CN1163414C - Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide - Google Patents
Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide Download PDFInfo
- Publication number
- CN1163414C CN1163414C CNB991155874A CN99115587A CN1163414C CN 1163414 C CN1163414 C CN 1163414C CN B991155874 A CNB991155874 A CN B991155874A CN 99115587 A CN99115587 A CN 99115587A CN 1163414 C CN1163414 C CN 1163414C
- Authority
- CN
- China
- Prior art keywords
- manganese
- manganese dioxide
- sulfate monohydrate
- dioxide
- chemical
- 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.)
- Expired - Fee Related
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to the field of chemistry, particularly to a method for producing chemical manganese dioxide by the pyrolysis of manganese sulfate monohydrate. In the method, manganese sulfate monohydrate is pyrolyzed to generate trimanganese tetraoxide, then the trimanganese tetraoxide is oxidized and reduced to manganic oxide, and finally, the chemical manganese dioxide is prepared from the manganic oxide by the techniques of disproportionation, an oxidation reaction, pickling, washing, neutralization, filtration by pressing, drying by baking, etc. The present invention has the advantages of little environment pollution, low investment for equipment, short production period, low production cost, stable and reliable product quality, etc.; besides all of the advantages of the existing chemical manganese dioxide, the chemical manganese dioxide produced by the present invention has higher short circuit current, higher load voltage and better discharge performance under heavy current and heavy load than the properties of electrolytic manganese dioxide.
Description
The present invention relates to chemical field, the method for chemical manganese bioxide is produced in particularly a kind of manganese sulfate monohydrate pyrolysis.
Since invention drying battery in 1868, Manganse Dioxide is the main positive electrode material of drying battery, and its quality quality plays decisive role to the performance of zinc-manganse dioxide dry cell.
The Manganse Dioxide that battery is used is divided into four big classes substantially: 1, natural discharge manganese (NMD); 2, activated manganese dioxide (AMD); 3, electrolytic manganese dioxide (EMD); 4, chemical manganese bioxide (CMD).
Electrolytic manganese dioxide is historical by existing existing more than 60 year from suitability for industrialized production in 1940.The Manganse Dioxide that makes with electrolytic process can satisfy the specification of quality of heavy body high power battery raw material, shortcomings such as regrettably the electrolytic process preparing manganese dioxide has the power consumption height, environmental pollution is big, facility investment is big, the production cycle is long, production cost height, cause valuable product, restricted the development of battery industry to a certain extent.Since the seventies, countries in the world active development chemical manganese bioxide is produced, and the most representative have a Belgian Saden horse company, and it produces chemical manganese bioxide with ammonium ammonium formiate method, and annual production reaches 40,000 tons, the production history in existing more than 20 year.Other also has the production of small dimension as Japan, the U.S., France.The chemical manganese bioxide that this method is produced and the Chemical Composition and crystalline structure (mainly all the being the r-type) basically identical of electrolytic manganese dioxide, do not exist together is physicals, the median size of electrolytic manganese dioxide is bigger 2 times than chemical manganese bioxide, and specific surface has only chemical manganese bioxide half, therefore chemical manganese bioxide is compared with electrolytic manganese dioxide, has Manganse Dioxide utilization ratio height, liquid absorption is big, the battery recovery performance is strong, advantages such as anti-leakage is good, shortcoming is that (being example with Belgian) chemical manganese bioxide internal resistance is bigger, short-circuit current and load voltage are low slightly, big electric current, heavy loading discharge property is lower than electrolytic manganese dioxide slightly, and facility investment is big, production cycle is long, the production cost height, and quality product can't guarantee (to follow compression process because of ammonia is arranged, whole process of production needs High Temperature High Pressure, restive every technic index).
It is few to the purpose of this invention is to provide a kind of facility investment, with short production cycle, stable and reliable product quality, and electrical property is better than the method for the manganese sulfate monohydrate pyrolysis production chemical manganese bioxide of electrolytic manganese dioxide.
Technical scheme of the present invention is: after the manganese sulfate monohydrate pyrolysis is generated trimanganese tetroxide, be manganic oxide with the trimanganese tetroxide redox again, then three Mn 3 Os made chemical manganese bioxide through technologies such as disproportionation, oxidizing reaction, pickling, washing, neutralization, press filtration and oven dry.
The further technical scheme of the present invention is: the sulfur dioxide high temperature gas that produces during the manganese sulfate monohydrate pyrolysis is earlier through UTILIZATION OF VESIDUAL HEAT IN, after making its temperature reduce to below 50 ℃, again through the gas preparing tank, content of sulfur dioxide is fitted on below 30%, and leaching Manganse Dioxide ore pulp is made manganese sulfate solution in the sulfurous gas reaction tower then.
The present invention further technical scheme is: after oxidizing reaction finishes, allow reaction solution precipitate, post precipitation reclaims mother liquor, again the mother liquor that reclaims is added sulfuric acid, after cooling, press filtration, removing sodium sulfate, joins and carries out disproportionation in the Manganse Dioxide ore pulp.
The present invention is owing to adopt as above technical scheme, compared with prior art, it is little to have environmental pollution, facility investment is few, (can go out product in three days) with short production cycle, production cost is low, stable and reliable product quality is (because of no ammonia follows compression process, whole process of production need not High Temperature High Pressure, be easy to control every technic index, be convenient to the operation) etc. advantage, the chemical manganese bioxide of production not only has Manganse Dioxide utilization ratio height, liquid absorption is big, the battery recovery performance is strong, anti-leakage waits all advantages of chemical manganese bioxide well, and its short-circuit current and load voltage and big electric current heavy loading discharge property all are better than electrolytic manganese dioxide.
Below in conjunction with embodiment technical scheme of the present invention is described further.
Embodiment 1: produce chemical manganese bioxide with Manganse Dioxide breeze roasting system manganous sulfate
Breeze roasting: get content and be about 60% manganese dioxide powder (fineness 200 orders) and put the roasting of rotation electric furnace, temperature 750-800 ℃, 2 hours time, the roasting of Manganse Dioxide breeze is become manganic oxide (Mn
2O
3).
Disproportionation: fetch and receive mother liquor 2800kg, content is the dilute sulphuric acid 800kg of 300g/l, the manganic oxide breeze 1200kg (solid-to-liquid ratio 1: 3) that roasting is good is mixed with ore pulp, puts to react between the inherent 92-96 ℃ of temperature of reactor and makes the manganese sulfate solution ore pulp in 60 minutes.
Deironing: with the good manganic oxide breeze of roasting, between temperature 90-96 ℃, evenly join in the manganese sulfate solution ore pulp while stirring, utilize manganic oxide breeze disproportionation reaction to need the vitriolic principle, the manganese sulfate solution pulp PH value is adjusted between the 5-5.5, as iron-free in the solution, get final product press filtration, obtaining product promptly is manganese sulfate solution, adds SDD solution in press filtration, and purpose is removed the heavy metal in the solution.
Manganese sulfate solution is refining: the manganese sulfate solution that will add SDD solution is static to be deposited 72 hours, the various foreign matter contents of sampling analysis solution, and press filtration afterwards up to standard obtains the POV manganese solution of BE ° of 23-24.
The pressure crystallization: the pressure crystallizing pan is provided with tensimeter, thermometer, blow-off valve, safety valve, stirrer 60-65 rev/min, and filter on top, bottom filter tap, electrothermal tube.Pressure 4kg, material is made with the stainless steel plate of 1 chromium, 13 nickel, 9 titaniums.
Pressing force pot total volume 80% adds the POV manganese solution, heating, and after pressure reached 2-5kg, constant voltage was opened filter tap after 1 hour, and clear liquid is put.Stop to stir, cut off electrothermal tube power, the opening pressure pot is poured out product, through centrifugal, deposits material-stored pool in again, sampling analysis, qualified after, can enter baking, standard water-content is below 3%.
The dehydration roasting: the dehydration roasting is with manganese sulfate monohydrate (MnSO
4.H
2O) water molecules in the lattice is removed, and is not meant surface water.
Manganese sulfate monohydrate is put the rotation electric furnace with 550-600 ℃ of temperature roasting 2 hours, make manganous sulfate become canescence and get final product by original white or micro mist redness.
Pyrolysis: the manganous sulfate after will dewatering places the rotation electric furnace, and temperature is controlled between 1000-1400 ℃, roasting in oxygen-rich air, and 2 hours time, make it to change trimanganese tetroxide, emit a large amount of sulfurous gas (SO simultaneously
2) gas.Sulfurous gas (SO
2) gas after do not have pressing waste heat boiler, water and drenching cooling tower, gas temperature is reduced to below 50 ℃, again through the gas preparing tank, sulfurous gas (SO
2) gas content is fitted on below 30%, for sulfurous gas (SO
2) reaction tower is used for leaching Manganse Dioxide and produces manganous sulfate and use.
Redox: the trimanganese tetroxide (Mn that pyrolysis is obtained
3O
4) insert roasting in the 700-850 ℃ of rotation electric furnace again, 2 hours time, carry out redox, make it be transformed into manganic oxide (Mn
2O
3).
Disproportionation. oxidation: disproportionation and oxidation two procedures carry out in same reactor, Manganse Dioxide (MnO when reacting for controlled oxidation
2) the nucleus amount, improve bulk specific gravity, save the vitriolic consumption, to adopt to divide and feed in raw material for three times, disproportionation and oxidation hocket.
Disproportionation for the first time: washup slag recycle-water 600kg, dilute sulphuric acid 300kg, manganic oxide powder 600kg, add reactor together and stir, temperature of reaction 92-94 ℃, in 1 hour reaction times, disproportionation finishes for the first time.
Oxidation for the first time: get sodium chlorate 90kg, once drop into 60kg, remaining 30kg visual response temperature adds, because of oxidizing reaction is a thermopositive reaction, when surpassing 95 ℃, temperature stops to feed in raw material, and reinforced when being lower than 91 ℃, oxidizing reaction temperature is controlled between 90-96 ℃, 2 hours reaction times extracted reaction solution the analysis acid content, reached about 70g/l, can carry out second disproportionation, be lower than 60g/l and prolong oxidation time again and make and reach more than the 70g/l.
Disproportionation for the second time: dilute sulphuric acid 100kg, washup slag recycle-water 350kg, manganic oxide powder 300kg add reactor together, treat that temperature is raised to 90 ℃ of timing, react after 30 minutes, can carry out the oxidation second time.
Oxidation for the second time: get sodium chlorate 40kg, at first drop into 20kg, remaining 20kg, the visual response temperature drops into, and react 2 hours, extracts reaction solution the analysis acid content, can carry out disproportionation for the third time about 60g/l, is lower than the 50g/l prolongation reaction times to make acid content reach 60g/l.
Disproportionation for the third time: with diluted acid 100kg, washup recycle-water 350kg, manganic oxide powder 300kg, add reactor together, treat that temperature is raised to 90 ℃ of timing, react after 30 minutes, can carry out oxidation for the third time.
Oxidation for the third time: get sodium chlorate 50kg, at first drop into 20kg, remaining 30kg, the visual response temperature drops into, thrown timing after the sodium chlorate, reacted 3 hours, extracted reaction solution and analyze manganous sulfate content, be lower than the 10g/l entire reaction and finish, be higher than 10g/l and prolong the reaction times again, make it be lower than 10g/l.
Chlorine reclaims produces Potcrate: owing to use sodium chlorate as oxygenant, so there is a large amount of chlorine to produce, now produce Potcrate by the chlorine recovery tower in production process, both can eliminate the chlorine environmental pollution, can create profit again.
Unslaked lime is made milk of lime by 1: 5 water, remove slag, put in the chlorine reaction tower as the chlorine absorption agent, reaction finishes when the solution pH value is neutral (7-7.5), and the slurry press filtration that reaction is good is removed slag, dark red liquid calcium chlorate solution.
Calcium chlorate solution is put reactor, temperature 90-94 ℃, add Repone K, carry out replacement(metathesis)reaction, again through press filtration, refining, condensing crystal, centrifugal, oven dry, Potcrate, purity reaches more than 98, article one, produce the production line of 1000 tons of chemical manganese bioxides (CMD) per year, utilize to reclaim chlorine, can produce 200 tons in Potcrate, per tonly press 5000 yuan of calculating, can create 1,000,000 yuan of sales revenue, 400,000 yuan of the profits of making profits.
Mother liquor reclaims and handles: after oxidizing reaction finishes, stop to stir, slip is put into pickling tank, use clear water 200kg again, reactor is rinsed well, put into pickling tank together, allow its natural sedimentation, put top mother liquor and reclaim, add the 800kg clear water again, stirred 10-15 minute, allow it heavy clear again, put mother liquor, and then the mother liquor in the slurry is blotted, be recovered into together and store bucket with the vacuum pump suction nozzle.Fetch and receive mother liquor to put complex acid poor, allocate sulfuric acid into, acid content is formulated into 300g/l again, and then pumps into the cooling of storage bucket, because a large amount of vitriolic add, sodium sulfate in the mother liquor is state of saturation, along with the cooling of liquid, separates out the formation crystallization gradually, again through press filtration, remove sodium sulfate, deposit dilute sulphuric acid in the diluted acid bucket, for disproportionation acid.
Pickling: content 300g/l diluted acid 1000kg is added pickling tank, add the 200kg clear water again, solid-to-liquid ratio is 1: 1, stir, temperature is controlled at about 98 ℃ reacted 60 minutes, the pickling end, the pickling mother liquor is the same with reaction mother liquor to be reclaimed (take a sample respectively before the reaction and after the reaction and divide plate acid content and manganous sulfate content, the front and back contrast can be found out pickling effect).
Washing: after the pickling mother liquor reclaims, allocated clear water into by 1: 1 again, put into washing after stirring, treat its heavy put top clear liquid clearly after, put into 85 ℃ of hot water again, stirred 15-20 minute, and stopped to stir, make it heavy clear, put top clear liquid, put into 75 ℃ of hot water again, sink behind the restir and put top clear liquid clearly, put into 75 ℃ of hot water again ....Repetitive scrubbing is washed the washing lotion pH value between the 2.8-3, can neutralize.
Neutralization: stop to stir, allow its precipitation, put top clear liquid, put into cold water again temperature is transferred to below 40 ℃, can neutralize, add hydrogen-carbonate by (NHH
4CO
3) the P H value that neutralizes 5-7, restir 30 minutes, pH value is constant, and neutralization finishes, and with the soft water washing once, stirs 10-15 minute again, and the press filtration oven dry gets final product.
Embodiment 2: produce chemical manganese bioxide with sulfurous gas leaching Manganse Dioxide system manganous sulfate
With sulfurous gas leaching Manganse Dioxide system manganous sulfate is main technique of the present invention, the required manganous sulfate of pyrolysis have 70% thus technology produce.
The slag 1200kg of a manganous sulfate was leached in the roasting of learning from else's experience, and fetching and receiving mother liquor 4700kg (solid-to-liquid ratio 1: 4) content is 300g/l dilute sulphuric acid 100kg, slurrying, pump into reaction tower, 2 hours time, it is 2% promptly qualified that sampling analysis slag manganese content is lower than, and pumps into the iron removal trough deironing.
Deironing: open stirrer and stir, add bicarbonate of ammonia (NHH then
4CO
3) pH value is transferred to 5-5.5, sampling analysis solution iron level gets final product press filtration after up to standard.The same SDD solvent that adds is gone into the thick liquid bucket of manganous sulfate refining crystallization during press filtration.
All the other technologies are with embodiment 1.
Claims (3)
1, the method of chemical manganese bioxide is produced in a kind of manganese sulfate monohydrate pyrolysis, it comprises behind the manganese sulfate monohydrate pyrolysis generation trimanganese tetroxide, be manganic oxide with the trimanganese tetroxide redox again, then with manganic oxide through disproportionation, oxidizing reaction, pickling, washing, in and press filtration and stoving process make chemical manganese bioxide, it is characterized in that the POV manganese solution is crystallized into manganese sulfate monohydrate adopts pressure crystalline method, pressing force pot total volume 80% adds the POV manganese solution, heating, stir, after pressure reached 2-5kg, constant voltage was after 1 hour, open filter tap, clear liquid is put, stopped to stir, cut off electrothermal tube power, the opening pressure pot, product is poured out, through centrifugal, deposited in material-stored pool again, sampling analysis, after qualified, can enter baking, standard water-content is below 3%.
2, the method for claim 1 is characterized in that stirring velocity is 60-65 rev/min.
3, method as claimed in claim 1 or 2 is characterized in that pressure is 4kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991155874A CN1163414C (en) | 1999-09-30 | 1999-09-30 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991155874A CN1163414C (en) | 1999-09-30 | 1999-09-30 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1290657A CN1290657A (en) | 2001-04-11 |
| CN1163414C true CN1163414C (en) | 2004-08-25 |
Family
ID=5278525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991155874A Expired - Fee Related CN1163414C (en) | 1999-09-30 | 1999-09-30 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1163414C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101110476B (en) * | 2006-06-07 | 2012-04-11 | 东曹株式会社 | Electrolytic manganese dioxide, positive electrode active material, and battery |
| CN101139111B (en) * | 2006-09-05 | 2014-01-15 | 湖南方程汇鑫化工有限公司 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
| CN102060332B (en) * | 2010-11-10 | 2013-01-23 | 湘西自治州兴湘科技开发有限责任公司 | Method for circularly producing mangano-manganic oxide by manganous sulfate |
| CN106186077B (en) * | 2016-08-11 | 2017-12-08 | 福州大学 | Preparation and its application without coating agent manganese base nanoporous assembled material |
| CN109336184B (en) * | 2018-10-31 | 2021-01-19 | 胡义华 | Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate |
-
1999
- 1999-09-30 CN CNB991155874A patent/CN1163414C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1290657A (en) | 2001-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105695751B (en) | A kind of purification technique of electrolytic manganese anode mud | |
| CN101838736B (en) | Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system | |
| CN100542968C (en) | Utilize the method for sodium hydroxide clean production of titanium dioxide | |
| CN101066827B (en) | Electroplating sludge treating and utilizing process | |
| CN102021345B (en) | Method for recycling vanadium pentoxide and sodium dichromate | |
| CN101857919B (en) | Method for preparing lead nitrate and lead oxide by using lead plaster of waste lead accumulator | |
| CN100396733C (en) | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN109825711A (en) | A kind of titanium dioxide waste acid by sulfuric acid process resource utilization method | |
| CN102382980A (en) | Method for directly purifying cadmium from sponge cadmium | |
| CN114934195A (en) | Lithium salt recovery method and recovery equipment for aluminum electrolysis waste | |
| CN101078059A (en) | Desulfurization and transformation method for waste lead accumulator regenerative lead | |
| CN112978805A (en) | Comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid | |
| CN100396734C (en) | Method for producing the yellow pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN1163414C (en) | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide | |
| CN1239720C (en) | Method for producing high purity metal zinc from zinc oxide ore | |
| CN1023694C (en) | Prepn. of manganese dioxide | |
| CN109913652B (en) | Comprehensive treatment method for waste refractory material in preparation process of ternary cathode material | |
| CN1311340A (en) | Method for producing manganese carbonate from manganese sulfate in waste manganese mud | |
| CN115305574B (en) | Method for rapidly preparing whisker by using phosphogypsum and saline | |
| CN1343623A (en) | Wet process for treating copper or arsenic sulfide | |
| CN1238536C (en) | Process for clean conversion of tantalum niobium ore | |
| CN100375716C (en) | Method of recovering V2O5 from Bayer process mother liquid | |
| CN100363264C (en) | Method of preparing tribasic lead sulphate utilizing spent lead battery plate grid and connecting piece | |
| CN102050495A (en) | Process for preparing tetrahydrate manganese chloride by leaching out rhodochrosite with waste acid | |
| CN107312925A (en) | One kind utilizes calcium hydroxide and sodium hydroxide（Potassium hydroxide）The method that mixed processing refractory metal mineral prepare correspondence oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: GUANGXI SHUANGDE MANGANESE INDUSTRY CO., LTD. Free format text: FORMER OWNER: DU ZUDE Effective date: 20070302 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070302 Address after: 546316, Guangxi City, Yizhou province leading rural manganese mine Patentee after: Guangxi Shuangde Manganese Industry Co., Ltd. Address before: 421001 No. 10 Heping South Road, Hunan, Hengyang Patentee before: Du Zude |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040825 Termination date: 20110930 |