CN1037785C - Arylamine reduction leaching method for marine manganese nodule - Google Patents
Arylamine reduction leaching method for marine manganese nodule Download PDFInfo
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- CN1037785C CN1037785C CN94117547A CN94117547A CN1037785C CN 1037785 C CN1037785 C CN 1037785C CN 94117547 A CN94117547 A CN 94117547A CN 94117547 A CN94117547 A CN 94117547A CN 1037785 C CN1037785 C CN 1037785C
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- Prior art keywords
- manganese nodule
- leaching
- acid
- marine
- reduction leaching
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- 239000011572 manganese Substances 0.000 title claims abstract description 45
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 43
- 238000002386 leaching Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 13
- -1 arylamine compound Chemical class 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 230000002829 reductive effect Effects 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
An arylamine reduction leaching method of ocean manganese nodule relates to a method for extracting valuable metals from ocean manganese nodule by reduction leaching. It is characterized by that it adopts arylamine compound as leaching agent. At normal temperature and pressure, the marine manganese nodule is crushed into pulp, acid and arylamine compound are added, the pulp is leached directly in a conventional leaching tank, the solid and the liquid are separated, the leaching residue is discarded, and the leaching liquid is sent to metal recovery. The reaction of reducing and acid-leaching the marine manganese nodule with arylamine compound has good dynamic characteristic, fast reaction speed, high leaching rate and simple equipment, so that the method has practical application prospect.
Description
The present invention relates to a kind ofly make reductive agent leaches valuable metal in the marine manganese nodule in acidic medium method with aromatic amine compounds.
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 inlay, metals such as copper, cobalt compose with the isomorph form and exist in the oxide mineral of manganese, iron, therefore, reclaim valuable metals such as nickel, steel, 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.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 aromatic amine compounds that adopts to make reductive agent directly leaches marine manganese nodule in acidic medium method.
Aromatic amine compounds as aniline, Ursol D, mphenylenediamine, O-Phenylene Diamine etc., all is stronger organic reducing agent, can be with MnO in acid solution (can be the acid solution of sulfuric acid, hydrochloric acid, nitric acid etc.)
2Reduction of dissolved.With aniline is example, uses H
2SO
4Make acidic medium, leach reaction:
Ni in obvious 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 arylamine reduction leaching method of marine manganese nodule, comprise that ore is pulverized, slurrying, it is characterized in that: adopt aniline, mphenylenediamine, O-Phenylene Diamine to make the reduction leaching agent, in the acidic medium that is selected from sulfuric acid, hydrochloric acid, nitric acid, leach, processing condition are: the manganese nodule granularity is＜0.5mm, ore pulp liquid-solid ratio (weight ratio) is 3: 1～10: 1, the acid consumption is 0.5～1.5g/g manganese nodule, the aromatic amine compounds consumption is 0.1～0.5g/g manganese nodule, extraction time is 10～30 minutes, and stirring velocity is 600～1500 rev/mins.
Adopt aromatic amine compounds to make reductive agent and in acidic medium, leach marine manganese nodule, 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, leach exothermic heat of reaction and make the slurry temperature rising can activate leaching process, need not cool off, in conventional leaching vat, can realize leaching process under the normal temperature and pressure, 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＜0.074mm accounts for 40～90% marine manganese nodule material and 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 aromatic amine compounds simultaneously, the acid consumption is 0.5～1.5g/g manganese nodule (consumption of acid depends on the grade of valuable metal in sour kind and the manganese nodule), reduction leaching agent consumption is 0.1～0.5g/g manganese nodule, 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 M10.35%, Cu0.40%, Ni0.66%, Co0.32% for＜0.074mBm.Extraction temperature is 19 ℃, and pressure is normal atmosphere.Experimental result sees Table 1.
Embodiment 2
The marine manganese nodule raw meal particle size that crushes accounts for 72%, contains Mn14.21%, CuO.34%, Ni0.58%, Co0.27% for＜0.074mm.Extraction temperature is 24 ℃, and pressure is normal atmosphere.Experimental result sees Table 2.
Embodiment 3
The marine manganese nodule raw meal particle size that crushes accounts for 65%, contains Mn10.35%, CuO40%, Ni0.66%, Co0.32% for＜0.074mm.21 ℃ of extraction temperatures, pressure are normal atmosphere.Experimental result sees Table 3.
Table 1
Annotate: reductive agent is an aniline 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 O-Phenylene Diamine 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 mphenylenediamine 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 (5)
1. the arylamine reduction leaching method of a marine manganese nodule comprises that ore is pulverized, slurrying, it is characterized in that: adopt aniline, mphenylenediamine, O-Phenylene Diamine to make the reduction leaching agent, in the acidic medium that is selected from sulfuric acid, hydrochloric acid, nitric acid, leach,
Processing condition are: the granularity of marine manganese nodule is＜0.5mm,
Ore pulp liquid-solid ratio (weight ratio) is 3: 1～10: 1,
The acid consumption is 0.5～1.5g/g manganese nodule,
Reduction leaching agent consumption is 0.1～0.5g/g manganese nodule,
Extraction time is 10～30 minutes,
Stirring velocity is 600～1500 rev/mins.
2. method according to claim 1 is characterized in that described reduction leaching agent is an aniline.
3. method according to claim 1 is characterized in that described reduction leaching agent is same phenylenediamine.
4. method according to claim 1 is characterized in that described reduction leaching agent is an O-Phenylene Diamine.
5. method according to claim 1 is characterized in that described acidic medium is a sulphuric acid soln.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117547A CN1037785C (en) | 1994-10-28 | 1994-10-28 | Arylamine reduction leaching method for marine manganese nodule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94117547A CN1037785C (en) | 1994-10-28 | 1994-10-28 | Arylamine reduction leaching method for marine manganese nodule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1126246A CN1126246A (en) | 1996-07-10 |
| CN1037785C true CN1037785C (en) | 1998-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94117547A Expired - Fee Related CN1037785C (en) | 1994-10-28 | 1994-10-28 | Arylamine reduction leaching method for marine manganese nodule |
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| Country | Link |
|---|---|
| CN (1) | CN1037785C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046965C (en) * | 1994-10-28 | 1999-12-01 | 北京矿冶研究总院 | Phenol reduction leaching method of manganese oxide ore |
| CN108910956A (en) * | 2018-07-17 | 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 aniline reduction electrolytic manganese anode mud |
| CN109097578A (en) * | 2018-07-17 | 2018-12-28 | 重庆上甲电子股份有限公司 | A method of manganese carbonate is produced using aniline reduction electrolytic manganese anode mud |
| CN108910958A (en) * | 2018-07-17 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of manganese sulfate is produced using aniline reduction electrolytic manganese anode mud |
| CN115140777B (en) * | 2022-07-13 | 2023-04-25 | 重庆上甲电子股份有限公司 | Method for producing ferromanganese composite material for soft magnetic by utilizing ocean manganese nodule |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992004474A1 (en) * | 1990-09-12 | 1992-03-19 | Cameco Corporation | Removal of molybdenum from uranium-bearing solutions |
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1994
- 1994-10-28 CN CN94117547A patent/CN1037785C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992004474A1 (en) * | 1990-09-12 | 1992-03-19 | Cameco Corporation | Removal of molybdenum from uranium-bearing solutions |
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| Publication number | Publication date |
|---|---|
| CN1126246A (en) | 1996-07-10 |
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