CN1037784C - Ascorbic acid reduction leaching method of manganese oxide ore - Google Patents
Ascorbic acid reduction leaching method of manganese oxide ore Download PDFInfo
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- CN1037784C CN1037784C CN94117546A CN94117546A CN1037784C CN 1037784 C CN1037784 C CN 1037784C CN 94117546 A CN94117546 A CN 94117546A CN 94117546 A CN94117546 A CN 94117546A CN 1037784 C CN1037784 C CN 1037784C
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- manganese oxide
- oxide ore
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- manganese
- leaching
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Abstract
A reduction leaching method of manganese oxide ore and ascorbic acid relates to a method for extracting valuable metals from manganese oxide ore, in particular to ocean manganese nodule by reduction leaching. The method is characterized in that ascorbic acid is used as a reduction leaching agent, manganese oxide ore materials are pulped at normal temperature and normal pressure, acid and ascorbic acid are added, and the manganese oxide ore materials are directly leached in a conventional leaching tank. The reaction of reducing and acid leaching manganese oxide ore by ascorbic acid has good dynamic characteristics, high reaction speed, high leaching rate and simple equipment, and is an effective manganese oxide ore treatment method.
Description
The present invention relates to a kind of ascorbic acid 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 xitix 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 ascorbic acid reduction leaching method of manganese oxide ore, comprise that ore is pulverized, slurrying, it is characterized in that adopting xitix to make the reduction leaching agent, in the acidic medium that is selected from sulfuric acid, hydrochloric acid, nitric acid, leach, processing condition: the granularity＜0.5mm of manganese oxide ore, ore pulp liquid-solid ratio (weight ratio) is 3: 1～10: 1, acid consumption: 0.5～1.5g/g manganese oxide ore, xitix consumption: 0.1～0.5g/g manganese oxide ore, extraction time: 10～15 minutes, stirring velocity: 600～1500 rev/mins.
Adopt xitix 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 is all more than 90%, the dynamics that leaches reaction is good, leaching velocity is fast, can finish leaching process at 10-30 minute, the medicine consumption rationally, do not need the ore pulp heating is leached exothermic heat of reaction and made the slurry temperature rising can activate leaching process, need not cool off, reacting no obnoxious flavour emits, can realize leaching process under the normal temperature and pressure in conventional leaching vat, equipment is simple, is a kind of effective manganese oxide ore treatment process therefore.
Xitix has another name called vitamins C, owing to contain enediol in its molecular formula
Functional group is a kind of 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.
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, preferably＜0.074mm accounts for 40～90% manganese oxide ore material and sizes mixing, and making the liquid-solid ratio (weight ratio) of slip is 3: 1～10: 1, simultaneously, add acid and xitix, sour consumption is 0.2～1.5g/g manganese oxide ore, and stirring velocity is 600～1500 rev/mins, after in conventional (uncovered) leaching vat, directly leaching 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 72% for＜0.074mm, and the valuable metal grade is Mn:14.21%, CuO.34%, Ni0.58%, Co0.27%.Extraction temperature is 23 ℃, and pressure is normal atmosphere.
Experimental result sees Table 1
Embodiment 2
The manganese oxide ore granularity that crushes accounts for 90%, contains Mn12.62% for＜0.074mm.Extraction temperature is 26 ℃, and pressure is normal atmosphere.
Experimental result sees Table 2.
Table 1
Annotate: reductive agent is an xitix 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 an xitix in the table, consumption unit: the g/g manganese oxide ore,
| Experiment condition as a result | Metal leaching rate (%) | Soak cinder grade (%) |
| Mn | Mn | |
| Reductive agent consumption: 0.4 sulfuric acid consumption: 1.5 liquid-solid ratioes: 10: 1 stirring velocitys: 1000 extraction times: 10 | 90.58 | 3.39 |
| Reductive agent consumption: 0.1 sulfuric acid consumption: 1.2 liquid-solid ratioes: 6: 1 stirring velocitys: 800 extraction times: 25 | 97.64 | 0.54 |
Acid is sulfuric acid, consumption unit: the g/g manganese oxide ore,
Stirring velocity unit: rev/min,
Extraction time unit: minute.
Claims (4)
1. the ascorbic acid reduction leaching method of a manganese oxide ore comprises ore powder essence, slurrying, it is characterized in that: adopt xitix to 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 xitix 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 acid solution is a sulphuric acid soln.
3. method according to claim 1 is characterized in that the manganese oxide ore granularity accounts for 40～90% for＜0.074mm.
4. method according to claim 1 is characterized in that described manganese oxide ore is a marine manganese nodule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117546A CN1037784C (en) | 1994-10-28 | 1994-10-28 | Ascorbic acid reduction leaching method of manganese oxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117546A CN1037784C (en) | 1994-10-28 | 1994-10-28 | Ascorbic acid reduction leaching method of manganese oxide ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1126245A CN1126245A (en) | 1996-07-10 |
| CN1037784C true CN1037784C (en) | 1998-03-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94117546A Expired - Fee Related CN1037784C (en) | 1994-10-28 | 1994-10-28 | Ascorbic acid reduction leaching method of manganese oxide ore |
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| CN (1) | CN1037784C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757269A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757444B (en) * | 2013-12-29 | 2015-05-13 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757429A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| DE102018101060A1 (en) | 2018-01-18 | 2019-07-18 | CHT Germany GmbH | Process for removing manganese oxide deposits from textile surfaces |
| DE102017125010A1 (en) | 2017-10-25 | 2019-04-25 | CHT Germany GmbH | Process for removing manganese oxide deposits from textile surfaces |
| WO2019081290A1 (en) | 2017-10-25 | 2019-05-02 | CHT Germany GmbH | Method for removing manganese oxide deposits from textile surfaces |
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1994
- 1994-10-28 CN CN94117546A patent/CN1037784C/en not_active Expired - Fee Related
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| CN1126245A (en) | 1996-07-10 |
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