put into 250 ml beakers, adds the dilute sulphur of 2 mol/L 100 ml of acid.
（4）Beaker is placed on magnetic stirrer and stirs 1 h, temperature 90oC。
（5）After leaching terminates, slurry is filtered while hot, that is, obtained rich in nickel, copper, the leachate of cobalt, can after filter residue drying Raw material as production gypsum.
Nickel, copper, cobalt leaching rate under different ratios of raw materials are observed by leaching rate curve, as shown in Figure 2.Roasted by calcification Burning-sulfuric acid leaching, it is seen that it is 1 that calcium oxide, which adds with low nickel matte mass ratio,:When 1, nickel, copper, the leaching rate of cobalt are higher, are attained by 90 More than %.
Embodiment 3：
(1) low nickel matte after 1 g lime powders and 1 g fine grindings is weighed first, then both are well mixed.
(2) after mixing, batch mixing is laid in crucible bottom, it is open, treat that resistance furnace rises to 1100oIt is put into during C, roasting is protected Warm 1-3 h.
(3) material after being calcined takes out after being rapidly cooled to room temperature, is put into 250 ml beakers, adds the dilute sulphur of 2 mol/L 100 ml of acid.
（4）Beaker is placed on magnetic stirrer and leaches 1 h, temperature 90oC。
（5）After leaching terminates, slurry is filtered while hot, that is, obtained rich in nickel, copper, the leachate of cobalt, can after filter residue drying Raw material as production gypsum.
Observed by leaching rate curve 1100oNickel, copper, the leaching rate of cobalt under C difference roasting times, as shown in Figure 3. Pass through calcification baking-sulfuric acid leaching, it is seen that for roasting time in the case of 2 h, nickel, copper, the leaching rate of cobalt have reached higher leaching Rate, it is attained by 90 more than %.

Claims (2)

1. it is a kind of by low nickel matte calcification baking-acidleach high efficiency extraction nickel, copper, cobalt method, it is characterised in that there is following mistake Journey and step：
A. it is in mass ratio with low nickel matte by calcium oxide（1~2）：1 ratio is well mixed, to make it fully react, low nickel matte Answer the levigate mesh of mistake 200；
B. mixed material is placed in crucible, it is open, then in certain temperature 500oC-1000 oUnder C, in resistance furnace It is calcined 1-3 h；
C. after the completion for the treatment of material roasting, sampling is cooled to room temperature；
D. the calcining after cooling being placed in beaker, the concentration for adding certain volume 50-150 ml is 2 mol/L dilute sulfuric acid, Beaker is placed on magnetic stirring apparatus and leached；Temperature is 90oC, extraction time 1-2 h；
E. after the completion of calcining leaches in beaker, mixture is filtered while hot, and beaker, filter residue is washed with deionized 3-4 times；
F. gained filtrate is rich in nickel, copper, the leachate of cobalt, can be used as extracting nickel, copper, cobalt；Leached mud is in drying in oven Afterwards, production gypsum raw material can be used as.
2. low nickel matte calcification baking according to claim 1-acidleach high efficiency extraction nickel, copper, the method for cobalt, its is most preferred Technological parameter is：Roasting additive is calcium oxide, and roasting time is 2 h, and the mass ratio of calcium oxide and low nickel matte is 1:1, roasting Temperature is 1100oC；Product of roasting is leached with 100 mL concentration for 2 mol/L dilute sulfuric acids；After extract filtering, filtrate is used as and carried Take the raw material of nickel, copper, cobalt.
CN201710574121.0A 2017-07-14 2017-07-14 A method of by low nickel matte calcification baking-acidleach high efficiency extraction nickel, copper, cobalt Active CN107475511B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113466215A (en) * 2021-09-02 2021-10-01 北矿检测技术有限公司 Method for simultaneously determining contents of gold, silver, platinum and palladium in low nickel matte and application
CN113621819A (en) * 2021-07-21 2021-11-09 广东邦普循环科技有限公司 Method for extracting valuable metals from low nickel matte converter slag
CN116287683A (en) * 2022-12-31 2023-06-23 广西中伟新能源科技有限公司 Leaching method of sulfide minerals

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CN101285128A (en) * 2008-03-18 2008-10-15 郑州永通特钢有限公司 Comprehensive reutilization method for laterite-nickel ore
CN101333601A (en) * 2008-07-11 2008-12-31 中南大学 Alkali breakdown process of molybdenum-vanadium multi-metal metallurgy smelting materials
CN102234721A (en) * 2011-06-15 2011-11-09 金川集团有限公司 Treatment method of nickel-cobalt material
CN103348026A (en) * 2012-02-07 2013-10-09 淡水河谷公司 Process to produce rough ferro-nickel product
CN105177307A (en) * 2015-09-06 2015-12-23 中南大学 Method for recycling copper-nickel-cobalt from low grade nickel matte through abrasive flotation separation
KR20160077399A (en) * 2014-12-22 2016-07-04 주식회사 포스코 Method for Producing Ferro Nickel

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1161379A (en) * 1997-01-15 1997-10-08 核工业北京化工冶金研究院 Method for extracting gold from refractory ore
CN1237641A (en) * 1999-06-15 1999-12-08 吉林省冶金研究院 Technological process for extracting Ni, Cu, Co and Mg from nickel sulfide preparation concentrate and making nickelferrite
CN1861817A (en) * 2005-05-13 2006-11-15 河南科技大学 Tech. of extracting metallic cobait from magnetic-iron ore tailing slag
CN101285128A (en) * 2008-03-18 2008-10-15 郑州永通特钢有限公司 Comprehensive reutilization method for laterite-nickel ore
CN101333601A (en) * 2008-07-11 2008-12-31 中南大学 Alkali breakdown process of molybdenum-vanadium multi-metal metallurgy smelting materials
CN102234721A (en) * 2011-06-15 2011-11-09 金川集团有限公司 Treatment method of nickel-cobalt material
CN103348026A (en) * 2012-02-07 2013-10-09 淡水河谷公司 Process to produce rough ferro-nickel product
KR20160077399A (en) * 2014-12-22 2016-07-04 주식회사 포스코 Method for Producing Ferro Nickel
CN105177307A (en) * 2015-09-06 2015-12-23 中南大学 Method for recycling copper-nickel-cobalt from low grade nickel matte through abrasive flotation separation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113621819A (en) * 2021-07-21 2021-11-09 广东邦普循环科技有限公司 Method for extracting valuable metals from low nickel matte converter slag
CN113621819B (en) * 2021-07-21 2022-11-15 广东邦普循环科技有限公司 Method for extracting valuable metals from low-grade nickel matte converter slag
CN113466215A (en) * 2021-09-02 2021-10-01 北矿检测技术有限公司 Method for simultaneously determining contents of gold, silver, platinum and palladium in low nickel matte and application
CN116287683A (en) * 2022-12-31 2023-06-23 广西中伟新能源科技有限公司 Leaching method of sulfide minerals

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