CN103757274A - Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid - Google Patents
Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid Download PDFInfo
- Publication number
- CN103757274A CN103757274A CN201310736426.9A CN201310736426A CN103757274A CN 103757274 A CN103757274 A CN 103757274A CN 201310736426 A CN201310736426 A CN 201310736426A CN 103757274 A CN103757274 A CN 103757274A
- Authority
- CN
- China
- Prior art keywords
- leaching
- sulfuric acid
- waste residue
- manganese carbonate
- carbonate ore
- 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.)
- Pending
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002386 leaching Methods 0.000 title claims abstract description 55
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 26
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 26
- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 26
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 26
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract 3
- 239000011572 manganese Substances 0.000 claims description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003978 infusion fluid Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明介绍的硫酸浸出碳酸锰矿产生的废渣的再浸出方法，是将硫酸浸出碳酸锰矿产生的废渣磨细到粒径≤180目后和≤1.5mm酒糟一并加入耐压、耐硫酸和硝酸腐蚀的反应釜中，加入硫酸和硝酸的混合溶液，并在密闭条件下进行搅拌浸出。The re-leaching method of the waste residue produced by sulfuric acid leaching of manganese carbonate ore introduced by the present invention is to grind the waste residue produced by sulfuric acid leaching of manganese carbonate ore to a particle size of ≤180 mesh and add pressure-resistant, sulfuric acid and nitric acid corrosion resistance together with distiller grains of ≤1.5mm Add the mixed solution of sulfuric acid and nitric acid into the reaction kettle, and carry out stirring and leaching under airtight conditions.
Description
Technical field
The present invention relates to a kind of leaching method again of the waste residue of sulfuric acid leaching manganese carbonate ore generation.
Background technology
Manganese carbonate ore is the important source material of producing the materials such as manganese metal, manganous sulfate, Manganse Dioxide, manganous nitrate.Wet processing is the main technique of producing above-mentioned materials, leaches the operation operation that is absolutely necessary in this technique.In producing the wet processing of manganese metal, manganous sulfate, Manganse Dioxide, substantially adopt sulfuric acid leaching system.Owing to containing certain MnO in manganese carbonate ore
2, MnO
2be insoluble to sulfuric acid, cause while adopting sulfuric acid leaching manganese carbonate ore, the leaching yield of metal target manganese is not high, causes the wasting of resources.Sulfuric acid leaching manganese carbonate ore produces at present waste residue generation and volume of cargo in storage are all very large, and waste residue, containing manganese approximately 6%, has recovery value again.Adopt wet processing can rely on existing technique, the facilities and equipment of the enterprise that produces this class waste residue to its recycling, than being easier to, implement, leaching operation is the requisite operation of wet processing, develops thus that leaching yield is high, leaching velocity is fast, energy consumption is low, can have larger practical value with the leaching method again that produces the waste residue that the existing technique of the enterprise of this class waste residue, sulfuric acid leaching manganese carbonate ore that facilities and equipment match produces.
Summary of the invention
The recycling problem of the waste residue producing for current sulfuric acid leaching manganese carbonate ore, the object of the invention is to find that a kind of leaching yield is high, leaching velocity is fast, energy consumption is low, can with the leaching method again that produces the waste residue that the existing technique of the enterprise of this class waste residue, sulfuric acid leaching manganese carbonate ore that facilities and equipment match produces, it is characterized in that the waste residue that sulfuric acid leaching manganese carbonate ore is produced be milled down to particle diameter≤180 order after and≤1.5mm vinasse add in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion in the lump.The mixing solutions that adds sulfuric acid and nitric acid, and carry out in confined conditions agitation leach.After leaching finishes, the slurry of emitting in reactor carries out solid-liquid separation, obtains required infusion solution.The infusion solution obtaining is for preparing the solution that leaches manganese carbonate ore.Starting point concentration for the mixing solutions sulfuric acid that leaches is 0.5mol/L～1mol/L, and the starting point concentration of nitric acid is 2g/L～10g/L.The add-on of sulfuric acid is by 100%～105% of the theoretical amount that in waste residue, all manganese leaches.The add-on of vinasse is counted MnO in waste residue with butt
2100%～130% of quality.The temperature of whole leaching process is 40 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min.Leached mud washes with water, and washing water are used for preparing sulphuric acid soln and leach for waste residue.Waste residue after washing send slag field to deposit.
The object of the present invention is achieved like this: in waste residue, can leach element is mainly manganese and iron, is substantially respectively MnO
2, Mn (OH)
2and Fe
2o
3state.Airtight and have under the condition that vinasse and nitric acid exists, mainly there is following chemical reaction in sulfuric acid leaching waste residue:
nC
6H
10O
5?+?nH
2SO
4?=n(C
5H
11O
5)HSO
4
n(C
5H
11O
5)HSO
4?+?nH
2O?=?nC
6H
12O
6?+?nH
2SO
4
C
6H
12O
6?+?8HNO
3?=?8NO?+?6CO
2?+?10H
2O
nC
6H
10O
5?+?8nHNO
3?=?8nNO?+?6nCO
2?+?9nH
2O
3MnO
2?+?2NO?+?3H
2SO
4?=?3MnSO
4?+?2HNO
3?+?2H
2O
3Fe
2O
3?+?2NO?+?6H
2SO
4?=?6FeSO
4?+?2HNO
3?+?5H
2O
Total reaction is:
12nMnO
2?+?nC
6H
10O
5?+?12nH
2SO
4?=?12nMnSO
4?+?6nCO
2?+?17nH
2O
12nFe
2O
3?+?nC
6H
10O
5?+?24nH
2SO
4?=?24nFeSO
4?+?6nCO
2?+?29nH
2O
In addition Mn (OH)
2there is following chemical reaction:
Mn(OH)
2?+?H
2SO
4?=?MnSO
4?+?H
2O
Other organism in vinasse also generates NO, CO with nitric acid reaction
2and H
2o, the NO of generation and MnO
2(or Fe
2o
3) and H
2sO
4by previous reaction, generate MnSO
4(or FeSO
4), HNO
3and H
2o.
Because the speed of response of nitric acid and vinasse is very fast, the NO of generation and MnO
2reaction also very fast, accelerate thus whole leaching process, and realize MnO in waste residue
2leach more completely.As long as control the add-on of sulfuric acid well, just can reduce the amount that Fe enters leach liquor.Yet sulphuric acid very little, will affect the leaching yield of leaching velocity and Mn, so in order to guarantee the leaching yield of Mn, it is inevitable that Fe leaches.Enter the Fe of leach liquor
2+to follow-up deironing (generally adopting neutralization precipitation method), can have a negative impact.Because the manganese content in waste residue is lower, the Mn of leach liquor
2+concentration is on the low side, and the existing purification of leaching liquor system of the direct Entry Firm of leach liquor also exists process matching problem.The leach liquor that present method is obtained leaches the required sulphuric acid soln of manganese carbonate ore for preparing, and can, according to the needs of the existing technique of enterprise, adjust flexibly the Mn of manganese carbonate ore leach liquor
2+concentration, realizes the matched well with existing technique.What is more important, contains some amount Fe in the leach liquor that the present invention obtains
2+, enter after manganese carbonate ore leaching system, there is following chemical reaction:
2FeSO
4?+?MnO
2?+?2H
2SO
4?=?Fe
2(SO
4)
3?+?MnSO
4?+?2H
2O
By above-mentioned reaction during by original sulfuric acid leaching manganese carbonate ore, the MnO that can not leach
2leach more completely, no longer produce new high Mn content waste residue.Meanwhile, Fe
2+be oxidized to Fe
3+, be conducive to follow-up purification of leaching liquor process, be equipped with completely with existing technique.
Outstanding advantages of the present invention is: through above-mentioned series reaction, the Mn in the waste residue that final sulfuric acid leaching manganese carbonate ore produces leaches substantially completely, reduces the wasting of resources, also to subsequent solution, does not purify and brings difficulty; Leaching process temperature is lower, and speed of response is very fast, and energy consumption is lower; Leach the leaching system that returns to manganese carbonate ore night, can improve the leaching yield of manganese in manganese carbonate ore, avoid producing new high manganese waste slag; Process is carried out in confined conditions, the environmental pollution of having avoided NO to overflow and produce.
specific implementation method
embodiment 1: it is in the lining titanium pressure reaction still of 5L that the waste residue that 2000g sulfuric acid leaching manganese carbonate ore is produced (containing manganese 6.2%, iron 15.1%, particle diameter 180 orders) and 125g vinasse (≤1.5mm) add volume, adding sulfuric acid concentration is the mixing solutions 4.52L that 0.5mol/L, concentration of nitric acid are 2g/L, at 40 ℃～50 ℃, 2h is leached in airtight stirring (stirring velocity 80r/min), leaches the washing of carrying out liquid-solid separation and leached mud after finishing.According to the assay result of the leached mud after cleaning, the leaching yield of manganese is 96.8%.
Embodiment 2: it is in the lining titanium pressure reaction still of 50L that the waste residue that 20kg sulfuric acid leaching manganese carbonate ore is produced (containing manganese 6.2%, iron 15.1%, particle diameter 180 orders) and 1.5kg vinasse (≤1.5mm) add volume, adding sulfuric acid concentration is the mixing solutions 33L that 0.7mol/L, concentration of nitric acid are 5g/L, and at 60 ℃～70 ℃, 1h is leached in airtight stirring (stirring velocity 70r/min).After finishing, leaching carries out the washing of liquid-solid separation and leached mud.According to the assay result of the leached mud after cleaning, the leaching yield of manganese is 99.2%.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736426.9A CN103757274A (en) | 2013-12-29 | 2013-12-29 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736426.9A CN103757274A (en) | 2013-12-29 | 2013-12-29 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103757274A true CN103757274A (en) | 2014-04-30 |
Family
ID=50524588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310736426.9A Pending CN103757274A (en) | 2013-12-29 | 2013-12-29 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103757274A (en) |
-
2013
- 2013-12-29 CN CN201310736426.9A patent/CN103757274A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 杨明平等: "酒糟-硫酸浸取锰矿尾矿中锰制备硫酸锰工艺", 《无机盐工业》 * |
| 粟海锋等: "木薯酒糟还原浸出低品位软锰矿工艺研究", 《无机盐工业》 * |
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140430 |
|
| RJ01 | Rejection of invention patent application after publication |