CN103757204A - Method for leaching manganese carbonate ore - Google Patents

Method for leaching manganese carbonate ore Download PDF

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Publication number
CN103757204A
CN103757204A CN201310736401.9A CN201310736401A CN103757204A CN 103757204 A CN103757204 A CN 103757204A CN 201310736401 A CN201310736401 A CN 201310736401A CN 103757204 A CN103757204 A CN 103757204A
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leaching
sulfuric acid
concentration
leach
leaches
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CN201310736401.9A
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CN103757204B (en
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龙炳清
李贵
林春
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Sichuan Normal University
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Sichuan Normal University
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    • 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

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  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a method for leaching manganese carbonate ore. The method comprises the steps of adding manganese carbonate ore powder and cocoanut shell powder together into a reaction kettle which is resistant to pressure and the corrosion of sulfuric acid and nitric acid, adding a sulfuric acid solution to carry out first-stage leaching, and exhausting CO2 which is generated during leaching from an exhaust opening; when CO2 is basically exhausted completely, adding nitric acid to carry out second-stage closed leaching; after the second-stage closed leaching is ended, introducing industrial pure oxygen to oxidize a leachate.

Description

The leaching method of manganese carbonate ore
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 to produce the main technique of above-mentioned materials, leaches the operation operation that is absolutely necessary in this technique.Producing in 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 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 by≤180 object manganous carbonate breezes and≤coconut shell powder of 1.5mm adds in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion in the lump, 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 nitric acid to carry out the airtight leaching of subordinate phase.Subordinate phase passes into industrial pure oxygen leach liquor is oxidized after leaching and finishing.After oxidation finishes, emit slurry and carry out solid-liquid separation, obtain 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.It is 103%～110% of theoretical consumption that in manganese carbonate ore, all manganese leaches that the sulfuric acid of leaching process adds total amount, and 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.The add-on of coconut shell powder is counted MnO in manganese carbonate ore with butt 2100%～130% of quality.Be used for the starting point concentration of the sulphuric acid soln sulfuric acid leaching by the Mn 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.
It is 2g/L～8g/L by the concentration of complete soln volumeter that subordinate phase leaches the nitric acid adding.
The temperature of whole leaching process is 40 ℃～70 ℃, and stirring velocity is 50 r/min～130 r/min.The extraction time of first stage is 2h～3h.The extraction time of subordinate phase is 1h～2h.It is 0.5h～1h 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 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, following chemical reaction mainly to occur:
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
Other organism in coconut shell powder 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.
At oxidation stage, mainly there is Fe 2+oxidizing reaction:
4FeSO 4?+?O 2?+?2H 2SO 4?=?2Fe 2(SO 4) 3?+?2H 2O
Fe 2(SO 4) 3?+?3H 2O?=?Fe 2O 3?+?3H 2SO 4
Because the speed of response of nitric acid and coconut shell powder is very fast, the NO of generation and MnO 2reaction also very fast, accelerate thus whole leaching process, and realize MnO 2leach more completely.As long as control the add-on of coconut shell powder and the add-on of sulfuric acid well, the amount that just can reduce Fe and enter leach liquor.But the add-on of coconut shell powder and 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.Pass through O 2oxidation is by Fe 2+be oxidized to Fe 3+, and then there is hydrolysis reaction, remove portion Fe.The Fe not eliminating does not need further oxidation follow-up except in Fe process.
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, thereby save production cost; Because the second leaching stage and leach liquor oxidation stage are thermopositive reaction, substantially do not need additional heat, leaching process is energy-conservation; Because nitric acid is easy to react with coconut shell powder, the NO of generation is easy to again and MnO 2reaction, so leaching process speed is fast; Leaching process carries out in confined conditions, the environmental pollution of having avoided the effusion of NO to produce; Due in leaching process by Fe 2+oxidation is from Fe 3+, can simplify the follow-up scavenging process of leach liquor.
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) and≤to add volume be in the lining titanium pressure reaction still of 5L to 1.5mm coconut shell powder 49g, under exhaust valve opening and the airtight condition of intake valve, add the sulphuric acid soln 2700ml of 2.0mol/L, at 60～70 ℃, stir (stirring velocity 80r/min) and leach 2h.Then add nitric acid 6g (with HNO 3meter), continue airtight leaching 1h.After this open O 2intake valve passes into O 2in Oxidation Leaching liquid 0.5h(reactor, relative pressure is 0.3MPa).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 99.1%.
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) and≤to add volume be in the lining titanium pressure reaction still of 150L to 1.5mm coconut shell powder 590g, the residual electrolyte that adds the sulphuric acid soln 120L(sulphuric acid soln of 0.446mol/L to be produced by electrolytic manganese factory under exhaust valve opening and the airtight condition of intake valve is prepared, and raffinate is containing Mn 2+13.5g/L, H 2sO 434.5g/L).At 50～60 ℃, stir (stirring velocity 70r/min) and leach 3h.Then add nitric acid 720g (with HNO 3meter), continue airtight leaching 2 h.After this pass into O 2in Oxidation Leaching liquid 1h(reactor, relative pressure is 0.1MPa).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 99.6%.

Claims (2)

1. a leaching method for manganese carbonate ore, it is characterized in that by≤180 object manganous carbonate breezes and≤coconut shell powder of 1.5mm adds in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion in the lump, adds sulphuric acid soln to carry out the leaching of first stage, leaches the CO producing 2from venting port, discharge, work as CO 2when gas is substantially drained, add nitric acid to carry out the airtight leaching of subordinate phase, after subordinate phase leaches and finishes, passing into industrial pure oxygen is oxidized leach liquor, after oxidation finishes, emit slurry and carry out solid-liquid separation, obtain required infusion solution, leached mud washes with water, washing water are used for preparing sulphuric acid soln for leaching, it is 103%～110% of theoretical consumption that in manganese carbonate ore, all manganese leaches that the sulfuric acid of leaching process adds total amount, 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, the add-on of coconut shell powder is counted MnO in manganese carbonate ore with butt 2100%～130% of quality.
For the starting point concentration of the sulphuric acid soln sulfuric acid that leaches by the Mn 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, it is 2g/L～8g/L by the concentration of complete soln volumeter that subordinate phase leaches the nitric acid adding, the temperature of whole leaching process is 40 ℃～70 ℃, stirring velocity is 50 r/min～130 r/min, the extraction time of first stage is 2h～3h, the extraction time of subordinate phase is 1h～2h, it is 0.5h～1h that leach liquor is carried out to oxidization time, the relative pressure of oxidising process is 0.1Mpa～0.3MPa.
CN201310736401.9A 2013-12-29 2013-12-29 The leaching method of manganese carbonate ore Expired - Fee Related CN103757204B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106435173A (en) * 2016-12-07 2017-02-22 铜仁学院 Impregnation liquid and leaching method for manganese ore

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1502710A (en) * 2002-11-26 2004-06-09 中南大学 Deep purification method of manganese sulfate solution
CN101070565A (en) * 2007-06-14 2007-11-14 重庆大学 Method for extracting high-valence manganese from manganese carbonate ore

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1502710A (en) * 2002-11-26 2004-06-09 中南大学 Deep purification method of manganese sulfate solution
CN101070565A (en) * 2007-06-14 2007-11-14 重庆大学 Method for extracting high-valence manganese from manganese carbonate ore

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106435173A (en) * 2016-12-07 2017-02-22 铜仁学院 Impregnation liquid and leaching method for manganese ore

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