CN1126244A - Phenol reduction leaching method of manganese oxide ore - Google Patents
Phenol reduction leaching method of manganese oxide ore Download PDFInfo
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- CN1126244A CN1126244A CN 94117545 CN94117545A CN1126244A CN 1126244 A CN1126244 A CN 1126244A CN 94117545 CN94117545 CN 94117545 CN 94117545 A CN94117545 A CN 94117545A CN 1126244 A CN1126244 A CN 1126244A
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Abstract
A phenol reduction leaching method of manganese oxide ores relates to a method for extracting valuable metals from manganese oxide ores, in particular to ocean manganese nodules by reduction leaching. It is characterized by that it adopts polyhydric phenol compound as leaching agent. Crushing manganese oxide ore into pulp at normal temperature and normal pressure, adding acid and polyphenol compounds, directly leaching in a conventional leaching tank, carrying out solid-liquid separation, discarding leaching residues, and sending the leaching solution to metal recovery. The reaction of reducing and acid leaching manganese oxide ore by using the polyphenol has good dynamic characteristics, high reaction speed, high leaching rate and simple equipment, so the method has practical application prospect.
Description
The present invention relates to a kind ofly make reductive agent with polyhydric phenols and in acidic medium, leach the particularly method of valuable metal in the marine manganese nodule of manganese oxide ore.
Marine manganese nodule is a kind of very huge prospect resource, and each ocean manganese nodule resource reserve of the world is 5,000 hundred million tons according to estimates.The treatment process of marine manganese nodule roughly can be 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, 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 (being mainly MnO2) and dilute acid soln be difficult to reaction, needs usually 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.The intermediates that russian patent (SU1715873,1993) discloses the natural sulfide enrichment of a kind of usefulness are made the manganese nodule acidleach method of reductive agent, and this method needs ore pulp heating (90-100 ℃), and extraction time is grown (2 hours).
In order to overcome the deficiencies in the prior art, be implemented under the normal temperature and pressure conditions, in the leaching vat of routine, leach, do not need ore pulp is heated or cooling and the fast purpose of leaching velocity, provide a kind of polyhydric phenols that adopts to make reductive agent directly leaches manganese oxide ore in acidic medium method.
Polyhydric phenols, as Resorcinol, pyrocatechol, pyrogallol, Phloroglucinol and naphthalenediol etc., it all is stronger organic reducing agent, can be in acid solution (can be the acid solution of sulfuric acid, hydrochloric acid, nitric acid etc.) by the MnO2 oxidation, simultaneously with among the MnO2+4 valency Mn are reduced at a low price manganese and it are dissolved in acid solution, Ni in while manganese, the iron oxide lattice, Cu, the high oxide of Co etc. also will be reduced dissolving.
The objective of the invention is to realize by the following technical solutions.
A kind of phenol reductin leaching method of manganese oxide ore, comprise that ore is pulverized, slurrying, it is characterized in that: adopt polyhydric phenols to make the reduction leaching agent, leach in acidic medium, processing condition are: the granularity＜0.5mm of manganese oxide ore, ore pulp liquid-solid ratio 3: 1～10: 1, acid consumption 0.5～1.5g/g manganese oxide ore, polyhydric phenols consumption 0.1～0.5g/g manganese oxide, extraction time 10～30 minutes, stirring velocity is 600～1500 rev/mins.
Adopt polyhydric phenols 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 minutes, 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, therefore has prospects for commercial application.
The present invention is further illustrated below in conjunction with embodiment.
Implementation method of the present invention is that the maximum particle size after pulverizing is no more than 0.5mm, preferably-manganese oxide ore material that 0.074mm accounts for 40-90% sizes mixing, the liquid-solid ratio that makes slip is 3: 1-10: 1, in normal temperature (room temperature), under normal pressure (room atmosphere pressure) condition, add acid and polyhydric phenols simultaneously, the acid consumption is 0.5-1.5g/g manganese oxide ore (consumption of acid depends on the grade of valuable metal in sour kind and the manganese oxide ore), the polyhydric phenols consumption is the 0.1-0.5g/g manganese oxide ore, stirring velocity is 600-1500 rev/min, after in conventional (uncovered) leaching vat, directly leaching 10-30 minute, carry out liquid-solid separation, abandon and soak slag, leach liquor gives next step metal recovery.
Embodiment 1
The marine manganese nodule material grain that crushes accounts for 65%, contains M10.35%, Cu0.40%, Ni0.66%, Co0.32% for-0074mm.Extraction temperature is 20, and pressure is normal atmosphere.Experimental result sees Table 1.
Embodiment 2
The marine manganese nodule material grain that crushes accounts for 72%, contains Mn14.21%, Co0.34%, Ni0.58%, Co0.27% for-0074mm.Extraction temperature is 23 ℃, and pressure is normal atmosphere.Experimental result sees Table 2.
Embodiment 3
The marine manganese nodule material grain that crushes accounts for 90% for-0074mm, contains Mn12.62%, and 20 ℃ of extraction temperatures, pressure are normal atmosphere.Experimental result sees Table 3.
Table 1
Annotate: reductive agent is a pyrogallol 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 Resorcinol 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 a pyrocatechol 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 phenol reductin leaching method of a manganese oxide ore comprises that ore is pulverized, slurrying, it is characterized in that: adopt the polyhydroxy aromatic compounds to make the reduction leaching agent, in acidic medium, leach,
Processing condition are: the granularity of manganese oxide ore is＜0.5mm,
The ore pulp liquid-solid ratio is 3: 1～10: 1,
The acid consumption is 0.5～1.5g/g manganese oxide ore,
The polyhydric phenols consumption is 0.1～0.5g/g manganese oxide ore,
Extraction time is 10～30 minutes,
Stirring velocity is 600～1500 rev/mins.
2. method according to claim 1 is characterized in that described polyhydric phenols is a pyrogallol.
3. method according to claim 1 is characterized in that described polyhydric phenols is a Resorcinol.
4. method according to claim 1 is characterized in that described polyhydric phenols is a pyrocatechol.
5. method according to claim 1 is characterized in that preferably sulfuric acid of described acidic medium.
6. method according to claim 1, the leaching granularity that it is characterized in that manganese oxide ore 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 (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94117545 CN1126244A (en) | 1994-10-28 | 1994-10-28 | Phenol reduction leaching method of manganese oxide ore |
| CN95106747A CN1046965C (en) | 1994-10-28 | 1995-06-22 | Phenol reduction leaching method of manganese oxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94117545 CN1126244A (en) | 1994-10-28 | 1994-10-28 | Phenol reduction leaching method of manganese oxide ore |
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| CN1126244A true CN1126244A (en) | 1996-07-10 |
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| CN 94117545 Pending CN1126244A (en) | 1994-10-28 | 1994-10-28 | Phenol reduction leaching method of manganese oxide ore |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618728A (en) * | 2011-10-10 | 2012-08-01 | 云南建水锰矿有限责任公司 | Method for producing manganese sulfate by leaching manganese alloy slag under normal pressure |
| CN103789542A (en) * | 2014-01-20 | 2014-05-14 | 中南大学 | Wet-process reduction leaching method of manganese oxide mineral |
| CN105903561A (en) * | 2016-04-16 | 2016-08-31 | 北京矿冶研究总院 | Method for recovering manganese from cobalt-manganese multi-metal oxidized ore |
| CN108910957A (en) * | 2018-07-18 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of soft magnetism mangano-manganic oxide is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN108910959A (en) * | 2018-07-18 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of manganese sulfate is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN109095503A (en) * | 2018-07-18 | 2018-12-28 | 重庆上甲电子股份有限公司 | A method of manganese carbonate is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN116621225A (en) * | 2023-07-12 | 2023-08-22 | 重庆上甲电子股份有限公司 | Flux and method for recovering manganese from perillaldehyde waste residues and application of flux and method for preparing trimanganese tetroxide for soft magnetism |
| CN116835971A (en) * | 2023-07-12 | 2023-10-03 | 华东师范大学 | Method for preparing high saturation magnetic induction density manganese-zinc ferrite material by using manganese waste residues and zinc waste residues |
-
1994
- 1994-10-28 CN CN 94117545 patent/CN1126244A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618728A (en) * | 2011-10-10 | 2012-08-01 | 云南建水锰矿有限责任公司 | Method for producing manganese sulfate by leaching manganese alloy slag under normal pressure |
| CN103789542A (en) * | 2014-01-20 | 2014-05-14 | 中南大学 | Wet-process reduction leaching method of manganese oxide mineral |
| CN103789542B (en) * | 2014-01-20 | 2015-10-07 | 中南大学 | A kind of wet reducing leaching method of manganese oxide mineral |
| CN105903561A (en) * | 2016-04-16 | 2016-08-31 | 北京矿冶研究总院 | Method for recovering manganese from cobalt-manganese multi-metal oxidized ore |
| CN105903561B (en) * | 2016-04-16 | 2018-06-29 | 北京矿冶研究总院 | Method for recovering manganese from cobalt-manganese multi-metal oxidized ore |
| CN108910957A (en) * | 2018-07-18 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of soft magnetism mangano-manganic oxide is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN108910959A (en) * | 2018-07-18 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of manganese sulfate is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN109095503A (en) * | 2018-07-18 | 2018-12-28 | 重庆上甲电子股份有限公司 | A method of manganese carbonate is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN116621225A (en) * | 2023-07-12 | 2023-08-22 | 重庆上甲电子股份有限公司 | Flux and method for recovering manganese from perillaldehyde waste residues and application of flux and method for preparing trimanganese tetroxide for soft magnetism |
| CN116835971A (en) * | 2023-07-12 | 2023-10-03 | 华东师范大学 | Method for preparing high saturation magnetic induction density manganese-zinc ferrite material by using manganese waste residues and zinc waste residues |
| CN116621225B (en) * | 2023-07-12 | 2024-01-23 | 重庆上甲电子股份有限公司 | Flux and method for recovering manganese from perillaldehyde waste residues and application of flux and method for preparing trimanganese tetroxide for soft magnetism |
| CN116835971B (en) * | 2023-07-12 | 2024-02-27 | 华东师范大学 | Method for preparing high saturation magnetic induction density manganese-zinc ferrite material by using manganese waste residues and zinc waste residues |
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