CN105903561A - Method for recovering manganese from cobalt-manganese multi-metal oxidized ore - Google Patents
Method for recovering manganese from cobalt-manganese multi-metal oxidized ore Download PDFInfo
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- CN105903561A CN105903561A CN201610237988.2A CN201610237988A CN105903561A CN 105903561 A CN105903561 A CN 105903561A CN 201610237988 A CN201610237988 A CN 201610237988A CN 105903561 A CN105903561 A CN 105903561A
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- manganese
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- flotation
- slag
- ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/005—Pretreatment specially adapted for magnetic separation
- B03C1/015—Pretreatment specially adapted for magnetic separation by chemical treatment imparting magnetic properties to the material to be separated, e.g. roasting, reduction, oxidation
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Abstract
The invention discloses a method for recovering manganese from cobalt-manganese multi-metal oxide ores, belonging to the field of comprehensive utilization of cobalt-manganese multi-metal ores. Carrying out wet reduction pretreatment on cobalt-manganese multi-metal oxide ores in an ammonia solution by using a reducing agent, chemically dissociating and activating manganese ores and impurity minerals, and then separating and recovering manganese through strong magnetic separation and flotation to obtain manganese concentrate. The method recovers manganese from the cobalt-manganese multi-metal oxide ore by chemical activation and physical ore dressing, and has simple process and low cost.
Description
Technical field
The invention belongs to cobalt manganese polymetallic ore field of comprehensive utilization, relate to a kind of method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit,
Especially by wet reducing pretreatment, the method that then manganese is reclaimed in ore dressing.
Background technology
Cobalt manganese multi-metal oxygen ore deposit refers to the multi-metal complex oxide ore rich in multiple valuable elements such as cobalt, nickel, copper, manganese, ferrum,
It is divided into land polymetallic nodules, seabed polymetallic nodules, seabed cobalt bearing crust, seabed cobalt tuberculosis etc., its main useful element bag
Include manganese, nickel, cobalt, copper etc., and the economic worth of manganese is maximum.Wherein deep sea polymetallic nodule is based on water iron and manganese oxides,
The a large amount of copper of association, cobalt, nickel and rare earth, dilute scattered valuable metal, belong to 21 century most extraction value oceanic mineral resources it
One, it is distributed mainly on the Pacific Ocean, the Atlantic Ocean and ocean submarine surface that the Indian Ocean depth of water is 2000～6000m, rich reserves.
Deep-sea cobalt bearing crust is as polymetallic nodules, and also belonging to a kind of is main submarine metallic ore thing with ferrimanganic hydrous oxide；But
Unlike polymetallic nodules, cobalt bearing crust cobalt content is high, reaches as high as more than 1.5%, and copper, nickel content are relatively low, due to
Its essential mineral is iron and manganese oxides, so also known as rich cobalt type Ferromanganese Crusts.But due to the manganese mineral in cobalt manganese polymetallic ore and stone-like pulse
Deng the tight symbiosis of impure mineral, direct physical ore dressing cannot separation and concentration, presently disclosed research method is all by directly smelting
Reclaim manganese, be roughly divided into pyrometallurgical smelting and hydrometallurgy.Cobalt manganese polymetallic ore is mainly at high temperature reduced by pyrometallurgical smelting
Melting, enters alloy by nickel, cobalt, copper reduction, and manganese is reduced in entrance smelting slag, owing to using high-temperature fusion reduction,
Energy consumption is high, and manganese fails to separate with gangue mineral impurity, causes the Fe content in slag low, affects following process.Hydrometallurgy
Being then to reclaim manganese in the method for acidic leaching from cobalt manganese polymetallic ore, but during acidleach, the metal such as nickel, cobalt, copper is the most immersed with manganese
Go out and enter in solution, cause beavy metal impurity content in manganese leachate high, need in advance will by methods such as precipitation, extract and separate
These impurity removes, and then carbonization precipitation reclaims manganese, and the synthetical recovery flow process of manganese is complicated, cost is high.
Summary of the invention
It is an object of the invention to provide a kind of with cobalt manganese multi-metal oxygen ore deposit as raw material, short route, the side of low cost synthetical recovery manganese
Method.
The present invention is achieved through the following technical solutions.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit, joins cobalt manganese multi-metal oxygen ore deposit in ammonia solution and stirs, and
Add reducing agent and carry out wet reducing pretreatment, then solid-liquid separation, obtain containing manganese slag and solution after pretreatment, manganese slag ore dressing will be contained
Obtain manganic concerntrate.Described ammonia solution is the one or many in ammonia-sal volatile, ammonia-ammonia sulfate solution or ammonia-ammonium chloride solution
The mixture planted, described reducing agent is one or more in sulfur dioxide, carbon monoxide, cuprous salt.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, described ore dressing is the one in high intensity magnetic separation and flotation or two
The combination planted, preferably direct flotation.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, described direct flotation, its process is: by described containing manganese slag
Mixing with suitable quantity of water, regulator, inhibitor, collecting agent and size mixing, then carry out flotation, the froth pulp of flotation output is through solid-liquid
Isolated manganic concerntrate.Described regulator can be sodium carbonate or sulphuric acid, and described inhibitor is waterglass, tannin, carboxymethyl cellulose
One or more in element, described collecting agent is in fatty-acid collector, hydrocarbyl sulfonic collecting agent, alkyl sodium sulfate collecting agent
One or more.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, described collecting agent be oxidized paraffin wax soap, oleic acid, 12
One or more in alkyl sodium sulfate.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, described high intensity magnetic separation and the combination of flotation two kinds, refer to by
After the described slag water containing manganese is sized mixing, roughly selecting with intensity magnetic separator, the magnetic product obtained is magnetic concentrate, then by magnetic concentrate with
The mixing of suitable quantity of water, regulator, inhibitor, collecting agent is sized mixing, then carries out flotation, and the froth pulp of flotation output is through solid-liquid separation
Obtain manganic concerntrate.Described regulator can be sodium carbonate or sulphuric acid, and described inhibitor is in waterglass, tannin, carboxymethyl cellulose
One or more, described collecting agent be the one in fatty-acid collector, hydrocarbyl sulfonic collecting agent, alkyl sodium sulfate collecting agent or
Multiple.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, the addition of described regulator is 0.8～2.4kg/t slag,
The addition of described inhibitor is 1.8～2.8kg/t slags, and the addition of described collecting agent is 0.5～2.5kg/t slag.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, described solution after pretreatment through extraction and recovery nickel therein,
The valuable element such as cobalt, copper, raffinate returns wet reducing pretreatment process and recycles.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, described cobalt manganese multi-metal oxygen ore deposit is seabed many metals knot
One or more in core, pelagite, seabed cobalt bearing crust, seabed cobalt tuberculosis, land manganese nodule, earthy cobalt.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit of the present invention, be by ammonia solution by the tetravalent manganese in Ore
It is reduced into bivalence, forms sub-manganese precipitation, thus realize and the dissociating of the impure mineral such as stone-like pulse, thus be Mineral separation and enrichment manganese
Create conditions.The advantage of the method is: (1) uses wet chemistry reduction pretreatment, can make manganese mineral and impure mineral solution
From thoroughly, the good separating effect of manganese；(2) preprocessing process can remove the heavy metals such as the nickel in Ore, cobalt, copper simultaneously and is harmful to miscellaneous
Matter, and synthetical recovery can be realized；(3) flow process is simple, low cost, and manganese recovery ratio is high, manganic concerntrate good product quality.
Accompanying drawing explanation
Accompanying drawing is the principle process chart of the inventive method.
Detailed description of the invention
Below in conjunction with accompanying drawing the present invention made and further illustrating.
The method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit, joins total ammonia density 60～160g/L by cobalt manganese multi-metal oxygen ore deposit
Ammonia solution stirs, in ore pulp, adds appropriate sulfur dioxide after mix homogeneously or the reducing agent such as carbon monoxide or cuprous salt is anti-
Answer 0.5～4h, solid-liquid separation, obtain containing manganese slag and solution after pretreatment.Solution after pretreatment has valency through extract and separate nickel, cobalt, copper etc.
Returning reduction pretreatment after element to use, the slag containing manganese utilizes high intensity magnetic separation, flotation or both combined recovery manganese.Reclaim when using flotation
It is configured to 15%～45% ore pulp during manganese, is subsequently adding regulator 0.8～2.4kg/t slag, inhibitor 1.8～2.8kg/t slag, collecting agent
0.5～2.5kg/t slag, flotation in flotation device, i.e. obtain manganic concerntrate after froth pulp solid-liquid separation.
In force, it is also possible to be high intensity magnetic separation and the combination of flotation two kinds, high intensity magnetic separation will be used after the described slag water in manganese sizes mixing
Machine is roughly selected, and the magnetic product obtained is magnetic concentrate, then by magnetic concentrate and suitable quantity of water, regulator, inhibitor, collecting agent
Mixing is sized mixing, then carries out flotation, and the froth pulp of flotation output obtains manganic concerntrate through solid-liquid separation.
Described regulator can be sodium carbonate or sulphuric acid, and described inhibitor is the one in waterglass, tannin, carboxymethyl cellulose or many
Kind, described collecting agent is one or more in fatty-acid collector, hydrocarbyl sulfonic collecting agent, alkyl sodium sulfate collecting agent.
With following nonlimiting examples, the method for the present invention is further described, with contribute to understanding present disclosure and
Its advantage, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Embodiment 1
Cobalt manganese multi-metal oxygen ore deposit is joined in total ammonia density 120g/L ammonia-sal volatile and stir, at ore pulp after mix homogeneously
The appropriate cuprous salt of middle addition is also passed through Carbon monoxide reduction process 4h, solid-liquid separation, obtains containing manganese slag and solution after pretreatment.Pre-place
After reason, liquid returns reducing leaching after the valuable elements such as extract and separate nickel, cobalt, copper and uses, and will contain manganese slag and add water and be configured to 35% ore deposit
Slurry, adds sulfuric acid solution regulation slurry pH 8～9, adds 2.8kg waterglass/t slag, 2.5kg enuatrol/t slag, stir 5
Flotation device is entered, through primary election manganic concerntrate productivity 63.4%, Fe content 37.2%, a total iron content 1.5% after minute.
Embodiment 2
Cobalt manganese multi-metal oxygen ore deposit is joined in total ammonia density 80g/L ammonia-ammonia sulfate solution and stir, after mix homogeneously in ore pulp
Add appropriate cuprous salt and be passed through Carbon monoxide reduction process 2h, solid-liquid separation, obtaining containing manganese slag and solution after pretreatment.Pretreatment
Rear liquid returns reducing leaching after the valuable elements such as extract and separate nickel, cobalt, copper and uses, and will contain manganese slag and add water and be configured to 35% ore pulp,
Add sulfuric acid solution regulation slurry pH 8～9, add 2.8kg waterglass/t slag, 2.5kg enuatrol/t slag, stir 5 points
Flotation device is entered, through primary election manganic concerntrate productivity 62.6%, Fe content 35.9%, a total iron content 1.3% after clock.
Embodiment 3
Cobalt manganese multi-metal oxygen ore deposit is joined in total ammonia density 60g/L ammonia-ammonia sulfate solution and stir, after mix homogeneously in ore pulp
Add appropriate cuprous salt and be passed through Carbon monoxide reduction process 4h, solid-liquid separation, obtaining containing manganese slag and solution after pretreatment.Pretreatment
Rear liquid returns reducing leaching after the valuable elements such as extract and separate nickel, cobalt, copper and uses, and will contain manganese slag and add water and be configured to 35% ore pulp,
Add sulfuric acid solution regulation slurry pH 8～9, add 2.8kg waterglass/t slag, 2.5kg sodium lauryl sulphate/t slag,
Flotation device is entered, through primary election manganic concerntrate productivity 61.4%, Fe content 35.5%, a total iron content 1.2% after stirring 5 minutes.
Embodiment 4
Cobalt manganese multi-metal oxygen ore deposit is joined in total ammonia density 60g/L ammonia-sal volatile and stir, after mix homogeneously in ore pulp
Add appropriate cuprous salt and be passed through Carbon monoxide reduction process 2h, solid-liquid separation, obtaining containing manganese slag and solution after pretreatment.Pretreatment
Rear liquid returns reducing leaching after the valuable elements such as extract and separate nickel, cobalt, copper and uses, and will contain manganese slag and add water and be configured to 35% ore pulp,
Add sulfuric acid solution regulation slurry pH 8～9, add 2.8kg carboxymethyl cellulose/t slag, 2.5kg enuatrol/t slag, stir 5
Flotation device is entered, through primary election manganic concerntrate productivity 62.3%, content 36.1%, a total iron content 1.2% after minute.
Embodiment 5
Cobalt manganese multi-metal oxygen ore deposit is joined in total ammonia density 100g/L ammonia-sal volatile and stir, at ore pulp after mix homogeneously
The appropriate cuprous salt of middle addition is also passed through Carbon monoxide reduction process 2h, solid-liquid separation, obtains containing manganese slag and solution after pretreatment.Pre-place
After reason, liquid returns reducing leaching use after the valuable elements such as extract and separate nickel, cobalt, copper, and will contain manganese slag carries out wet high-intensity magnetic separation,
Then the high intensity magnetic mineral obtained is added water and be configured to 35% ore pulp, add sulfuric acid solution regulation slurry pH 8～9, add 2.8kg
Waterglass/t slag, 2.5kg enuatrol/t slag, after stirring 5 minutes enter flotation device, through a flotation obtain manganic concerntrate productivity 52.1%,
Fe content 39.2%, total iron content 0.5%.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, and any
Those familiar with the art in the technical scope that the invention discloses, the change that can readily occur in or replacement, all should contain
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with scope of the claims.
Claims (10)
1. the method reclaiming manganese from cobalt manganese multi-metal oxygen ore deposit, it is characterised in that: cobalt manganese multi-metal oxygen ore deposit is joined in ammonia solution and stir,
And add reducing agent and carry out wet reducing pretreatment, then solid-liquid separation, obtain containing manganese slag and solution after pretreatment, manganese slag ore dressing will be contained and obtain manganic concerntrate.
Method the most according to claim 1, it is characterised in that described ammonia solution be ammonia-sal volatile, ammonia-ammonia sulfate solution or ammonia-
One or more in ammonium chloride solution, described reducing agent is one or more in sulfur dioxide, carbon monoxide, cuprous salt.
Method the most according to claim 1, it is characterised in that described ore dressing is one or both the combination in high intensity magnetic separation and flotation.
Method the most according to claim 1, it is characterised in that described ore dressing is direct flotation, its process is: by described containing manganese slag with appropriate
The mixing of water, regulator, inhibitor, collecting agent is sized mixing, and then carries out flotation, and the froth pulp of flotation output obtains manganic concerntrate through solid-liquid separation.
Method the most according to claim 3, it is characterised in that described high intensity magnetic separation and the combination of flotation two kinds, is containing manganese slag water by described
After sizing mixing, roughly selecting with intensity magnetic separator, the magnetic product obtained is magnetic concentrate, then by magnetic concentrate and suitable quantity of water, regulator, inhibitor, catch
Receiving agent mixing to size mixing, then carry out flotation, the froth pulp of flotation output obtains manganic concerntrate through solid-liquid separation.
6., according to the method described in claim 4 or 5, it is characterised in that described regulator can be sodium carbonate or sulphuric acid, described inhibitor is water
One or more in glass, tannin, carboxymethyl cellulose, described collecting agent is fatty-acid collector, hydrocarbyl sulfonic collecting agent, alkyl sodium sulfate
One or more in collecting agent.
Method the most according to claim 6, it is characterised in that described collecting agent is in oxidized paraffin wax soap, oleic acid, sodium lauryl sulphate
One or more.
8. according to the method described in claim 4 or 5, it is characterised in that the addition of described regulator is 0.8～2.4kg/t slag, described suppression
The addition of agent is 1.8～2.8kg/t slags, and the addition of described collecting agent is 0.5～2.5kg/t slag.
Method the most according to claim 1, it is characterised in that described solution after pretreatment has valency through extraction and recovery nickel therein, cobalt, copper etc.
Element, raffinate returns wet reducing pretreatment process and recycles.
Method the most according to claim 1, it is characterised in that described cobalt manganese multi-metal oxygen ore deposit is seabed polymetallic nodules, seabed manganese knot
One or more in core, seabed cobalt bearing crust, seabed cobalt tuberculosis, land manganese nodule, earthy cobalt.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114192274A (en) * | 2021-12-02 | 2022-03-18 | 中南大学 | Manganese ore resource utilization method combining smelting and selecting materials |
| CN115094230A (en) * | 2022-06-23 | 2022-09-23 | 中国地质科学院矿产综合利用研究所 | Method for extracting rare earth, phosphorus and manganese elements from deep sea rare earth-rich sediments |
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| US3983017A (en) * | 1972-12-01 | 1976-09-28 | Kennecott Copper Corporation | Recovery of metal values from manganese deep sea nodules using ammoniacal cuprous leach solutions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114192274A (en) * | 2021-12-02 | 2022-03-18 | 中南大学 | Manganese ore resource utilization method combining smelting and selecting materials |
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| CN115094230A (en) * | 2022-06-23 | 2022-09-23 | 中国地质科学院矿产综合利用研究所 | Method for extracting rare earth, phosphorus and manganese elements from deep sea rare earth-rich sediments |
| CN115094230B (en) * | 2022-06-23 | 2024-03-08 | 中国地质科学院矿产综合利用研究所 | Method for extracting rare earth, phosphorus and manganese elements from deep sea rare earth-rich sediment |
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