CN102226235A - Method for producing manganese electrolyte by using continuous countercurrent leaching - Google Patents

Method for producing manganese electrolyte by using continuous countercurrent leaching Download PDF

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Publication number
CN102226235A
CN102226235A CN2011101589679A CN201110158967A CN102226235A CN 102226235 A CN102226235 A CN 102226235A CN 2011101589679 A CN2011101589679 A CN 2011101589679A CN 201110158967 A CN201110158967 A CN 201110158967A CN 102226235 A CN102226235 A CN 102226235A
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CN
China
Prior art keywords
leaching
neutral
manganese
anolyte
acid
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Pending
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CN2011101589679A
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Chinese (zh)
Inventor
张飞
杨智勇
杨绍泽
邓相尧
刘波
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CHONGQING WULING MANGANESE INDUSTRY Corp
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CHONGQING WULING MANGANESE INDUSTRY Corp
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Priority to CN2011101589679A priority Critical patent/CN102226235A/en
Publication of CN102226235A publication Critical patent/CN102226235A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a method for producing a manganese electrolyte by using continuous countercurrent leaching, the method comprises the following steps: the qualified manganese mine powder or a manganese mine slurry is mixed with inorganic acid in a neutral reaction device, a mixed liquor treated through a neutral leaching reaction is performed a solid-liquid separating process, a supernatant is obtained for an oxidizing treatment and an vulcanizing treatment; leaching slag is obtained by filtering and performed an acidic leaching, the mixed liquor in an acidic leaching device is filtered, the filtered acidic supernatant is taken as an anolyte and added in the neutral leaching apparatus for circularly using; an obtained electrolytic qualified liquid is filtered after a vulcanizing reaction. The invention has the advantages of high utilization rate of equipment, low investment, less energy consumption, high metal leaching rate and easy realization of mechanization and automation; and is capable of improving the recovery rate of manganese.

Description

The continuous countercurrent leaching-type is produced the method for manganese electrolyte
Technical field
The present invention relates to a kind of continuous countercurrent leaching-type and produce the method for producing electrolyte of electrolytic metal Mn.
Background technology
Electrolytic solution in the electrolytic metal Mn is to go out to obtain manganese salt with manganese ore through acidleach, the elemental metals that send electrolytic tank electrolysis to separate out again; The processing method that the electrolytic solution that electrolytic manganese needs is commonly used is: draw purified manganese sulfate solution through " sedimentation---filtering---deep purifying---filters ", add additive after, enter electrolytic tank electrolysis as electrolytic solution, produce manganese metal.
The production method of prior art electrolytic solution, the not enough main following points of its existence: 1, facility investment, initial cost are big, occupation of land is more, and the relevant device that needs is bigger, and usage ratio of equipment is not high; 2, metal leaching rate is lower, and the rate of recovery of manganese ore is lower, and raw and auxiliary materials such as the sulfuric acid of consumption, liquefied ammonia, oxygenant are higher, and non-ferrous metal (as nickel, cobalt etc.) is not wherein all comprehensively reclaimed usually, has caused the waste of resource; 3, unit labour productivity is lower, and the pollution of production environment is more serious, and operator's body and mind is had certain detrimentally affect.
Summary of the invention
The above-mentioned deficiency that the manganese electrolyte that the present invention is directed to prior art manganese metal electrolysis production needs is produced, provide a kind of plant factor height, reduced investment, occupation of land less, resource utilization height, the continuous countercurrent leaching-type of the raising labour productivity method of producing manganese electrolyte.
Technical scheme of the present invention: the continuous countercurrent leaching-type is produced the method for manganese electrolyte, it is characterized in that comprising the steps:
(1) the neutral leaching with qualified manganese ore powder or manganese ore slurry and the ratio adding of mineral acid according to processing requirement, mixed in reaction unit, and the pH value of mixed solution is remained between the 3.5-6;
(2) neutrality is leached reacted mixed solution and carry out solid-liquid separation;
(3) neutral neutral leach liquor and the neutral supernatant liquor that leaches that leaches solid-liquid separation carries out oxide treatment and sulfidizing, and supernatant liquor is placed in the oxidation unit, adds oxygenant according to processing requirement and carries out oxide treatment; After the oxide treatment, carry out sulfidizing according to processing requirement; Filter behind the vulcanization reaction, the qualifying liquid after the filtration is the electrolysis qualifying liquid;
(4) the neutral leached mud that neutrality leaching back solid-liquid separation is obtained carries out the acidity leaching, and neutral leached mud is placed into acid the leaching in the device, and the anolyte of adding electrolytic manganese carries out acidity and leaches; The ratio of anolyte and leached mud is (4-9): 1, leach 60-150min;
The mixed solution that acidity is leached in the device filters, and the acid supernatant liquor that filtration obtains enters neutral the leaching in the device as anolyte and recycles.
Further feature is: described mineral acid is a sulfuric acid, or adds the anolyte of the electrolytic manganese that meets the processing requirement ratio in sulfuric acid.
The mode that described solid-liquid separation process uses pressure filter to combine with thickener.
Described oxygenant is ammoniacal liquor, Manganse Dioxide, hydrogen peroxide or air.
Continuous countercurrent leaching-type of the present invention is produced the method for manganese electrolyte, with respect to prior art, has following characteristics:
1, have the plant factor height, reduced investment, energy consumption consumption is few, and it is low by 40% that unit consumption of energy is interrupted leaching on year-on-year basis, the metal leaching rate height, raw and auxiliary material consumes low, and labor condition is good, easily realizes mechanize and automatization;
2, use pressure filter to combine and mainly improve the pressure filter utilization ratio, reduce facility investment, raise labour productivity with thickener;
3, the comprehensive recovery of cleaning section consideration non-ferrous metal (nickel, cobalt) stored up separately the sulfuration slag.
4, the intermittent type in the present industry is made into the continous way operation, purpose is to save occupation area of equipment, can realize automatization.
Description of drawings
Fig. 1 is a process method flow chart of the present invention.
Embodiment
In Fig. 1, continuous countercurrent leaching-type of the present invention is produced the production method of manganese electrolyte, it is characterized in that comprising the steps:
1, the neutral leaching, qualified manganese ore powder or manganese ore slurry and the mineral acid ratio according to processing requirement is added, in reaction unit (neutral leaching barrel), mix, the pH value of mixed solution is remained between 3.5-6, mineral acid commonly used is a sulfuric acid etc., or adds the anolyte of the electrolytic manganese that meets the processing requirement ratio in sulfuric acid; Neutral leaching of task is to guarantee that the manganese content of neutral leach liquor is between 32g/l-40g/l, spent acid pH value remains between 3.5-6, sulfuric acid is reacted completely with the manganese ore powder as far as possible, and when breeze contacted with the sulfuric acid leaching agent, manganese in the breeze and sulfuric acid reaction entered MnCO in the solution 3+ H 2SO 4=MnSO 4+ co 2+ H 2O.
Reach home fast for the assurance leaching process, neutral extraction time was controlled at 60 minutes-150 minutes, and the leaching yield of leaching process is controlled at 65%-90%.
The neutral leaching is to guarantee that sulfuric acid is inexcessive, reacts with it with excessive breeze and achieves the goal.Neutral leaching of task is that the most of manganese in the manganese ore powder is entered in the solution, and utilizes the neutralization precipitation method to remove the impurity such as iron that enter solution from the manganese ore powder.
After neutral leaching reaction finished, the refrigerant liquid separation with the upper strata obtained the neutral supernatant liquor that leaches.
2, neutrality is leached reacted mixed solution and carry out solid-liquid separation, solid-liquid separation process adopts thickener to combine with filter, guarantees that solids enters next section acidleach operation prevented from caking, reaches abundant reaction in the time of the rate of recovery of assurance solution.
3, neutral neutral leach liquor and the neutral supernatant liquor that leaches that leaches solid-liquid separation (filtration) carries out oxide treatment and sulfidizing, neutral leach liquor and the neutral supernatant liquor that leaches are placed into (oxidation bucket) in the oxidation unit, regulate pH value between 6.2-6.7 with ammoniacal liquor, (additional proportion of the oxygenant of different concns, heterogeneity is different to add oxygenant according to the ratio of processing requirement, add according to concrete processing requirement during operation), described oxygenant is ammoniacal liquor, Manganse Dioxide, hydrogen peroxide, air etc.; After the oxide treatment, (sulfuration bucket) carries out sulfidizing in vulcanizing plant, vulcanizing agent is a SDD(good fortune magnesium sodium), reaction times 30---90min removes iron in the solution, nickel, cobalt etc. to being that qualifying liquid enters electrowinning process with carrying out the solid-liquid separation supernatant liquor behind the deleterious heavy metal of electrolysis, enters the slag field after slag has valency to reclaim and focuses on.Oxide treatment and sulfidizing are not further described at this as prior art.
4, the neutral leached mud that filtration is obtained (containing a large amount of manganese) carries out the acidity leaching, and neutral leached mud is placed into acid the leaching in the device (bucket), and the anolyte (it contains a large amount of sulfuric acid) that adds electrolytic manganese carries out acidity and leaches; The ratio of anolyte and leached mud is generally (4-9): 1, and promptly liquid-solid ratio is (4-9): 1, leach 60-150min, final acidity generally is controlled at more than the 3g/l; The acid purpose that leaches be with excessive acid with the manganese in the neutral leached mud of stripping to greatest extent, guarantee the utilization ratio maximization of resource, guarantee that leaching yield reaches (interruption lixiviation process manganese leaching yield is generally about 90%) more than 97%.
The mixed solution that acidity is leached in the device filters, and filters operation and uses pressure filter to combine with existing thickener; The acid supernatant liquor that filtration obtains enters the neutral device that leaches as anolyte and recycles.The slag that filtration obtains enters the slag field and focuses on.The washings that the flushing of pressure filter, thickener is obtained also as anolyte, enters the neutral device that leaches.
The condition control of continuous countercurrent extract technology process of the present invention
The condition control of 1, oxidation, sulfidation
⑴, sulfuration liquid specification of quality
Element Manganese Mng/L Fe Ni PH
Content 32---40 Little or do not have Do not have 6.2-7
⑵, ammoniacal liquor specification of quality: ammonia content 5-10%
⑶, SDD solution quality require: SDD content 10%
⑷ heavy metals such as, oxidation, sulfuration deironing, nickel, cobalt.
2, the condition of neutral leaching process control
⑴, the neutral supernatant liquor specification of quality that leaches: contain manganese 32-40 g/L, PH=3.5-6.
⑵, anolyte specification of quality: contain manganese 11-15g/L, contain acid 25-50 g/L.
⑶, ore pulp specification of quality: liquid-solid ratio 1:1, solid holdup 50%.
⑷, the neutral purpose that leaches: guarantee to obtain containing the more stable leach liquor of manganese, reduce vitriolic and expend, also reduced consumption simultaneously with the liquefied ammonia neutralisation of sulphuric acid.
3, the condition of acid leaching process control
⑴, the acid supernatant liquor specification of quality that leaches:
Element Mng/L PH Leach liquor contains acid
Content 15—25 Below 2 More than the 3g/L
⑵, acid infusion solution extraction time 60-150 minute leach terminal point PH below 2, and the leach liquor terminal point contains more than the sour 3g/L.Leach liquor contains manganese 15-25 g/L.
⑶, the acid main purpose that leaches as far as possible fully leach the manganese in the neutral leached mud come, and improve the leaching yield of manganese to greatest extent.
System liquid of the present invention workshop section chemical combination operation takes continuous leaching+two a section leaching to combine, one section neutral leaching, two sections acid leachings, be manganese ore powder and electrolytic anode liquid by a certain percentage, successive is finished the leaching operation process by several series connection leaching vat, the press filtration operation that combines with pressure filter through thickener is carried out thick press filtration then, and then solution carried out segmentation oxidation, purification, pressure-sizing, enter electrolysis at last.

Claims (4)

1. the continuous countercurrent leaching-type is produced the method for manganese electrolyte, it is characterized in that comprising the steps:
(1) the neutral leaching with qualified manganese ore powder or manganese ore slurry and the ratio adding of mineral acid according to processing requirement, mixed in reaction unit, and the pH value of mixed solution is remained between the 3.5-6;
(2) neutrality is leached reacted mixed solution and carry out solid-liquid separation;
(3) neutral neutral leach liquor and the neutral supernatant liquor that leaches that leaches solid-liquid separation carries out oxide treatment and sulfidizing, and supernatant liquor is placed in the oxidation unit, adds oxygenant according to processing requirement and carries out oxide treatment; After the oxide treatment, carry out sulfidizing according to processing requirement; Filter behind the vulcanization reaction, the qualifying liquid after the filtration is the electrolysis qualifying liquid;
(4) the neutral leached mud that neutrality leaching back solid-liquid separation is obtained carries out the acidity leaching, and neutral leached mud is placed into acid the leaching in the device, and the anolyte of adding electrolytic manganese carries out acidity and leaches; The ratio of anolyte and leached mud is (4-9): 1, leach 60-150min;
The mixed solution that acidity is leached in the device filters, and the acid supernatant liquor that filtration obtains enters neutral the leaching in the device as anolyte and recycles.
2. according to the method for the described continuous countercurrent leaching-type production of claim 1 manganese electrolyte, it is characterized in that: described mineral acid is a sulfuric acid, or adds the anolyte of the electrolytic manganese that meets the processing requirement ratio in sulfuric acid.
3. the method for producing manganese electrolyte according to the described continuous countercurrent leaching-type of claim 1 is characterized in that: the mode that described solid-liquid separation process uses pressure filter to combine with thickener.
4. according to the method for the described continuous countercurrent leaching-type production of claim 1 manganese electrolyte, it is characterized in that: described oxygenant is ammoniacal liquor, Manganse Dioxide, hydrogen peroxide or air.
CN2011101589679A 2011-06-14 2011-06-14 Method for producing manganese electrolyte by using continuous countercurrent leaching Pending CN102226235A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436914A (en) * 2013-09-04 2013-12-11 宁夏天元锰业有限公司 Recovering treatment method of electrolytic manganese metal anode slime
CN103451423A (en) * 2013-09-04 2013-12-18 宁夏天元锰业有限公司 Solution preparation method of electrolytic manganese metal
CN103451673A (en) * 2013-08-08 2013-12-18 秀山县嘉源矿业有限责任公司 Production method of electrolytic manganese metal
CN103469247A (en) * 2013-09-04 2013-12-25 宁夏天元锰业有限公司 Method for reducing ammonia consumption in production of electrolytic manganese metal
CN103469246A (en) * 2013-09-04 2013-12-25 宁夏天元锰业有限公司 Iron removal method in production of manganese metal through electrolysis
CN110373540A (en) * 2019-07-05 2019-10-25 宁夏天元锰业集团有限公司 A kind of countercurrent leaching process of manganese electrolyte processed

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Publication number Priority date Publication date Assignee Title
CN1034517C (en) * 1992-11-02 1997-04-09 冶金工业部长沙冶研究院 Preparation of highly pure manganese sulfate with high yield rate

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103451673A (en) * 2013-08-08 2013-12-18 秀山县嘉源矿业有限责任公司 Production method of electrolytic manganese metal
CN103451673B (en) * 2013-08-08 2016-03-16 秀山县嘉源矿业有限责任公司 The production method of electrolytic metal Mn
CN103436914A (en) * 2013-09-04 2013-12-11 宁夏天元锰业有限公司 Recovering treatment method of electrolytic manganese metal anode slime
CN103451423A (en) * 2013-09-04 2013-12-18 宁夏天元锰业有限公司 Solution preparation method of electrolytic manganese metal
CN103469247A (en) * 2013-09-04 2013-12-25 宁夏天元锰业有限公司 Method for reducing ammonia consumption in production of electrolytic manganese metal
CN103469246A (en) * 2013-09-04 2013-12-25 宁夏天元锰业有限公司 Iron removal method in production of manganese metal through electrolysis
CN103436914B (en) * 2013-09-04 2016-10-26 宁夏天元锰业有限公司 A kind of electrolytic metal manganese anode slag recovery and treatment method
CN110373540A (en) * 2019-07-05 2019-10-25 宁夏天元锰业集团有限公司 A kind of countercurrent leaching process of manganese electrolyte processed
CN110373540B (en) * 2019-07-05 2021-05-11 宁夏天元锰业集团有限公司 Countercurrent leaching process of manganese preparation electrolyte

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Application publication date: 20111026