CN103757247A - Method for leaching manganese carbonate ore - Google Patents
Method for leaching manganese carbonate ore Download PDFInfo
- Publication number
- CN103757247A CN103757247A CN201310736404.2A CN201310736404A CN103757247A CN 103757247 A CN103757247 A CN 103757247A CN 201310736404 A CN201310736404 A CN 201310736404A CN 103757247 A CN103757247 A CN 103757247A
- Authority
- CN
- China
- Prior art keywords
- leaching
- sulfuric acid
- concentration
- add
- leach
- 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
- 238000002386 leaching Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 31
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 19
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 14
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 14
- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 14
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000011572 manganese Substances 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000005260 corrosion Methods 0.000 claims abstract description 3
- 230000007797 corrosion Effects 0.000 claims abstract description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 17
- 235000011149 sulphuric acid Nutrition 0.000 claims description 13
- 239000001117 sulphuric acid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000013022 venting Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 2
- 239000003978 infusion fluid Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000008103 glucose 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
- 239000002245 particle Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 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
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002829 reductive effect Effects 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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明酸锰矿的浸出方法是将碳酸锰矿粉加入耐硫酸腐蚀和耐压的反应釜中，加入硫酸溶液和亚硫酸钠进行浸出。The leaching method of manganese acid ore of the present invention is to add manganese carbonate ore powder into a sulfuric acid corrosion-resistant and pressure-resistant reaction kettle, and add sulfuric acid solution and sodium sulfite for leaching.
Description
Technical field
The present invention relates to a kind of leaching method of manganese carbonate ore.
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.Although add Fe in Leaching Systems
2+, the reductive agent such as glucose can improve the leaching yield of manganese, but add Fe
2+can increase the weight of the burden that subsequent solution purifies, add the leaching velocity of glucose etc. slower, leach energy consumption and strengthen.The leaching method that exploitation leaching yield is high, leaching velocity is fast, energy consumption is low, do not increase the manganese carbonate ore of subsequent process burden has larger practical value.
Summary of the invention
The problem leaching for current 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, do not increase the leaching method of the manganese carbonate ore of subsequent process burden, it is characterized in that granularity≤180 object manganous carbonate breeze to add in sulfuric acid corrosion resistant and withstand voltage reactor, under the condition of reactor Exhaust Open and inlet close, add sulphuric acid soln to carry out the leaching of first stage, leach the CO producing
2from venting port, discharge.Work as CO
2when gas is substantially drained, add sodium sulfite solution, close venting port and carry out the airtight leaching of subordinate phase.After subordinate phase leaches and finishes, pass into industrial pure oxygen and be oxidized leaching, the slurry of emitting in reactor after oxidation finishes carries out solid-liquid separation, obtains required infusion solution.Leached mud washes with water, and washing water are used for preparing sulphuric acid soln for leaching, and the waste residue after washing send slag field to deposit.The sulfuric acid of leaching process add total amount be manganese in manganese carbonate ore theoretical consumption 105%～120%, sulfuric acid adds total amount to comprise newly to add contained sulfuric acid amount in the solution that returns to leaching process that sulfuric acid amount and subsequent process produce, washing water.Mn for the starting point concentration of the sulphuric acid soln sulfuric acid that leaches in required leach liquor
2+concentration is determined, is calculated as follows:
Mn in sulfuric acid concentration=required leach liquor
2+the sulphuric acid soln Mn of concentration-for leaching
2+starting point concentration (1)
Each concentration unit of calculating formula is mol/L.
For leach in the breeze weight of kg with for leaching the ratio in the volume of the solution of L, be called for short solid-to-liquid ratio and be calculated as follows definite:
Solid-to-liquid ratio=1: leach the required sulfuric acid total amount ÷ sulfuric acid concentration (2) of every kg breeze
In calculating formula, leach the required sulfuric acid total amount of every kg breeze in g, sulfuric acid concentration is in g/L.
The temperature of leaching process is 50 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min.The add-on of S-WAT is by MnO contained in breeze
2restore All is Mn
2+103%～120% of required theoretical amount.
The extraction time of first stage is 1h～2h.The extraction time of subordinate phase is 1h～2h.It is 0.5h～1.5h that leach liquor is carried out to oxidization time, and the relative pressure of oxidising process is 0.1Mpa～0.3MPa.
The object of the present invention is achieved like this: the object of the present invention is achieved like this: the leaching process of first stage is mainly by sulfuric acid and MnCO
3, FeCO
3, Fe
2o
3there is following chemical reaction:
MnCO
3 + H
2SO
4 = MnSO
4 + CO
2 + H
2O
FeCO
3 + H
2SO
4 = FeSO
4 + CO
2 + H
2O
Fe
2O
3 + 3H
2SO
4 = Fe
2(SO
4)
3 + 3H
2O
Fe
2(SO
4)
3 + 6H
2O = 2Fe(OH)
3 + 3H
2SO
4
In the first leaching stage, most MnCO
3leached and enter solution, part Fe is leached, and along with the carrying out of leaching process, the acidity of solution reduces, and enters the part Fe of solution
3+hydrolysis reaction occurs to be entered in leached mud.
In the second leaching stage, except proceeding, the reaction of first stage, MnO mainly to occur
2and Fe
3+reduction reaction:
MnO
2 + Na
2SO
3 + H
2SO
4 = MnSO
4 + Na
2SO
4 + H
2O
Fe
2(SO
4)
3 + Na
2SO
3 + H
2O = 2FeSO
4 +Na
2SO
4 + H
2SO
4
MnO
2 + 2FeSO
4 + 2H
2SO
4 = Fe
2(SO
4)
3 + MnSO
4 + 2H
2O
Due to Na
2sO
3reductibility stronger, MnO
2oxidisability also stronger, both are easy to occur chemical reaction, realize thus MnO
2leach more completely.Because reaction is carried out in confined conditions, Na
2sO
3the SO decompositing under acidic conditions
2by stirring, enter solution (SO
2in solution, have certain solubleness) and MnO
2reaction is consumed, and whole system is carried out under pressure-fired.
Because the reduction of subordinate phase is leached, the Fe in solution is partly Fe
2+form, unfavorable to follow-up deironing (generally adopting neutralization precipitation method), so pass into oxygen, be oxidized to Fe
3+.
Outstanding advantages of the present invention is: through above-mentioned series reaction, finally make the Mn in manganese carbonate ore substantially leach completely, improved the leaching yield of Mn, reduce the wasting of resources, also to subsequent solution, do not purify and bring difficulty, thereby save production cost; Due to Na
2sO
3be easy to and MnO
2reaction, so reduction leaching process speed is fast, reduction leaching process carries out in confined conditions, has avoided SO
2the environmental pollution that produces of effusion; Can be according to the needs of subsequent process, according to the grade of manganous carbonate breeze with for the Mn of the sulphuric acid soln of leaching process
2+concentration (Mn
2+rework solution by subsequent process is brought into), the sulfuric acid total concn that is used for the sulphuric acid soln of leaching process by control is carried out flexible, adapts to wide.
specific implementation method
embodiment 1: 1000g manganous carbonate breeze (is contained to bivalent manganese 25.2%, tetravalence manganese 3.1%, Fe
2o
310.7%, particle diameter 180 orders) adding volume is in the stainless steel cauldron of 5L, adds the sulphuric acid soln 2700ml of 2.0mol/L, stirs (stirring velocity 80r/min) and leach 1h at 60～70 ℃.Then add Na
2sO
3solution 300mL is (containing Na
2sO
374g), continue airtight agitation leach 1h at this temperature.After finishing, leaching passes into the airtight stirring oxidation of industrial pure oxygen 0.5h(relative pressure 0.1MPa).After finishing, oxidation carries out the washing of liquid-solid separation and leached mud.According to the assay result of the leached mud after cleaning, leach 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 98.5%.
Embodiment 2: 10kg manganous carbonate breeze (is contained to bivalent manganese 25.2%, tetravalence manganese 3.1%, Fe
2o
310.7%, particle diameter 180 orders) adding volume is in the stainless steel cauldron of 200L, the residual electrolyte that adds the sulphuric acid soln 160L(sulphuric acid soln of 0.35mol/L to be produced by electrolytic manganese factory, and raffinate is containing Mn
2+13.5g/L, H
2sO
434.5g/L).At 50～60 ℃, stir (stirring velocity 70r/min) and leach 2h.Then add Na
2sO
3solution 3L is (containing Na
2sO
3760g), continue airtight agitation leach 2h at this temperature.After finishing, leaching passes into the airtight stirring oxidation of industrial pure oxygen 1h(relative pressure 0.3MPa).After finishing, oxidation 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 99.3%.
Claims (1)
1. the leaching method of a manganese carbonate ore, it is characterized in that granularity≤180 object manganous carbonate breeze to add in sulfuric acid corrosion resistant and withstand voltage reactor, under the condition of reactor Exhaust Open and inlet close, add sulphuric acid soln to carry out the leaching of first stage, leach the CO producing
2from venting port, discharge, work as CO
2when gas is substantially drained, add sodium sulfite solution, close venting port and carry out the airtight leaching of subordinate phase, after subordinate phase leaches and finishes, passing into industrial pure oxygen is oxidized leaching, the slurry of emitting in reactor after oxidation finishes carries out solid-liquid separation, obtain required infusion solution, leached mud washes with water, washing water are used for preparing sulphuric acid soln for leaching, waste residue after washing send slag field to deposit, the sulfuric acid of leaching process add total amount be manganese in manganese carbonate ore theoretical consumption 105%～120%, the solution that returns to leaching process that sulfuric acid adds total amount to comprise newly to add sulfuric acid amount and subsequent process to produce, contained sulfuric acid amount in washing water, Mn for the starting point concentration of the sulphuric acid soln sulfuric acid that leaches in required leach liquor
2+concentration is determined, is calculated as follows: Mn in sulfuric acid concentration=required leach liquor
2+the sulphuric acid soln Mn of concentration-for leaching
2+starting point concentration, each concentration unit of calculating formula is mol/L, for leach in the breeze weight of kg with for leaching the ratio in the volume of the solution of L, being called for short solid-to-liquid ratio is calculated as follows definite: solid-to-liquid ratio=1: leach the required sulfuric acid total amount ÷ sulfuric acid concentration of every kg breeze, in calculating formula, leach the required sulfuric acid total amount of every kg breeze in g, sulfuric acid concentration is in g/L, the temperature of leaching process is 50 ℃～70 ℃, stirring velocity is 50 r/min～130 r/min, and the add-on of S-WAT is by MnO contained in breeze
2restore All is Mn
2+103%～120% of required theoretical amount, the extraction time of first stage is 1h～2h, and the extraction time of subordinate phase is 1h～2h, and it is 0.5h～1.5h that leach liquor is carried out to oxidization time, and the relative pressure of oxidising process is 0.1Mpa～0.3MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736404.2A CN103757247A (en) | 2013-12-29 | 2013-12-29 | Method for leaching manganese carbonate ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736404.2A CN103757247A (en) | 2013-12-29 | 2013-12-29 | Method for leaching manganese carbonate ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103757247A true CN103757247A (en) | 2014-04-30 |
Family
ID=50524561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310736404.2A Pending CN103757247A (en) | 2013-12-29 | 2013-12-29 | Method for leaching manganese carbonate ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103757247A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2799362C1 (en) * | 2022-11-25 | 2023-07-05 | Валерий Геннадьевич Побежимов | Method for processing carbonate manganese ore |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210893A (en) * | 1997-09-09 | 1999-03-17 | 邓建成 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
| CN1502710A (en) * | 2002-11-26 | 2004-06-09 | 中南大学 | Deep purification method of manganese sulfate solution |
| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN1884099A (en) * | 2006-07-07 | 2006-12-27 | 广西大学 | Method for preparing manganese sulfate by reduction leaching of manganese ore using discard molasses and sulfuric acid |
| CN102021331A (en) * | 2010-12-11 | 2011-04-20 | 付春平 | Processing method for comprehensively recovering high manganese asbolite |
| US20120177551A1 (en) * | 2009-08-19 | 2012-07-12 | Yava Technologies Inc. | Selective leach recovery of minerals from composite ores |
| CN103014320A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for preparing manganese sulfate by using sulfur-containing carbonaceous manganese carbonate ore |
-
2013
- 2013-12-29 CN CN201310736404.2A patent/CN103757247A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210893A (en) * | 1997-09-09 | 1999-03-17 | 邓建成 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
| CN1502710A (en) * | 2002-11-26 | 2004-06-09 | 中南大学 | Deep purification method of manganese sulfate solution |
| CN1587423A (en) * | 2004-07-21 | 2005-03-02 | 清华大学 | Method for recovering manganese from low content manganese carbonate raw ore |
| CN1884099A (en) * | 2006-07-07 | 2006-12-27 | 广西大学 | Method for preparing manganese sulfate by reduction leaching of manganese ore using discard molasses and sulfuric acid |
| US20120177551A1 (en) * | 2009-08-19 | 2012-07-12 | Yava Technologies Inc. | Selective leach recovery of minerals from composite ores |
| CN102021331A (en) * | 2010-12-11 | 2011-04-20 | 付春平 | Processing method for comprehensively recovering high manganese asbolite |
| CN103014320A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for preparing manganese sulfate by using sulfur-containing carbonaceous manganese carbonate ore |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2799362C1 (en) * | 2022-11-25 | 2023-07-05 | Валерий Геннадьевич Побежимов | Method for processing carbonate manganese ore |
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Application publication date: 20140430 |