CN101139111B - Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide - Google Patents
Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims description 14
- 239000011572 manganese Substances 0.000 claims abstract description 40
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 29
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 10
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 238000005554 pickling Methods 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 238000006479 redox reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000003252 repetitive effect Effects 0.000 claims description 6
- 238000005201 scrubbing Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 238000002242 deionisation method Methods 0.000 claims description 4
- 239000006210 lotion Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000008234 soft water Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 30
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000000843 powder Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ANFIEGWCRSNVFS-UHFFFAOYSA-N [Na].OCl(=O)=O Chemical compound [Na].OCl(=O)=O ANFIEGWCRSNVFS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- -1 after stirring Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a method to produce chemical manganese dioxide by water manganese sulfate pyrolysis including the technics steps of mineral powder roasting, disproportionation reaction, iron removing, manganese sulfate solution preparation, pressure crystallization, dewatering roasting, pyrolysis, redox, disproportionation.oxidation reaction, pickling, repeat washing, neutralization, pressure filtration and drying, etc. The trimanganese tetroxide after pyrolysis is pumped in the oxygen-enriched air with an oxygen content of 60 to 50 percent during redox reaction to lead part of the trimanganese tetroxide to be directly reduced to rough manganese dioxide with the manganese dioxide of more than 75 percent and lead the content of the r-shaped structure of the crystalline structure in manganese dioxide products to be improved from 75 percent to 98 percent, reduce the specific surface of the products and improve the heavy current discharge performance. Through the improvement on the technical skill, the chemical manganese dioxide produced by the present invention has become superior materials to produce alkaline manganese dry cells. The main content of the products produced by the present invention has been improved from 92 percent to 95 to 95.5 percent and the content of impurities has been reduced in large scale. The present invention is suitable for alkaline manganese cell production.
Description
Technical field
The present invention relates to the production method of the chemical manganese bioxide of chemical field, specially refer to the method that monohydrated mangnese sulfate pyrolysizing is produced chemical manganese bioxide.
Background technology
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 making by electrolytic process can meet the specification of quality of heavy body high power battery raw material, regrettably electrolytic process preparing manganese dioxide has the shortcomings such as power consumption is high, environmental pollution is large, facility investment is large, the production cycle is long, production cost is high, cause valuable product, restricted to a certain extent the development of battery industry.Eighties of last century is since the seventies, and 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 by ammonium ammonium formiate method, and annual production reaches 40,000 tons, the production history of existing more than 20 year.Other is as Japan, the U.S., the French production that also has small dimension.The chemical manganese bioxide that this method is produced and Chemical Composition and the crystalline structure (being all mainly r-type) of electrolytic manganese dioxide are basically identical, do not exist together is physicals, the median size of electrolytic manganese dioxide is than the large twice of chemical manganese bioxide, and specific surface only has chemical manganese bioxide half, therefore chemical manganese bioxide is compared with electrolytic manganese dioxide, there is Manganse Dioxide utilization ratio high, liquid absorption is large, battery recovery performance is strong, the advantages such as anti-leakage is good, shortcoming is that (take Belgian is example) chemical manganese bioxide internal resistance is larger, short-circuit current and load voltage are slightly low, large electric current, heavy loading electric discharge property is slightly lower than electrolytic manganese dioxide, and facility investment is large, production cycle is long, production cost is high, quality product cannot guarantee (because there being ammonia to follow compression process, whole production process needs High Temperature High Pressure, restive every technic index).
For addressing the above problem, the applicant has applied for " monohydrated mangnese sulfate pyrolysizing is produced the method for chemical manganese bioxide " patent of invention on September 30th, 1999, it is to adopt monohydrated mangnese sulfate pyrolysizing to generate after trimanganese tetroxide, by trimanganese tetroxide redox, be manganic oxide again, then by manganic oxide through disproportionation, oxidizing reaction, pickling, washing, in and the technique such as press filtration oven dry make chemical manganese bioxide, it is when crystallizing into manganese sulfate monohydrate by POV manganese solution, what adopt is the method for pressure crystallization: pressing force pot total volume 80% adds POV manganese solution, heating, stir, pressure reaches after 2-5kg, after constant voltage 1 hour, open filter tap, clear liquid is put, stop stirring, cut off electrothermal tube power, opening pressure pot, product is poured out, again through centrifugal, deposit material-stored pool in, sampling analysis, after qualified, be baked to standard water-content below 3%.It is little that the method has environmental pollution, and facility investment is few, (within three days, can go out product) with short production cycle, production cost is low, and (because following compression process without ammonia, whole production process is without High Temperature High Pressure for stable and reliable product quality, be easy to control every technic index, convenient operation) etc. advantage.But along with scientific technological advance, Battery Industry is modified into alkaline Mn cell by original acid battery.And the chemical manganese bioxide that the method is produced is not suitable for production alkaline Mn cell, thereby part technique must be improved.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art and provide a kind of facility investment few, with short production cycle, stable and reliable product quality, electrical property is better than electrolytic manganese dioxide, is applicable to produce the method that the monohydrated mangnese sulfate pyrolysizing of alkaline Mn cell is produced chemical manganese bioxide.
Technical scheme of the present invention is: the method that monohydrated mangnese sulfate pyrolysizing is produced chemical manganese bioxide comprises breeze roasting, disproportionation, deironing, manganese sulfate solution is refining, pressure crystallization, dehydration roasting, pyrolysis, redox, disproportionation. oxidizing reaction, pickling, repetitive scrubbing, neutralization, the processing steps such as press filtration oven dry, it is characterized in that the trimanganese tetroxide generating after pyrolysis is when redox reaction, pass into oxygen level and be 60-50% oxygen-rich air, oxidization time is 2.5-6 hours, make the direct oxidation of part trimanganese tetroxide be reduced into containing Manganse Dioxide more than 75% thick Manganse Dioxide, can reduce oxygenant chloric acid sodium consumption 30%, make content that crystalline structure in manganese dioxide product is " r " type structure bring up to 98% by original 75%, increase the micropore of product particle, aperture, reduce specific surface area, improve product heavy-current discharge performance.
The further technical scheme of the present invention is: at disproportionation. in oxidation reaction process, during each disproportionation reaction, solid-to-liquid ratio must be controlled at 1:2-3, but after disproportionation reaction completes, while adding sodium chlorate oxidation, should solid-to-liquid ratio be reduced to 1:1.5-2.5 along with reaction times prolongation, to reduce the specific surface area of product and to be controlled at 24-30m
2/ g scope, improves bulk specific gravity and is controlled within the scope of 1.65-1.75g/ml, improves product fill-up, thereby improves drying battery discharge capacity.
The present invention further technical scheme is: at disproportionation. in the process of oxidizing reaction, when each oxidizer is carried out oxidizing reaction, the reaction times of oxidizing reaction is controlled to 3.1-6 hours, manganous sulfate content in while detection reaction solution, be strict controlled in below 10g/L, to have prevented that manganic oxide from bringing product into.
The present invention further technical scheme is: when repetitive scrubbing, washing lotion pH value is washed between 2.0-2.5 and with sodium carbonate, neutralized, and without bicarbonate of ammonia neutralization, to prevent product tape ammonium ion, be applicable to alkaline Mn cell; After neutralization finishes, with the washing of deionization soft water, the impurity in planar water in order to avoid product is in the suds.
The present invention is by the improvement in above Technology, it is high that the chemical manganese bioxide of producing not only has Manganse Dioxide utilization ratio, liquid absorption is large, battery recovery performance is strong, anti-leakage waits well all advantages of chemical manganese bioxide, its short-circuit current and load voltage and large electric current heavy loading electric discharge property are all better than electrolytic manganese dioxide, become the high quality raw material of producing alkali manganese type drying battery, the main content of its product brings up to 95%-95.5% by original 92%, foreign matter content significantly reduces, there is environmental pollution little, facility investment is few, (within three days, can go out product) with short production cycle, production cost is low, stable and reliable product quality is (because following compression process without ammonia, whole production process is without High Temperature High Pressure, be easy to control every technic index, convenient operation) advantage such as, be applicable to produce alkaline Mn cell.
The Manganse Dioxide breeze roasting of take below manganous sulfate processed is produced chemical manganese bioxide and detailed structure of the present invention is further described as example.
Embodiment
Embodiment mono-: the method that monohydrated mangnese sulfate pyrolysizing is produced chemical manganese bioxide comprises the steps:
Breeze roasting: get the manganese dioxide powder that content is 60% left and right (fineness 200 orders) and put the roasting of rotation electric furnace, 750-800 ℃ of temperature, time 2 h, becomes manganic oxide (Mn2O3) by the roasting of Manganse Dioxide breeze.
Disproportionation: fetch and receive mother liquor 2800kg, content is the dilute sulphuric acid 800kg of 300g/L, roasting manganic oxide breeze 1200kg (solid-to-liquid ratio 1:3) is mixed with ore pulp, puts between the temperature of 92-96 ℃ of reactor inherences and reacts and within 60 minutes, make manganese sulfate solution ore pulp.
Deironing: with roasting manganic oxide breeze, between 90-96 ℃ of temperature, evenly join while stirring in manganese sulfate solution ore pulp, utilize manganic oxide breeze disproportionation reaction to need the principle of sulfuric acid, manganese sulfate solution pulp PH value is adjusted between 5-5.5, as iron-free in solution, get final product press filtration, obtaining product is manganese sulfate solution, adds SDD solution in press filtration, and object is removed the heavy metal in solution.
Manganese sulfate solution is refining: deposits 72 hours the manganese sulfate solution that adds SDD solution is static, and the various foreign matter contents of sampling analysis solution, rear press filtration up to standard, obtains the POV manganese solution of BE ° 23-24.
Pressure crystallization: pressure crystallizing pan is provided with 60-65 revs/min, tensimeter, thermometer, blow-off valve, safety valve, stirrer, filter on top, bottom filter tap, electrothermal tube, pressing force pot total volume 80% adds POV manganese solution, heating, pressure reaches after 2-5kg, and constant voltage is after 1 hour, open filter tap, clear liquid is put.Stop stirring, cut off electrothermal tube power, opening pressure pot, pours out product, then through centrifugal, deposits material-stored pool in, sampling analysis, qualified after, can enter baking, standard water-content is below 3%.
Dehydration roasting: dehydration roasting is that the water molecules in manganese sulfate monohydrate (MnSO4.H2O) lattice is removed, do not refer to surface water, manganese sulfate monohydrate is put to rotation 550-600 ℃ of temperature roastings 2 hours for electric furnace, make manganous sulfate become canescence by original white or micro mist redness.
Pyrolysis: the manganous sulfate after dehydration is placed in to rotation electric furnace, and temperature is controlled between 1000-1400 ℃, roasting in oxygen-rich air, time 2 h, makes it to become trimanganese tetroxide.
Redox: the trimanganese tetroxide that pyrolysis is obtained is inserted in 700-850 ℃ of rotation electric furnaces again, pass into oxygen level and be 60-50% oxygen-rich air, roasting in oxygen-rich air, 2.5-6 hours time, make part trimanganese tetroxide be direct oxidation into containing Manganse Dioxide more than 75% thick Manganse Dioxide, can reduce oxygenant chloric acid sodium consumption 30%, make content that crystalline structure in manganese dioxide product is " r " type structure bring up to 98% by original 75%, increase micropore, the aperture of product particle, reduce specific surface area, improve product heavy-current discharge performance; Also have part trimanganese tetroxide to be transformed into manganic oxide.
Disproportionation. oxidation: disproportionation carries out in same reactor with oxidation two procedures, and Manganse Dioxide nucleus amount, improves bulk specific gravity when controlling oxidizing reaction, saves the consumption of sulfuric acid, adopt minutes three times reinforced, disproportionation and oxidation hocket; And during each disproportionation reaction, solid-to-liquid ratio must be controlled at 1:2-3, but after disproportionation reaction completes, while adding sodium chlorate oxidation, should solid-to-liquid ratio be reduced in the scope of 1:1.5-2.5 along with reaction times prolongation, to reduce the specific surface area of product, (be controlled at 24-30m
2/ g scope), improve bulk specific gravity (being controlled within the scope of 1.65-1.75g/ml), improve product fill-up, thereby improve drying battery discharge capacity.
Disproportionation for the first time: washup slag recycle-water 900kg, dilute sulphuric acid 300kg, manganic oxide powder 600kg, add together reactor to stir, 92-94 ℃ of temperature of reaction, 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 oxidizing reaction is a thermopositive reaction, when surpassing 95 ℃, temperature stops feeding in raw material, reinforced during lower than 91 ℃, oxidizing reaction temperature is controlled between 90-96 ℃ to 3.1 hours reaction times, manganous sulfate content in detection reaction solution is strict controlled in below 10g/L simultaneously, can prevent that like this manganic oxide is entrained into product completely; In reaction solution, acid content reaches about 70g/L, can carry out the second disproportionation, lower than 60g/L, extends more than oxidation time makes to reach 70g/L again.
Disproportionation for the second time: dilute sulphuric acid 100kg, washup slag recycle-water 500kg, manganic oxide powder 300kg add reactor together, treat that temperature is raised to 90 ℃ of timing, react after 30 minutes, can be oxidized for the second time;
Be oxidized for the second time: sodium chlorate 40kg, first drop into 20kg, remaining 20kg visual response temperature drops into, 4.5 hours reaction times, manganous sulfate content in detection reaction solution is strict controlled in below 10g/L simultaneously, can prevent that like this manganic oxide is entrained into product completely; In reaction solution, acid content can be carried out disproportionation for the third time in about 60g/L, extends the reaction times make acid content reach 60g/L lower than 50g/L.
Disproportionation for the third time: by diluted acid 100kg, washup recycle-water 500kg, manganic oxide powder 300kg, add together reactor, treat that temperature is raised to 90 ℃ of timing, react after 30 minutes, can be oxidized for the third time;
Oxidation for the third time: get sodium chlorate 50kg, first drop into 20kg, remaining 30kg visual response temperature drops into, finish timing after sodium chlorate, 6 hours reaction times, manganous sulfate content in detection reaction solution is strict controlled in below 10g/L simultaneously, can prevent that like this manganic oxide is entrained into product completely.
Pickling: content 300g/L diluted acid 1000kg is added to pickling tank, add again 200kg clear water, solid-to-liquid ratio is 1:1, stir, temperature is controlled at about 98 ℃ reactions 60 minutes, pickling finishes, and pickling mother liquor is the same with reaction mother liquor to be reclaimed (before reaction with after reacting, sample respectively minute plate acid content and manganous sulfate content, front and back contrast can be found out pickling effect).
Washing: after pickling mother liquor reclaims, then allocate clear water into by 1:1, put into washing after stirring, after clear liquid above its supernatant is put, then put into 85 ℃ of hot water, stir 15-20 minutes, stop stirring, allow its supernatant, put clear liquid above, then put into 75 ℃ of hot water, after stirring, supernatant is put clear liquid above again, put into again 75 ℃ of hot water ..., repetitive scrubbing, washes washing lotion pH value between 2.0-2.5 and neutralizes.
Neutralization: stop stirring, allow it precipitate, put clear liquid above, then put into cold water temperature is transferred to below 40 ℃, can neutralize, add sodium carbonate neutralization and without bicarbonate of ammonia neutralization, be not suitable for alkaline Mn cell to prevent product clip band ammonium ion; PH value 5-7 is arrived in neutralization, then stirs 30 minutes, and pH value is constant, and neutralization finishes, then with deionization soft water, washs the impurity in planar water in order to avoid product is in the suds; Washing is once stirred 10-15 minutes again, and press filtration is dried.
Embodiment bis-: the method that monohydrated mangnese sulfate pyrolysizing is produced chemical manganese bioxide comprises disproportionation. oxidizing process, get washup slag recycle-water 1500kg, dilute sulphuric acid 300kg during disproportionation for the first time, manganic oxide powder 600kg adds reactor reaction together; Get for the second time washup slag recycle-water 800kg, dilute sulphuric acid 100kg during disproportionation, manganic oxide powder 300kg adds reactor reaction together; Get washup recycle-water 800kg, diluted acid 100kg, manganic oxide powder 300kg during disproportionation for the third time, add together reactor reaction.All the other techniques are identical with embodiment mono-.
The present invention is by the improvement in above Technology, and the chemical manganese bioxide of producing becomes the high quality raw material of producing alkali manganese type drying battery, and the main content of its product brings up to 95%-95.5% by original 92%, and foreign matter content significantly reduces.
Claims (5)
1. a monohydrated mangnese sulfate pyrolysizing is produced the method for chemical manganese bioxide, it comprises that breeze roasting, disproportionation, deironing, manganese sulfate solution are refining, pressure crystallization, dehydration roasting, pyrolysis, redox, disproportionation-oxidizing reaction, pickling, repetitive scrubbing, neutralization, press filtration stoving process step, it is characterized in that the trimanganese tetroxide generating after pyrolysis is when redox reaction, pass into oxygen level and be 60-50% oxygen-rich air, oxidization time is 2.5-6 hours.
2. monohydrated mangnese sulfate pyrolysizing according to claim 1 is produced the method for chemical manganese bioxide, it is characterized in that in disproportionation-oxidation reaction process, during each disproportionation reaction, solid-to-liquid ratio must be controlled at 1:2-3, after disproportionation reaction completes, while adding sodium chlorate oxidation, should solid-to-liquid ratio be changed to 1:1.5-2.5 along with reaction times prolongation.
3. monohydrated mangnese sulfate pyrolysizing according to claim 1 and 2 is produced the method for chemical manganese bioxide, it is characterized in that in the process of disproportionation-oxidizing reaction, when each oxidizer is carried out oxidizing reaction, the reaction times of oxidizing reaction is controlled to 3.1-6 hours, manganous sulfate content in detection reaction solution, is strict controlled in below 10g ∕ L simultaneously.
4. monohydrated mangnese sulfate pyrolysizing according to claim 1 and 2 is produced the method for chemical manganese bioxide, it is characterized in that when repetitive scrubbing, and washing lotion pH value is washed between 2.0-2.5 and with sodium carbonate, neutralized; After neutralization finishes, with the washing of deionization soft water.
5. monohydrated mangnese sulfate pyrolysizing according to claim 3 is produced the method for chemical manganese bioxide, it is characterized in that when repetitive scrubbing, and washing lotion pH value is washed between 2.0-2.5 and with sodium carbonate, neutralized; After neutralization finishes, with the washing of deionization soft water.
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| CN1290657A (en) * | 1999-09-30 | 2001-04-11 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1290657A (en) * | 1999-09-30 | 2001-04-11 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
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| Title |
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| JP昭62-30620A 1987.02.09 |
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