CN1037786C - Polyhydroxy aromatic acid reduction leaching method for manganese oxide ore - Google Patents
Polyhydroxy aromatic acid reduction leaching method for manganese oxide ore Download PDFInfo
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- CN1037786C CN1037786C CN94117548A CN94117548A CN1037786C CN 1037786 C CN1037786 C CN 1037786C CN 94117548 A CN94117548 A CN 94117548A CN 94117548 A CN94117548 A CN 94117548A CN 1037786 C CN1037786 C CN 1037786C
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- acid
- manganese oxide
- oxide ore
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- polyhydroxy aromatic
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Abstract
A polyhydroxy aromatic acid reduction leaching method of manganese oxide ore relates to a method for extracting valuable metals from manganese oxide ore, in particular to ocean manganese nodule. It is characterized by that it adopts polyhydroxy aromatic acid as reducing leaching agent. Under normal temperature and pressure, manganese oxide ore material is made into pulp, acid and polyhydroxy aromatic acid are added, and the pulp is directly leached in a conventional leaching tank. The reaction kinetics of reduction and acid leaching of manganese oxide ore by polyhydroxy aromatic acid is good, the reaction speed is high, the leaching rate is high, and the equipment is simple, so that the method is an effective manganese oxide ore treatment method.
Description
The present invention relates to a kind of polyhydroxy aromatic acids reduction leaching method of manganese oxide ore, particularly the method for valuable metal in the marine manganese nodule is leached in reduction.
Marine manganese nodule is a very huge prospect resource, and each ocean manganese nodule resource reserve of the world is about 5,000 hundred million tons according to estimates.The treatment process of marine manganese nodule is broadly divided into pyrometallurgical smelting and wet method leaches two big classes.Wherein wet method leaches and to mainly contain acidleach and ammonia soaks two class methods.Manganese in the manganese nodule mainly exists with the high oxidation state of+4 valencys, and metals such as nickel, copper, cobalt exist in the oxide mineral of manganese, iron with the tax of isomorph form, therefore to reclaim valuable metals such as nickel, copper, cobalt, manganese effectively, at first must realize the decomposition of high oxidation state manganese phase.Because manganese+4 valency oxide compounds (are mainly MnO
2) be difficult to reaction with dilute acid soln, usually need to add reductive agent, make+4 valency Mn are converted into+divalent Mn just is easy to dissolve in acid medium.As United States Patent (USP) [4872909,1989] announced the manganese oxide ore acidleach method of manganese nodule especially of making reductive agent with hydrogen peroxide, slurry temperature preferably maintained normal temperature (about 25 ℃) when this method required to leach, temperature raises, metal leaching rate reduces, the hydrogen peroxide consumption increases (poor heat stability that contains hydrogen peroxide in the assorted dilute solution), and this leaching reaction is a reaction of emitting a large amount of heats, be enough to slurry temperature is raised to 45 ℃, so need to cool off ore pulp in the leaching process.And for example day disclosure special permission communique [clear 56-119743] discloses a kind of method that leaches marine manganese nodule with the sulfur dioxide gas reduction, this method is owing to will constantly feed sulfur dioxide gas when leaching in ore pulp, thereby reaction can only be carried out in encloses container, also to make slurry temperature remain on 50～100 ℃ simultaneously, so this method is not ideal enough.Russian patent (SU1715873,1993) discloses the manganese nodule acidleach method of the intermediates of the natural sulfide enrichment of a kind of usefulness as reductive agent, and this method need heat (90～100 ℃) to ore pulp, and extraction time is grown (2 hours).
Purpose of the present invention is exactly the deficiency that exists in the above-mentioned technology in order to overcome, be implemented under the normal temperature and pressure conditions, use conventional (uncovered) leaching vat to leach, do not need ore pulp is cooled off or heats and purpose that leaching velocity is fast, the present invention adopts polyhydroxy aromatic to make reductive agent and directly leach manganese oxide ore in acidic medium.
The objective of the invention is to realize by the following technical solutions.
A kind of polyhydroxy aromatic acids reduction leaching method of manganese oxide ore, comprise the ore pulverizing, slurrying, it is characterized in that adopting (3,4,5)-trihydroxybenzoic acid, (3,4)-resorcylic acid, between the position-two condensed gallic acids, polyhydroxy aromatics such as polymer Weibull are made the reduction leaching agent, be selected from sulfuric acid, nitric acid, leach in the acidic medium of hydrochloric acid, processing condition: the granularity＜0.5mm of manganese oxide ore, ore pulp liquid-solid ratio (weight ratio): 3: 1～10: 1, sour consumption: 0.5～1.5g/g manganese oxide ore, polyhydroxy aromatic consumption: 0.1～0.5g/g manganese oxide ore, extraction time: 10～15 minutes, stirring velocity: 600～1500 rev/mins.
The polyhydroxy aromatic compounds, as (3,4,5)-trihydroxybenzoic acid (being gallic acid), (3,4)-resorcylic acid, Weibull promptly between position-two condensed gallic acids, polymer Weibull etc. all is strong organic reducing agent, can be by MnO in acid solution (can be the acid solution of sulfuric acid, hydrochloric acid, nitric acid etc.)
2Oxidation is simultaneously with MnO
2In+4 valency Mn are reduced at a low price manganese and it are dissolved in acid solution, the Ni in this moment manganese, the iron oxide lattice, and Cu, the high oxide of Co etc. also will be reduced dissolving.
Adopt the polyhydroxy aromatic compounds to make reductive agent and in acidic medium, leach manganese oxide ore, manganese wherein and the copper in the marine manganese nodule, nickel, valuable metals such as cobalt all obtain the ideal leaching yield, leaching yield reaches as high as more than 90%, the dynamics that leaches reaction is good, leaching velocity is fast, can finish leaching process at 10～30 minutes, the medicine consumption rationally, do not need ore pulp is heated, leaching exothermic heat of reaction makes the slurry temperature rising can activate leaching process, need not cool off, react no obnoxious flavour and emit, can realize leaching process under the normal temperature and pressure in conventional leaching vat, equipment is simple, therefore be a kind of effective manganese oxide ore treatment process, have prospects for commercial application.
The invention will be further described to provide embodiment below.
Implementation method of the present invention is, maximum particle size after pulverizing is no more than 0.5mm, and preferably＜0.074mm accounts for 40～90% manganese oxide ore material and size mixing, the liquid-solid ratio that makes slip is (weight ratio) 3: 1～10: 1, simultaneously, add acid and poly-hydroxy virtue compounds, sour consumption is 0.5～1.5g/g manganese oxide ore, and stirring velocity is 600～1500 rev/mins, in conventional leaching vat, directly leach after 10～30 minutes, carry out liquid-solid separation, abandon and soak slag, leach liquor gives next step metal recovery.
Embodiment 1
The marine manganese nodule raw meal particle size that crushes accounts for 65%, contains Mn:10.35%, Cu0.40%, Ni0.66%, Co0.32% for＜0.074mm.Extraction temperature is 21 ℃, and pressure is normal atmosphere.Experimental result sees Table 1.
Embodiment 2
The marine manganese nodule granularity that crushes accounts for 72%, contains Mn14.21%, Cu0.34% for＜0.074mm.Ni0.58％，Co0.27％。Extraction temperature is 23 ℃, and pressure is normal atmosphere.
Experimental result sees Table 2.
Embodiment 3
The manganese oxide ore granularity that crushes accounts for 90% for＜0.074mm, contains Mn12.62%, and extraction temperature is 23 ℃, and pressure is normal atmosphere.
Experimental result sees Table 3.
Table 1
Annotate: reductive agent is a gallic acid in the table, consumption unit: the g/g manganese nodule,
Acid is sulfuric acid, consumption unit: the g/g manganese nodule,
Stirring velocity unit: rev/min,
Extraction time unit: minute.
Table 2
Annotate: reductive agent is a Weibull in the table, consumption unit: the g/g manganese nodule,
Acid is sulfuric acid, consumption unit: the g/g manganese nodule,
Stirring velocity unit: rev/min,
Extraction time unit: minute.
Table 3
Annotate: reductive agent is (3,4)-resorcylic acid in the table, consumption unit: the g/g manganese oxide ore,
Acid is sulfuric acid, consumption unit: the g/g manganese oxide ore,
Stirring velocity unit: rev/min,
Extraction time unit: minute.
Claims (7)
1. the polyhydroxy aromatic acids reduction leaching method of a manganese oxide ore, comprise ore powder essence, slurrying, it is characterized in that: adopt (3,4,5)-trihydroxybenzoic acid, (3,4)-polyhydroxy aromatics such as resorcylic acid, a position-two condensed gallic acid, polymer Weibull make the reduction leaching agent, leach in the acidic medium that is selected from sulfuric acid, hydrochloric acid, nitric acid
Processing condition are:
Granularity＜the 0.5mm of manganese oxide ore,
Ore pulp liquid-solid ratio (weight ratio): 3: 1～10: 1,
The acid consumption: 0.5～1.5g/g manganese oxide ore,
The polyhydroxy aromatic consumption: 0.1～0.5g/g manganese oxide ore,
Extraction time: 10～15 minutes,
Stirring velocity: 600～1500 rev/mins.
2. method according to claim 1 is characterized in that described reduction leaching agent is a gallic acid.
According to claim 1 fast method, it is characterized in that described reduction leaching agent is a Weibull.
4. method according to claim 1 is characterized in that described reduction leaching agent (3,4)-resorcylic acid.
5. method according to claim 1 is characterized in that described acidic medium is a sulphuric acid soln.
6. method according to claim 1 is characterized in that the manganese oxide ore granularity accounts for 40～90% for＜0.074mm.
7. method according to claim 1 is characterized in that described manganese oxide ore can be a marine manganese nodule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117548A CN1037786C (en) | 1994-10-28 | 1994-10-28 | Polyhydroxy aromatic acid reduction leaching method for manganese oxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117548A CN1037786C (en) | 1994-10-28 | 1994-10-28 | Polyhydroxy aromatic acid reduction leaching method for manganese oxide ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1126247A CN1126247A (en) | 1996-07-10 |
| CN1037786C true CN1037786C (en) | 1998-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94117548A Expired - Fee Related CN1037786C (en) | 1994-10-28 | 1994-10-28 | Polyhydroxy aromatic acid reduction leaching method for manganese oxide ore |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54155923A (en) * | 1978-05-31 | 1979-12-08 | Agency Of Ind Science & Technol | Wet treating method for manganese nodule |
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1994
- 1994-10-28 CN CN94117548A patent/CN1037786C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54155923A (en) * | 1978-05-31 | 1979-12-08 | Agency Of Ind Science & Technol | Wet treating method for manganese nodule |
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| CN1126247A (en) | 1996-07-10 |
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