CN107739845A - A kind of cleaning procedure of reducing leaching Africa heterogenite - Google Patents

A kind of cleaning procedure of reducing leaching Africa heterogenite Download PDF

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Publication number
CN107739845A
CN107739845A CN201710772951.4A CN201710772951A CN107739845A CN 107739845 A CN107739845 A CN 107739845A CN 201710772951 A CN201710772951 A CN 201710772951A CN 107739845 A CN107739845 A CN 107739845A
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CN
China
Prior art keywords
heterogenite
cleaning procedure
africa
reducing
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.)
Pending
Application number
CN201710772951.4A
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Chinese (zh)
Inventor
钟晖
徐定源
吴理觉
汤依伟
彭灿
张颖
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.)
Hunan Jiana Energy Technology Co Ltd
Guangdong Jiana Energy Technology Co Ltd
Original Assignee
Hunan Jiana Energy Technology Co Ltd
Guangdong Jiana Energy Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hunan Jiana Energy Technology Co Ltd, Guangdong Jiana Energy Technology Co Ltd filed Critical Hunan Jiana Energy Technology Co Ltd
Priority to CN201710772951.4A priority Critical patent/CN107739845A/en
Publication of CN107739845A publication Critical patent/CN107739845A/en
Pending legal-status Critical Current

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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
    • 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
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction 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
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • 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

Abstract

The invention discloses a kind of cleaning procedure of reducing leaching Africa heterogenite, comprise the following steps:Required solid-to-liquid ratio ore pulp is modulated into after heterogenite ball milling with water, required sulfuric acid is added, is warming up to and requires temperature, reducing agent is added by 0.5 ~ 1 times of amount of cobalt amount of metal.Reaction to required time can complete reducing leaching process;The reducing agent is hydrazine hydrate and/or azanol.The cleaning procedure of the reducing leaching Africa heterogenite of the present invention has the characteristics of safe, environment-friendly type is good, technique is simple and cost is cheap.

Description

A kind of cleaning procedure of reducing leaching Africa heterogenite
Technical field
The present invention relates to metallurgical technology technical field, particularly a kind of cleaning procedure of reducing leaching Africa heterogenite.
Background technology
The extract technology of current African heterogenite is to add reducing agent to carry out reduction acidleach with sulfuric acid:Heterogenite passes through wet method ball After mill, after ore pulp adjusts ore pulp ratio, add sulfuric acid and acidic reduction leaching is carried out at higher than 70 DEG C.Due to having portion in heterogenite It is trivalent to divide cobalt, it is impossible to is directly leached by sulfuric acid.Therefore a certain amount of reducing agent is added in leaching process.It is routinely added to Reducing agent be sodium sulfite(Or sodium pyrosulfite, sulfur dioxide gas etc.).Leach complete after, by temperature rise to 90 DEG C with On, add oxidant(Typically sodium chlorate)Will be ferrous oxidising into ferric iron in solution, add sodium carbonate(Or carbonic acid Hydrogen ammonium)Carry out yellow sodium(Ammonium)Siderotil iron removaling, 40 DEG C or so are cooled the temperature to afterwards, into extraction, workshop section carries out deep purifying and cobalt Nickel is analyzed.
The shortcomings that this method is:One is the increase in the salt in leachate, easily causes salt and separates out plugging;Second, increase , potential safety hazard be present in environmental protection pressure.
It is deep because because reducing agent is added in a manner of salt, necessarily increasing the salt in leachate to study carefully its.With cobalt content Exemplified by 30g/L leachate, its ion concentration amounts up to nearly 200g/L.The ion concentration that wherein reducing agent is brought into exceedes 40g/L, just account for more than 1/5 proportion.In addition during the chemical subtraction in later stage, substantial amounts of chemical reagent is also added, Cause the salt of liquid after cleaning too high.Before extraction deep purifying and separation is entered, the temperature of solution is by by chemical subtraction More than 90 DEG C are down to 40 DEG C, and this temperature-fall period will have substantial amounts of salt and separate out.Here it is cause cobalt salt production line pre-treatment There is the immediate cause of pipeline obstruction in Duan Jingchang.
High additionally, due to Leach reaction temperature, in reduction process, the spilling of sulfur dioxide gas is unavoidable.Therefore exist A set of gas elution retracting device will be had by leaching process, and absorption processing is carried out to the sulfur dioxide gas of spilling.Add ring Border is born, and potential safety hazard be present..
The content of the invention
The main purpose of the present invention is the provision of a kind of cleaning procedure of reducing leaching Africa heterogenite, has safety Property it is high, environment-friendly type is good, technique is simple and cost is cheap the characteristics of.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of cleaning procedure of reducing leaching Africa heterogenite, comprise the following steps:
Required solid-to-liquid ratio ore pulp is modulated into after heterogenite ball milling with water, required sulfuric acid is added, is warming up to and requires temperature, by cobalt 0.5 ~ 1 times of amount of amount of metal adds reducing agent.Reaction to required time can complete reducing leaching process;
The reducing agent is hydrazine hydrate and/or azanol.
Further, the scope of described solid-to-liquid ratio is 1t:3.5~5m3
Further, the addition of required sulfuric acid is 3.5~4.5 times of cobalt metal quality.
Further, it is desirable to which the scope of temperature is more than 70 DEG C.
Further, the scope of required time is 4~6 hours.
The cleaning procedure of reducing leaching Africa of the present invention heterogenite has following beneficial technique effect:
For the cleaning procedure of the present invention, present invention uses a kind of reducing agent that will not bring salt into, leachate is reduced Salt, while without toxic and harmful gas produce.The reducing agent that prior art uses can bring salt into, while can also produce Malicious pernicious gas, increase environmental protection pressure.The reducing agent that the present invention selects:Hydrazine hydrate and azanol etc, the final product of reaction are Nitrogen and water, the two caused problems of prior art can be avoided simultaneously, the salt content 40g/L in leachate can be reduced More than.And produced without toxic and harmful gas, reduce environmental protection pressure..
Embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment and to this Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of cleaning procedure of reducing leaching Africa heterogenite, comprise the following steps:
Required solid-to-liquid ratio ore pulp is modulated into after heterogenite ball milling with water, required sulfuric acid is added, is warming up to and requires temperature, by cobalt 0.5 ~ 1 times of amount of amount of metal adds reducing agent.Reaction to required time can complete reducing leaching process;
The reducing agent is hydrazine hydrate and/or azanol.
In the present embodiment, the scope of described solid-to-liquid ratio is 1t:3. 5m3.The addition of required sulfuric acid is cobalt metal 4 times of quality.It is required that the scope of temperature is more than 70 DEG C.The scope of required time is 4 hours.
Embodiment 2
The invention discloses a kind of cleaning procedure of reducing leaching Africa heterogenite, comprise the following steps:
Required solid-to-liquid ratio ore pulp is modulated into after heterogenite ball milling with water, required sulfuric acid is added, is warming up to and requires temperature, by cobalt 0.5 ~ 1 times of amount of amount of metal adds reducing agent.Reaction to required time can complete reducing leaching process;
The reducing agent is hydrazine hydrate and/or azanol.
In the present embodiment, the scope of described solid-to-liquid ratio is 1t:4.2m3.The addition of required sulfuric acid is cobalt metal 3.5 times of quality.It is required that the scope of temperature is more than 70 DEG C.The scope of required time is 6 hours.
Embodiment 3
The invention discloses a kind of cleaning procedure of reducing leaching Africa heterogenite, comprise the following steps:
Required solid-to-liquid ratio ore pulp is modulated into after heterogenite ball milling with water, required sulfuric acid is added, is warming up to and requires temperature, by cobalt 0.5 ~ 1 times of amount of amount of metal adds reducing agent.Reaction to required time can complete reducing leaching process;
The reducing agent is hydrazine hydrate and/or azanol.
In the present embodiment, the scope of described solid-to-liquid ratio is 1t:3.5m3.The addition of required sulfuric acid is cobalt metal 4.5 times of quality.It is required that the scope of temperature is more than 70 DEG C.The scope of required time is 5 hours.
Embodiment 4
The invention discloses a kind of cleaning procedure of reducing leaching Africa heterogenite, comprise the following steps:
Required solid-to-liquid ratio ore pulp is modulated into after heterogenite ball milling with water, required sulfuric acid is added, is warming up to and requires temperature, by cobalt 0.5 ~ 1 times of amount of amount of metal adds reducing agent.Reaction to required time can complete reducing leaching process;
The reducing agent is hydrazine hydrate and/or azanol.
In the present embodiment, the scope of described solid-to-liquid ratio is 1t:4m3.The addition of required sulfuric acid is cobalt metallic 3.8 times of amount.It is required that the scope of temperature is more than 70 DEG C.The scope of required time is 5 hours.
Application Example 1
The composition of heterogenite:Co:12.288%、Cu:1.434%.The good heterogenite of ball milling is pressed into liquid-solid ratio 4.5:1 sizes mixing, by cobalt 3.8 times of amount of metal add needed for sulfuric acid, be warming up to 75 DEG C, during add cobalt 0.5 times of hydrazine hydrate of amount of metal by several times in batches. Extraction time is 5 hours.Cobalt is 0.22% in the leached mud finally given, copper 0.15%;The leaching rate of cobalt copper is respectively:97.4%、 84.3%
Application Example 2
The composition of heterogenite:Co:12.288%、Cu:1.434%.The good heterogenite of ball milling is pressed into liquid-solid ratio 3.8:1 sizes mixing, by cobalt 4.2 times of amount of metal add needed for sulfuric acid, be warming up to 90 DEG C, during add cobalt 0.8 times of azanol of amount of metal by several times in batches.Leaching Go out the time for 4 hours.Cobalt is 0.19% in the leached mud finally given, copper 0.14%;The leaching rate of cobalt copper is respectively:98.8%、 85%。
For the cleaning procedure of the present invention, present invention uses a kind of reducing agent that will not bring salt into, leaching is reduced Go out the salt of liquid, while produced without toxic and harmful gas.The reducing agent that prior art uses can bring salt into, while can also produce Raw toxic and harmful gas, increases environmental protection pressure.The reducing agent that the present invention selects:Hydrazine hydrate, the final product of reaction be nitrogen and Water, the two caused problems of prior art can be avoided simultaneously, more than the salt content 40g/L in leachate can be reduced. And produced without toxic and harmful gas, reduce environmental protection pressure.
The foregoing is only a preferred embodiment of the present invention, not makees any formal limitation to the present invention;It is all The those of ordinary skill of the industry can be shown in by specification and described above and swimmingly implement the present invention;It is but all familiar Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents A little variation, modification and evolution equivalent variations, be the present invention equivalent embodiment;Meanwhile all realities according to the present invention Variation, modification and evolution of any equivalent variations that matter technology is made to above example etc., still fall within the technology of the present invention Within the protection domain of scheme.

Claims (5)

1. the cleaning procedure of a kind of reducing leaching Africa heterogenite, it is characterised in that comprise the following steps:
Required solid-to-liquid ratio ore pulp is modulated into after heterogenite ball milling with water, required sulfuric acid is added, is warming up to and requires temperature, by cobalt 0.5 ~ 1 times of amount of amount of metal adds reducing agent, and reducing leaching process can be completed by reacting to required time;
The reducing agent is hydrazine hydrate and/or azanol.
2. the cleaning procedure of reducing leaching Africa according to claim 1 heterogenite, it is characterised in that:Described solid-to-liquid ratio Scope be 1t:3.5~5m3
3. the cleaning procedure of reducing leaching Africa according to claim 1 or 2 heterogenite, it is characterised in that:Required sulphur The addition of acid is 3.5~4.5 times of cobalt metal quality.
4. the cleaning procedure of reducing leaching Africa according to claim 3 heterogenite, it is characterised in that:It is required that the model of temperature Enclose for more than 70 DEG C.
5. the cleaning procedure of reducing leaching Africa according to claim 4 heterogenite, it is characterised in that:The model of required time Enclose for 4~6 hours.
CN201710772951.4A 2017-08-31 2017-08-31 A kind of cleaning procedure of reducing leaching Africa heterogenite Pending CN107739845A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110184455A (en) * 2019-06-20 2019-08-30 东北大学 A kind of leaching method of difficult leaching cobalt ore
CN110951977A (en) * 2019-12-11 2020-04-03 沈阳有色金属研究院有限公司 Method for leaching cobaltite by using biomass reducing agent
CN113278817A (en) * 2021-05-06 2021-08-20 广东佳纳能源科技有限公司 Impurity removal method for cobalt ore and crude cobalt salt sulfuric acid leaching solution and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63137128A (en) * 1986-11-27 1988-06-09 Agency Of Ind Science & Technol Acid treatment of manganese nodule
RU2095451C1 (en) * 1997-01-23 1997-11-10 Товарищество с ограниченной ответственностью "Инженер" Method for extraction of cobalt
RU2106417C1 (en) * 1996-09-25 1998-03-10 Сергеев Валерий Владимирович Method for recovery of cobalt from middlings containing cobalt oxides
CN101509069A (en) * 2009-03-30 2009-08-19 南通新玮镍钴科技发展有限公司 Method for selective solvent extraction of heterogenite with full-wet-process
CN101994003A (en) * 2010-12-10 2011-03-30 中南大学 Process for selectively extracting copper and cobalt from heterogenite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63137128A (en) * 1986-11-27 1988-06-09 Agency Of Ind Science & Technol Acid treatment of manganese nodule
RU2106417C1 (en) * 1996-09-25 1998-03-10 Сергеев Валерий Владимирович Method for recovery of cobalt from middlings containing cobalt oxides
RU2095451C1 (en) * 1997-01-23 1997-11-10 Товарищество с ограниченной ответственностью "Инженер" Method for extraction of cobalt
CN101509069A (en) * 2009-03-30 2009-08-19 南通新玮镍钴科技发展有限公司 Method for selective solvent extraction of heterogenite with full-wet-process
CN101994003A (en) * 2010-12-10 2011-03-30 中南大学 Process for selectively extracting copper and cobalt from heterogenite

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110184455A (en) * 2019-06-20 2019-08-30 东北大学 A kind of leaching method of difficult leaching cobalt ore
CN110951977A (en) * 2019-12-11 2020-04-03 沈阳有色金属研究院有限公司 Method for leaching cobaltite by using biomass reducing agent
CN113278817A (en) * 2021-05-06 2021-08-20 广东佳纳能源科技有限公司 Impurity removal method for cobalt ore and crude cobalt salt sulfuric acid leaching solution and application thereof

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Application publication date: 20180227