CN108220998A - A kind of method of manganese sulfate electrolyte purification dechlorination - Google Patents

A kind of method of manganese sulfate electrolyte purification dechlorination Download PDF

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Publication number
CN108220998A
CN108220998A CN201810189479.6A CN201810189479A CN108220998A CN 108220998 A CN108220998 A CN 108220998A CN 201810189479 A CN201810189479 A CN 201810189479A CN 108220998 A CN108220998 A CN 108220998A
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manganese
purification
bismuth
sulfuric acid
slag
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CN108220998B (en
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刘伟锋
杨天足
张杜超
陈霖
唐攒浪
孙百奇
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation

Abstract

A kind of method of manganese sulfate electrolyte purification dechlorination, bismuth oxide activates in concentrated sulfuric acid first makes it be converted into sulfuric acid oxygen bismuth, secondly activation slag is added to manganese sulfate solution and adjusts solution ph to initial value with manganese salt, the chlorion in solution is made to be precipitated in the form of chlorine oxygen bismuth, purification slag concentrated sulfuric acid digestion is eventually adding bismuth ion remaining in liquid after manganese powder displacement purge to remove chlorine and realize that precipitating reagent regenerates again.The essence of the present invention makes bismuth oxide be converted into active preferable sulfuric acid oxygen bismuth first, and then the characteristics of utilizing chlorine oxygen bismuth solubility product small, the chlorine in manganese sulfate electrolyte is removed with sulfuric acid oxygen bismuth, reuse the property that hydrogen chloride is easy to volatilization, chlorine oxygen bismuth is made to be regenerated as sulfuric acid oxygen bismuth, finally using the electrode potential property lower than bismuth of manganese, make bismuth displacement recycling remaining in liquid after purification.The present invention has the advantages that short technical process, good product quality and at low cost.

Description

A kind of method of manganese sulfate electrolyte purification dechlorination
Technical field
The present invention relates to a kind of method of manganese sulfate electrolyte purification, the purification removing chlorine particularly in manganese sulfate solution Wet-process metallurgy method.
Background technology
Manganese metal is a kind of bright argenteous transition metal, and matter is hard and crisp, and chemical property is active, being of existence form Close object.Manganese is mainly used for the desulfurization and deoxidation of steel in steel and iron industry, also serves as alloy addition to improve the intensity of steel, hard Degree, elastic limit, wearability and corrosion resistance etc.；In high-alloy steel, austenite combined elements are also served as, it is stainless for refining Steel, special alloy steel, stainless steel electrode etc..In addition, it is additionally operable to non-ferrous metal, chemical industry, medicine, electronics and agricultural etc..
The major product of manganese has manganese metal and manganese dioxide, their production process is all using leaching-purification-electrolysis Technique obtains manganese sulfate solution after manganese ore raw material sulfuric acid leaching first, then manganese sulfate solution is net using sulfurization-precipitation method Change removing beavy metal impurity, qualified manganese sulfate solution obtains manganese product by electrolysis, both product electrolytic processes are slightly different, Manganese metal is deposited on cathode plate, and manganese dioxide is then deposited on anode plate.The primary raw material of manganese smelting process is soft manganese at present Ore deposit and manganese spar, although their processing method different from, finally all using the manganese sulfate solution of output qualification as final mesh 's.Due to the continuous consumption of ANOMALY IN FINE QUALITY MANGANESE DEPOSITS resource, ore raw materials grade is lower and lower and impurity is continuously increased, manganese sulfate electrolyte Dedoping step it is more and more important, such as：Sulphur, phosphorus, silicon and impurity metal components in manganese ore can be to the smelting of manganese and product matter Amount causes extreme influence, especially when chloride ion content is excessively high in electrolyte, chlorine may be precipitated in anode, chlorine is not only Metal polar plate can be corroded, redissolve the manganese that cathode is precipitated, but also productive labor environment can be influenced, pole is generated to the electrolytic process of manganese For detrimental effect, it can not only increase production cost, but also the product quality of cathode manganese can be influenced.
At present, the technology about manganese sulfate electrolyte dechlorination having been reported that is broadly divided into Physical and chemical method, Physical Then it is broadly divided into blow-off method and vacuum method.Vacuum method is to be heated to boiling by solution under vacuum conditions, generates vapor, is utilized Bubble takes away chlorine so as to achieve the purpose that dechlorination；Blow-off method be by air add in dechlorinator in, filler superficial air with it is molten Liquid contacts dechlorination.（The removing of chlorion and the recycling of dechlorination mantoquita research Gansu in Wu An east manganese spars powder and manganese electrolyte Lanzhou Lanzhou University, 2015）
Chemical method mainly include the stannous chloride precipitation method, the oxychloride tin precipitation method, silver nitride precipitation method, bismuth oxide dechlorination method and from Sub- exchange process etc..The stannous chloride precipitation method are that copper ion is added in into solution, recycle oxidant or reducing agent, make in solution Copper ion is changed into cuprous ion and is precipitated with chloride binding, to achieve the purpose that dechlorination（The such as Li Chun stannous chlorides precipitation is de- The research hydrometallurgys .2001,3 (9) of chlorine reaction balance:152-155;In Wu An east manganese spars powder and manganese electrolyte chlorine from The removing of son and the recycling research Gansu Lanzhou Lanzhou University of dechlorination mantoquita, 2015.）.The oxychloride tin precipitation method are to be electrolysed Tin compound is added in liquid, adjusts pH value of solution=1.0-3.0, precipitates generation oxychloride tin, filter residue is regenerated with sodium hydroxide solution It returns and uses afterwards（The such as stone Aiwa are a kind of to remove chlorine method application numbers in zinc or manganese electrolyte with tin compound: 201110305907.5.）.Silver nitride precipitation method is typically that the larger silver salt of solubility such as silver nitrate are added in into solution, makes silver Ion and chlorion are precipitated into silver chlorate to achieve the purpose that dechlorination, but due to silver-colored higher price, and silver nitride precipitation filters Poor-performing, silver raising recovery rate is relatively low, causes production cost excessively high, so using less in industry.Bismuth oxide dechlorination method is to use Bismuth is converted into ionic species and added in into manganese sulfate solution by the acid means such as molten, and adjustment pH value makes bismuth hydrolysis generation hard to tolerate BiOCl is precipitated, and realizes the purpose of dechlorination in solution（The dechlorination slag bismuth oxychloride regeneration cycle use of the such as Wu Wenhua zinc electrolytes is ground Study carefully China YouSes metallurgy, 2015,1 (2): 71-73.）；Ion-exchange is to utilize the exchangeable ion on ion exchange resin It is swapped with the chlorion in solution, the chlorion adsorbed is taken away by resin, realizes the removing of chlorion（The such as Wang Xiaodan The experimental study Yunnan metallurgies 2010,4 (8) that ion-exchange dechlorinates from zinc electrolyte: 33-36.）, but ion exchange The efficiency of method dechlorination is generally relatively low, and resin regeneration water consumption is big, brings the process problem of a large amount of chloride ion-containing sewage.
Although chlorine removal rate is one of main indexes for evaluating each method quality, the recycling of antichlor is still It is so an important evaluation index.The gained common processing method of protochloride copper ashes is in alkali in the stannous chloride precipitation method It is heated in solution, is allowed to transform into cuprous oxide or cuprous hydroxide, then again returned to and do antichlor use, however this time There are two main problems for receipts method, are that in the conversion process, copper-base may oxidation by air generation copper oxide or hydroxide first Copper can not directly return to use.For this problem, there is method of the scholar using reagents such as addition glucose, sodium thiosulfate, Although the problem of regenerating transformed rate is low solves therewith, production cost also accordingly increases；Another problem is that in conversion process chlorine from Son enters in solution, and the chloride ion-containing waste water of formation becomes new environmental issue；The recycling of antichlor in the oxychloride tin precipitation method Method is identical with regeneration method used in the stannous chloride precipitation method；The dechlorination slag main component of bismuth oxide dechlorination method is bismuth oxychloride, The regenerating transformed bismuth oxide that becomes returns to use typically under the high-alkali environment of high temperature（The such as Wu Wenhua zinc electrolytes dechlorination slag chlorine Bismuth oxide regeneration cycle use research China YouSes are metallurgical, 2015,1 (2):71-73.）, which, which still can generate, contains Chlorine ion wastewater.
It is not difficult to find out, the technological difficulties of manganese sulfate solution dechlorination at present are other than removal efficiency, the also antichlor rate of recovery And the problem of cost recovery.Traditional antichlor recycling round-robin method all there is it is of all kinds the problem of, produced after being such as circulated throughout Antichlor use can not be directly done, and then cause to locate after having given birth to new pollutant-chloride ion-containing sewage or reclaiming Manage the increase of cost.For these problems, it is proposed that the Wet-process metallurgy method of manganese sulfate electrolyte purification removing chlorine.
Invention content
In order to overcome the shortcomings of manganese sulfate electrolyte conventional purge dechlorination method, the present invention provides a kind of manganese sulfate electrolyte Removing chlorine, and the preparation method that technical process is short, operating index is good and at low cost are purified with bismuth oxide.
The technical solution adopted by the present invention is in order to achieve the above objectives：Bismuth oxide activates in concentrated sulfuric acid first makes it Sulfuric acid oxygen bismuth is converted into, activation slag is secondly added to manganese sulfate solution and adjusts solution ph to initial value with manganese salt, is made Chlorion in solution is precipitated in the form of chlorine oxygen bismuth, and purification slag concentrated sulfuric acid digestion is to remove chlorine and realize precipitating reagent again again It is raw, it is eventually adding bismuth ion remaining in liquid after manganese powder displacement purge.The essence of the present invention makes bismuth oxide be converted into activity first It the characteristics of preferable sulfuric acid oxygen bismuth and then small utilization chlorine oxygen bismuth solubility product, is removed in manganese sulfate electrolyte with sulfuric acid oxygen bismuth Chlorine reuses the property that hydrogen chloride is easy to volatilization, chlorine oxygen bismuth is made to be regenerated as sulfuric acid oxygen bismuth, finally using manganese than bismuth pole current potential Low property makes bismuth displacement removing remaining in liquid after purification；These process tight associations, collective effect are realized with three oxidations two The purpose that bismuth dechlorinates from manganese sulfate electrolyte purification.
Specific technical process and parameter are as follows：
1 concentrated sulfuric acid activates
Bismuth oxide activates in concentrated sulfuric acid makes it be converted into sulfuric acid oxygen bismuth；By bismuth oxide and the concentrated sulfuric acid in mass ratio 1/1~4 It is uniformly mixed, is then heated to 150~250 DEG C of 5~15min of reaction, treats that yellow bismuth oxide is converted into white Stop heating after sediment, activation slag send purification to be used except chlorine process；Concentrated sulfuric acid activation process main chemical reactions are：
Bi2O3+H2SO4=(BiO)2SO4++H2O （1）
2 purification dechlorinations
Activation slag is added in manganese sulfate electrolyte and adjusts solution ph, removes Chlorine in Solution ion generation chlorine oxygen bismuth precipitation It goes；Activation slag is added in manganese sulfate electrolyte, control activation the ratio between slag amount kg and liquid volume L are 1/100 ~ 150, are held It is 30~80 DEG C to continue stirring and keep temperature, while it is initial value to add in manganese salt to maintain solution ph, continues to be stirred to react 0.5 ~1.5h, using vacuum filtration mode solid-liquor separation, purification slag send subsequent regeneration process, mainization that purification occurs except chlorine process It is as follows to learn reaction：
(BiO)2SO4+2HCl=2BiOCl↓+H2SO4（2）
3 purification slags regenerate
Purification slag concentrated sulfuric acid digestion with remove chlorine and realize precipitating reagent regenerate；By purification slag and the concentrated sulfuric acid in mass ratio 1/2 ~ 5 It is uniformly mixed, is then heated to 150~250 DEG C of 20~30min of reaction, treats that solids is converted into white by light gray Stop heating after sediment, used after volatilization acid mist condensation as hydrochloric acid, sediment returns to purification except chlorine process uses, after purification Liquid send manganese powder replacement process；Purification slag regenerative process main chemical reactions are：
2BiOCl+H2SO4 =(BiO)2SO4+2HCl↑ （3）
4 manganese powders are replaced
The bismuth ion of manganese powder displacement remaining is added in into liquid after purification；Manganese powder is added in into liquid after purification, control manganese powder adds in matter It is 1/1000~1500 to measure the ratio between kg and liquor capacity L, after 60~85 DEG C of temperature of holding the reaction was continued 0.5~1.5h, using true Empty suction filtration mode realizes solid-liquor separation, and replacement slag returns to concentrated sulfuric acid digestion activation process, and displaced liquid produces for electrolytic manganese；Manganese The main chemical reactions of powder substitution process are as follows：
(BiO)2SO4+3Mn+2H2SO4=2Bi+3MnSO4+2H2O （4）
Bi in bismuth oxide of the present invention2O3Mass percentage is not less than 99.90%.
The concentrated sulfuric acid and manganese powder of the present invention are technical grade reagent, their mass percentage is not less than respectively 98.0% and 99.0%.
The manganese salt is one or both of technical grade manganese carbonate or manganous hydroxide.
The present invention is dechlorinated with manganese sulfate electrolyte tradition compared with method, is had the advantage that：1st, it is of the invention by activation products sulphur Sour oxygen bismuth is used to remove the chlorion in manganese sulfate electrolyte, and dechlorination rate reaches more than 95.0%；2nd, digestion is lived in concentrated sulfuric acid Change makes bismuth oxide be converted into sulfuric acid oxygen bismuth, and reaction efficiency is greatly improved, and bismuth utilization rate is more than more than 98.0%；3rd, it is net Slugging uses concentrated sulfuric acid digestion, not only realizes except chlorine reagent regenerates, but also volatile hydrogen chloride recycles, and has prevented discharge of wastewater； 4th, using bismuth remaining in liquid after manganese powder displacement purge, bi concns are less than 1.0mg/L in displaced liquid, prepare for follow-up electrolytic process Quality raw materials；5th, the present invention has the advantages that short technical process, good product quality and production cost are low etc..
Description of the drawings
Fig. 1：Present invention process flow diagram.
Specific embodiment
Embodiment 1：
Bi in bismuth oxide of the present invention2O3Mass percentage is not less than 99.90%, the technical grade concentrated sulfuric acid (H2SO4≥ 98.0%), technical grade manganese powder (Mn >=99.0%) and manganese carbonate (MnCO3≥98.0%).Bismuth oxide and the concentrated sulfuric acid are pressed into quality It is uniformly mixed than 1/4, is then heated to 210 DEG C of reaction 10min, treats that yellow bismuth oxide is converted into white precipitate Stop heating after object, activation slag is added in manganese sulfate electrolyte, control activation the ratio between slag amount kg and liquid volume L are 1/ 120, it is 70 DEG C persistently to stir and keep temperature, while it is initial value 2.30 to add in manganese carbonate to maintain solution ph, continues to stir Reaction 1.0h is mixed, using vacuum filtration mode solid-liquor separation, chlorion is reduced to 22mg/L in liquid after purification, and dechlorination rate reaches 96.80%。
Purification slag and the concentrated sulfuric acid in mass ratio 1/2 are uniformly mixed, are then heated to 210 DEG C of reaction 25min, Stop heating after solids is converted into white depositions by light gray, used after volatilization acid mist condensation as hydrochloric acid, sediment Purification is returned except chlorine process uses；Manganese powder is added in into liquid after purification, control manganese powder adds in the ratio between quality kg and liquor capacity L and is 1/1100, after keeping 80 DEG C of temperature the reaction was continued 1.0h, solid-liquor separation is realized using vacuum filtration mode, replacement slag returns to dense sulphur Activation process is boiled in acidleach, and bi content is 0.1mg/L in displaced liquid.

Claims (1)

  1. A kind of 1. method of manganese sulfate electrolyte purification dechlorination, it is characterised in that include the following steps：
    （1）The concentrated sulfuric acid activates
    Bismuth oxide and the concentrated sulfuric acid in mass ratio 1/1~4 are uniformly mixed, are then heated to 150~250 DEG C instead 5~15min is answered, stops heating after yellow bismuth oxide is converted into white depositions, activation slag send purification except chlorine process makes With；
    （2）Purification dechlorination
    Activation slag is added in manganese sulfate electrolyte, control activation the ratio between slag amount kg and liquid volume L are 1/100 ~ 150, It is 30~80 DEG C persistently to stir and keep temperature, while it is initial value to add in manganese salt to maintain solution ph, continues to be stirred to react 0.5~1.5h, using vacuum filtration mode solid-liquor separation, purification slag send subsequent regeneration process；
    （3）Purification slag regenerates
    Purification slag and the concentrated sulfuric acid in mass ratio 1/2 ~ 5 are uniformly mixed, are then heated to 150~250 DEG C of reactions 20 ~30min stops heating after solids is converted into white depositions by light gray, makes after volatilization acid mist condensation as hydrochloric acid With sediment returns to purification except chlorine process uses, and liquid send manganese powder replacement process after purification；
    （4）Manganese powder is replaced
    Manganese powder is added in into liquid after purification, it is 1/1000~1500 that control manganese powder, which adds in the ratio between quality kg and liquor capacity L, is kept After 60~85 DEG C of temperature the reaction was continued 0.5~1.5h, solid-liquor separation is realized using vacuum filtration mode, replacement slag returns to the concentrated sulfuric acid Digestion activation process, displaced liquid produce for electrolytic manganese.
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CN109173340A (en) * 2018-11-08 2019-01-11 中南大学 A method of the adsorbing and removing chlorine from strongly acidic solution
CN110129563A (en) * 2019-05-31 2019-08-16 广东璞睿泰科环保科技有限公司 The preparation method and chloride ion removal technique of chloride ion cleanser in a kind of manganese electrolyte
CN111893521A (en) * 2020-08-10 2020-11-06 江苏兴广包装科技有限公司 Electroforming method capable of controlling distance change of holographic anti-counterfeiting nickel plate pattern
CN112080764A (en) * 2020-09-15 2020-12-15 西北矿冶研究院 Method for removing chlorine from zinc electrolyte
CN112323103A (en) * 2020-11-04 2021-02-05 江苏兴广包装科技有限公司 Hot-pressing type makeup method for holographic anti-counterfeiting plate
CN112520819A (en) * 2020-12-02 2021-03-19 西安建筑科技大学 Bismuth-series three-dimensional microsphere heterojunction photoelectrode and preparation and application thereof
CN113957483A (en) * 2021-11-08 2022-01-21 田世超 Method for preparing electrolytic manganese qualified liquid by using hydroxyl combined liquid phase reduction
CN114314928A (en) * 2022-01-04 2022-04-12 湖南烯富环保科技有限公司 Integrated production line and method for removing chloride ions and regenerating dechlorination agent from dechlorination slag
CN114307909A (en) * 2022-01-04 2022-04-12 湖南烯富环保科技有限公司 Full-automatic regeneration dechlorination agent production line and production method for dechlorination slag
CN116864851A (en) * 2023-09-05 2023-10-10 赣州市力道新能源有限公司 Process for deeply removing phosphorus from retired battery recovery feed liquid

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109173340A (en) * 2018-11-08 2019-01-11 中南大学 A method of the adsorbing and removing chlorine from strongly acidic solution
CN109173340B (en) * 2018-11-08 2020-11-17 中南大学 Method for removing chlorine from strong acidic solution by adsorption
CN110129563A (en) * 2019-05-31 2019-08-16 广东璞睿泰科环保科技有限公司 The preparation method and chloride ion removal technique of chloride ion cleanser in a kind of manganese electrolyte
CN111893521A (en) * 2020-08-10 2020-11-06 江苏兴广包装科技有限公司 Electroforming method capable of controlling distance change of holographic anti-counterfeiting nickel plate pattern
CN112080764A (en) * 2020-09-15 2020-12-15 西北矿冶研究院 Method for removing chlorine from zinc electrolyte
CN112323103A (en) * 2020-11-04 2021-02-05 江苏兴广包装科技有限公司 Hot-pressing type makeup method for holographic anti-counterfeiting plate
CN112520819A (en) * 2020-12-02 2021-03-19 西安建筑科技大学 Bismuth-series three-dimensional microsphere heterojunction photoelectrode and preparation and application thereof
CN112520819B (en) * 2020-12-02 2023-08-22 西安建筑科技大学 Bismuth-system three-dimensional microsphere heterojunction photoelectrode and preparation and application thereof
CN113957483A (en) * 2021-11-08 2022-01-21 田世超 Method for preparing electrolytic manganese qualified liquid by using hydroxyl combined liquid phase reduction
CN114314928A (en) * 2022-01-04 2022-04-12 湖南烯富环保科技有限公司 Integrated production line and method for removing chloride ions and regenerating dechlorination agent from dechlorination slag
CN114307909A (en) * 2022-01-04 2022-04-12 湖南烯富环保科技有限公司 Full-automatic regeneration dechlorination agent production line and production method for dechlorination slag
CN114314928B (en) * 2022-01-04 2023-09-08 湖南烯富环保科技有限公司 Integrated production line and method for chloride ion removal and chlorine removal slag regeneration chlorine removal agent
CN116864851A (en) * 2023-09-05 2023-10-10 赣州市力道新能源有限公司 Process for deeply removing phosphorus from retired battery recovery feed liquid
CN116864851B (en) * 2023-09-05 2023-11-21 赣州市力道新能源有限公司 Process for deeply removing phosphorus from retired battery recovery feed liquid

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