CN1046965C - Phenol reduction leaching method of manganese oxide ore - Google Patents
Phenol reduction leaching method of manganese oxide ore Download PDFInfo
- Publication number
- CN1046965C CN1046965C CN95106747A CN95106747A CN1046965C CN 1046965 C CN1046965 C CN 1046965C CN 95106747 A CN95106747 A CN 95106747A CN 95106747 A CN95106747 A CN 95106747A CN 1046965 C CN1046965 C CN 1046965C
- Authority
- CN
- China
- Prior art keywords
- leaching
- manganese oxide
- oxide ore
- manganese
- phenolic compound
- 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.)
- Expired - Fee Related
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
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 phenolic compound as reducing agent. Crushing manganese oxide ore into pulp at normal temperature and normal pressure, adding acid and phenolic compounds, directly leaching in a conventional leaching tank, carrying out solid-liquid separation, discarding leaching residues, and delivering the leaching solution to metal recovery. The reaction of reducing acid and leaching manganese oxide ore by phenol 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 phenolic compound 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 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 the patent of USSR (Union of Soviet Socialist Republics) (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, the invention provides a kind of phenolic compound that adopts and make reductive agent directly leaches manganese oxide ore in acidic medium method.
Phenolic compound, is the Resorcinol that proposes in 94117545.6 " a kind of phenol reductin leaching method of manganese oxide ore " as the applicant at application number, pyrocatechol, pyrogallol, polyhydric phenols such as Phloroglucinol and naphthalenediol, it all is stronger organic reducing agent, at acid solution (can be sulfuric acid, hydrochloric acid, the acid solution of nitric acid etc.) can be in 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, while manganese, Ni in the iron oxide lattice, Cu, the high oxide of Co etc. also will be reduced dissolving.Confirm that through further experiment phenol also has the performance of above-mentioned polyphenol in the phenolic compound.
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 phenolic compound 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, phenolic compound consumption 0.1～0.5g/g manganese oxide, extraction time 10～30 minutes, stirring velocity is 600～1500 rev/mins.
Phenolic compound of the present invention comprises phenol, Resorcinol, pyrogallol, Phloroglucinol and naphthalenediol.
Adopt phenolic compound 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 phenolic compound 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 phenolic compound consumption is the 0.1-0.5g/g manganese oxide ore, stirring velocity is 600-1500 rev/min, in conventional leaching vat, directly leach after 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 raw meal particle size that crushes accounts for 65%, contains Mn10.35%, Cu0.40%, Ni0.66%, Co0.32% for＜0.074nm.Extraction temperature is 20 ℃, and pressure is normal atmosphere.Adopt pyrogallol to make reductive agent, experimental result sees Table 1.
Embodiment 2
The marine manganese nodule raw meal particle size that crushes accounts for 72%, contains Mn14.21%, Cu0.34%, Ni0.58%, Co0.27% for＜0.074mm.Extraction temperature is 23 ℃, and pressure is normal atmosphere.Adopt Resorcinol to make reductive agent, experimental result sees Table 2.
Example 3
The manganese oxide ore raw meal particle size that crushes accounts for 90% for＜0.074mm, contains Mn12.62%, and 20 ℃ of extraction temperatures, pressure are normal atmosphere.Adopt pyrocatechol to make reductive agent, experimental result sees Table 3.
Embodiment 4
The marine manganese nodule raw meal particle size that crushes accounts for 72%, contains Mn14.21%, Cu0.34%, Ni0.58%, Co0.27% for＜0.074mm.25 ℃ of extraction temperatures, pressure are normal atmosphere.Adopt phenol to do also agent.Experimental result sees Table 4.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.
Table 4
Annotate: reductive agent is a phenol 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.
Claims (8)
1. the phenol reductin leaching method of a manganese oxide ore comprises that ore is pulverized, slurrying, it is characterized in that: adopt phenolic compound 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 phenolic compound 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 phenolic compound is a phenol.
3. method according to claim 1 is characterized in that described phenolic compound is a pyrogallol.
4. method according to claim 1 is characterized in that described phenolic compound is a Resorcinol.
5. method according to claim 1 is characterized in that described phenolic compound is a pyrocatechol.
6. method according to claim 1 is characterized in that described acidic medium is a sulfuric acid.
7. method according to claim 1, the leaching granularity that it is characterized in that manganese oxide ore accounts for 40-90% for＜0.074mm.
8. 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 |
|---|---|---|---|
| CN95106747A CN1046965C (en) | 1994-10-28 | 1995-06-22 | Phenol reduction leaching method of manganese oxide ore |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117545.6 | 1994-10-28 | ||
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1155586A CN1155586A (en) | 1997-07-30 |
| CN1046965C true CN1046965C (en) | 1999-12-01 |
Family
ID=25743522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95106747A Expired - Fee Related CN1046965C (en) | 1994-10-28 | 1995-06-22 | Phenol reduction leaching method of manganese oxide ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046965C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534209B (en) * | 2012-02-23 | 2014-05-07 | 中南大学 | Reduction leaching method of manganese oxide ores |
| CN102560107A (en) * | 2012-02-23 | 2012-07-11 | 中南大学 | Reduction leaching method for manganese oxide |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4872909A (en) * | 1988-08-08 | 1989-10-10 | The United States Of America, As Represented By The Secretary Of The Interior | Process for acid leaching of manganese oxide ores aided by hydrogen peroxide |
| CN1126246A (en) * | 1994-10-28 | 1996-07-10 | 北京矿冶研究总院 | Arylamine reduction leaching method for marine manganese nodule |
-
1995
- 1995-06-22 CN CN95106747A patent/CN1046965C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4872909A (en) * | 1988-08-08 | 1989-10-10 | The United States Of America, As Represented By The Secretary Of The Interior | Process for acid leaching of manganese oxide ores aided by hydrogen peroxide |
| CN1126246A (en) * | 1994-10-28 | 1996-07-10 | 北京矿冶研究总院 | Arylamine reduction leaching method for marine manganese nodule |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1155586A (en) | 1997-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11459636B2 (en) | Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore | |
| Cote | Hydrometallurgy of strategic metals | |
| US7473413B2 (en) | Method for recovering metal values from metal-containing materials using high temperature pressure leaching | |
| CN1325668C (en) | Leaching method for complicated cupric sulfide aurin ore | |
| CN1333089C (en) | Method for processing cobalt copper alloy | |
| AU2001277182A1 (en) | Method for Recovering Copper from Sulfide Ore Materials Using High Temperature Pressure Leaching, Solvent Extraction and Electrowinning | |
| CN102560100A (en) | Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy | |
| EP0028634A1 (en) | Method for producing cobalt metal powder. | |
| CN113265532A (en) | Method for leaching nickel-ammonia solution from nickel-iron alloy by wet method and application | |
| CN112458280A (en) | Method for extracting valuable metals by leaching low grade nickel matte with acidic etching solution | |
| CN1126244A (en) | Phenol reduction leaching method of manganese oxide ore | |
| CN117926027A (en) | Comprehensive utilization method of laterite nickel ore | |
| CN1046965C (en) | Phenol reduction leaching method of manganese oxide ore | |
| CN1037785C (en) | Arylamine reduction leaching method for marine manganese nodule | |
| CN1037784C (en) | Ascorbic acid reduction leaching method of manganese oxide ore | |
| AU672200B2 (en) | Process for the separation of cobalt from nickel | |
| CN110564961B (en) | Method for reducing leached hydrocobaltite | |
| CN103526020A (en) | Method for lixiviating manganese ore containing manganous silicate | |
| CN1037786C (en) | Polyhydroxy aromatic acid reduction leaching method for manganese oxide ore | |
| CN113735179A (en) | Method for preparing high-purity ferric sulfate by using ferro-manganese | |
| CN113621835A (en) | Method for efficiently removing molybdenum based on extraction-precipitation combination | |
| CN111004921A (en) | Method for recovering copper in scrap copper smelting slag | |
| CN115786602B (en) | Method for preparing hematite by using iron-aluminum slag | |
| CN114921649B (en) | Method for recycling soluble tungstate in tungsten-containing waste | |
| US6139602A (en) | Carbon catalyzed leaching of metal-containing ores |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |