CN103011297A - Method for production of high purity manganese sulfate by using pyrolusite as raw material - Google Patents
Method for production of high purity manganese sulfate by using pyrolusite as raw material Download PDFInfo
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- CN103011297A CN103011297A CN2012105198429A CN201210519842A CN103011297A CN 103011297 A CN103011297 A CN 103011297A CN 2012105198429 A CN2012105198429 A CN 2012105198429A CN 201210519842 A CN201210519842 A CN 201210519842A CN 103011297 A CN103011297 A CN 103011297A
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- manganese
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- fluoride
- pyrolusite
- manganous
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 51
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 37
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 37
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002994 raw material Substances 0.000 title abstract description 7
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 10
- 230000002829 reductive effect Effects 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 13
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 8
- 239000002817 coal dust Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 8
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 claims description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 239000011572 manganese Substances 0.000 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 2
- 239000001099 ammonium carbonate Substances 0.000 abstract 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 235000006748 manganese carbonate Nutrition 0.000 abstract 1
- 239000011656 manganese carbonate Substances 0.000 abstract 1
- 229940093474 manganese carbonate Drugs 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 description 4
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- RLBLFSQXAKQALA-UHFFFAOYSA-N [Na].[K].[Mg].[Ca] Chemical compound [Na].[K].[Mg].[Ca] RLBLFSQXAKQALA-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- -1 feed Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a production method for high purity manganese sulfate. The production method is characterized in that pyrolusite is used as a raw material and is reduced by using a carbon fire method, then an acid is added for leaching, a vulcanizing agent is used to remove heavy metals consisting of cobalt and nickel, a fluoride is employed to remove calcium and magnesium, then filtering is carried out, ammonium bicarbonate or ammonium carbonate is added into a filtrate for deposition of manganese to realize separation of potassium and sodium, an obtained filtrate is used for recovery of the by-product ammonia sulfate for usage as an additive for metal manganese, the filter residue manganese carbonate is washed and then subjected to acid dissolution so as to obtain a manganese sulfate solution, and then crystallization is carried out to obtain a high purity manganese sulfate product, wherein mother liquor can be returned to a high purity system for reutilization. With the method provided by the invention, the high purity manganese sulfate product in which MnSO4 content is more than 99.8% and respective content of impurities consisting of Ca, Mg, K and Na is lower than 10 ppm is produced.
Description
Technical field
The present invention relates to a kind of production method of high-purity manganese sulphate, specifically relating to pyrolusite is raw material, adopts carbon fire reduction, Ore Leaching to produce manganese sulfate monohydrate content more than 99.8%, calcium magnesium potassium sodium impurity all less than the method for the high-purity sulphuric acid manganese product of 30ppm.
Background technology
Manganous sulfate is a kind of traditional manganese product salt, and purposes is very extensive.At present, domestic production of manganese sulfate as, mainly take pyrolusite as raw material, divide two kinds of reduction of carbon fire reduction and wet reducing (reductive agents such as sulfurous iron ore, ferrous sulfate or titanium white waste acid) acidleach extract technology technology, and then carry out simple oxidation-hydrolysis deironing, sulfuration removing heavy metals, filter, staticly settle, solution crystallization, centrifuge dehydration oven dry, obtain technical grade, feed grade or three kinds of other manganese sulfate products of level of elaboration level, be used for the fields such as chemical fertilizer, feed, paint, agricultural chemicals.In recent years, along with the development of New Energy Sources lithium manganate battery technology, more and more come into one's own take high purity manganese sulfate as the raw material production lithium manganate, Technology is also more and more ripe.And consider that for various reasons such as environment protection, cost consumptions particularly the developed countries such as America and Europe, Japan and Korea S almost do not have manganous sulfate production abroad; China has become in the world main manganous sulfate producing country and supply country, about 150,000 tons of annual output.Therefore, overseas lithium manganate battery manufacturer wishes to seek high-purity manganous sulfate material in China, is used for tapping a new source of energy lithium cell.
Product specification requires as follows: Mn:32.2%MIN, Fe:0.0005%MAX, K:0.01% MAX, Na:0.01% MAX, Co:0.003% MAX, Zn:0.001% MAX, Ca:0.01%MAX, Mg:0.01%MAX, Ni:0.003%MAX.
And no matter domestic production of manganese sulfate as technology is wet method or pyrogenic process, and the purification and impurity removal technology all only rests on oxidation-hydrolysis deironing, sulfuration removing heavy metals simple process stage, the low (MnSO of product master content
4H
2O is between 98% ~ 98.5%), foreign matter content high (calcium-magnesium content all more than 1200ppm, each about 600ppm of potassium sodium content), can't reach above high purity manganese sulfate technical requirement far away.Therefore, from original ore powder, expect to make the product that meets high-purity index request, mainly be will calcium magnesium and potassium sodium are technical to make a breakthrough and improve purifying.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of high-purity manganese sulphate, the Manganous sulfate monohydrate content of producing are greater than 99.6%, and the content of calcium, magnesium, sodium, potassium impurity all is lower than 30ppm.
Take pyrolusite as raw material, after adding sulfuric acid leaching, the first step adopts barium sulphide except cobalt nickel, second step is controlled 90 ℃ of temperature of reaction, pH value in reaction 5.0～7.0 well, remove calcium-magnesium removing with Neutral ammonium fluoride, the manganese sulfate solution that obtains after the filtration of the 3rd step adds bicarbonate of ammonia and generates the manganous carbonate precipitation with separating potassium sodium, and filter liquor reclaims to get the ammonium sulfate byproduct, the molten high-purity sulphuric acid manganese solution that gets of filter residue manganous carbonate washing acid gets the high-purity sulphuric acid manganese product with solution crystallization.For achieving the above object, technical scheme of the present invention is:
The production method of 99.6% high-purity manganese sulphate may further comprise the steps:
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water are pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration is 98% sulfuric acid, and sulphuric acid is 1.05～1.1 times of theoretical acid, at 60～90 ℃ of lower stirring reaction time 1～2h, then add deironing manganese powder iron removal by oxidation 0.5～1h, the add-on of manganese powder is 1.05～1.1 times of theoretical requirement, adds vulcanizing agent, and the add-on of vulcanizing agent is 1% of reduced ore dry weight, normal-temperature reaction 30～60min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds fluorochemical, and add-on is 4～6 times of theoretical molar quality, at 80～90 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.1～1.3 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 350～500g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
Above-mentioned vulcanizing agent is a kind of in manganese sulfide, Iron sulfuret, barium sulphide, ammonium sulfide, zinc sulphide and the hydrogen sulfide or their composition.
Above-mentioned fluorochemical is a kind of in manganous fluoride, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride and the barium fluoride or their composition.
Advantage of the present invention:
1. the present invention produces high-purity manganese sulphate, and production process does not need to add expensive chemical reagent, and production cost is low, and is easy to operate, and the controllability of quality and circulation ratio are high, and quality is guaranteed.
2. the recyclable ammonium sulfate byproduct of the present invention is used as the additive that manganese metal is produced, but primary crystallization gets the high-purity sulphuric acid manganese product, and is therefore simple to operate, allows easily producers grasp.
Embodiment
Embodiment 1
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water were pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration was 98% sulfuric acid, and sulphuric acid is 1.05 times of theoretical acid, at 60 ℃ of lower stirring reaction time 2h, then add the deironing manganese powder, iron removal by oxidation 1h, the add-on of manganese powder is 1.05～1.1 times of theoretical requirement, add ammonium sulfide, the add-on of ammonium sulfide is 1% of reduced ore dry weight, and normal-temperature reaction 60min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds barium fluoride, and add-on is 4 times of theoretical molar quality, at 80 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.1 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 350g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
Embodiment 2
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water are pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration is 98% sulfuric acid, and sulphuric acid is 1.07 times of theoretical acid, at 70 ℃ of lower stirring reaction time 1.5h, then add deironing manganese powder iron removal by oxidation 0.7h, the add-on of manganese powder is 1.06 times of theoretical requirement, adds manganese sulfide, and the add-on of manganese sulfide is 1% of reduced ore dry weight, normal-temperature reaction 40min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds manganous fluoride, and add-on is 5 times of theoretical molar quality, at 85 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.2 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 400g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
Embodiment 3
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water are pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration is 98% sulfuric acid, and sulphuric acid is 1.08 times of theoretical acid, at 80 ℃ of lower stirring reaction time 2h, then add deironing manganese powder iron removal by oxidation 1h, the add-on of manganese powder is 1.1 times of theoretical requirement, adds hydrogen sulfide, and the add-on of hydrogen sulfide is 1% of reduced ore dry weight, normal-temperature reaction 45min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds barium fluoride, and add-on is 6 times of theoretical molar quality, at 90 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.3 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 450g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
Embodiment 4
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 850～900 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water are pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration is 98% sulfuric acid, and sulphuric acid is 1.1 times of theoretical acid, at 60～90 ℃ of lower stirring reaction time 1.5h, then add deironing manganese powder iron removal by oxidation 1h, the add-on of manganese powder is 1.06 times of theoretical requirement, adds Iron sulfuret, and the add-on of Iron sulfuret is 1% of reduced ore dry weight, normal-temperature reaction 50min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds Potassium monofluoride, and add-on is 4.5 times of theoretical molar quality, at 90 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.25 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 460g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
Embodiment 5
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 880～900 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water are pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration is 98% sulfuric acid, and sulphuric acid is 1.1 times of theoretical acid, at 75 ℃ of lower stirring reaction time 2h, then add deironing manganese powder iron removal by oxidation 0.5h, the add-on of manganese powder is 1.1 times of theoretical requirement, adds barium sulphide, and the add-on of barium sulphide is 1% of reduced ore dry weight, normal-temperature reaction 60min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds Sodium Fluoride, and add-on is 5 times of theoretical molar quality, at 90 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.15 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 380g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
Embodiment 6
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 800～850 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water are pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration is 98% sulfuric acid, and sulphuric acid is 1.08 times of theoretical acid, at 70 ℃ of lower stirring reaction time 2h, then add deironing manganese powder iron removal by oxidation 1h, the add-on of manganese powder is 1.08 times of theoretical requirement, adds zinc sulphide, and the add-on of zinc sulphide is 1% of reduced ore dry weight, normal-temperature reaction 30min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds Neutral ammonium fluoride, and add-on is 5 times of theoretical molar quality, at 90 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.3 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 420g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
Table 1 obtains manganese content and the foreign matter content result of manganese sulfate product for embodiment
It can be seen from the table the present invention produce the manganous sulfate that the method for high-purity manganese sulphate produces purity all greater than more than 99.8%, the content of the impurity such as calcium magnesium potassium sodium is all less than 30ppm.
Claims (3)
1. the production method of a high-purity manganese sulphate is characterized in that: may further comprise the steps:
A. the carbon of pyrolusite fire reduction-leaching: with pyrolusite powder, after the reduction coal dust is pressed the quality proportioning mixing of 100:18, drop in the reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after the discharging cooling, after reducing material and deionized water are pressed the solid-to-liquid ratio pulp of 1:4, the adding weight concentration is 98% sulfuric acid, and sulphuric acid is 1.05～1.1 times of theoretical acid, at 60～90 ℃ of lower stirring reaction time 1～2h, then add deironing manganese powder iron removal by oxidation 0.5～1h, the add-on of manganese powder is 1.05～1.1 times of theoretical requirement, adds vulcanizing agent, and the add-on of vulcanizing agent is 1% of reduced ore dry weight, normal-temperature reaction 30～60min filters;
B. remove calcium, magnesium addition: the filtrate that obtains to step a adds fluorochemical, and add-on is 4～6 times of theoretical molar quality, at 80～90 ℃ of lower reaction 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate that obtains to step b adds bicarbonate of ammonia or volatile salt, and add-on is 1.1～1.3 times of theoretical amount, generates the manganous carbonate precipitation, filter, by liquid-solid ratio 3:1 with 60 ℃ of deionized water wash manganous carbonate throw outs;
D. dissolving and crystallization: be manganous carbonate after 50% sulfuric acid dissolution step c washs with weight concentration, make MnSO
4Concentration is the manganese sulfate solution of 350～500g/L, leaves standstill, and solution carries out normal pressure crystallization manganous sulfate crystal, dries with the whizzer centrifuge dehydration, and drying obtains high-purity manganese sulphate again.
2. the production method of high-purity manganese sulphate as claimed in claim 1 is characterized in that: described vulcanizing agent is a kind of in manganese sulfide, Iron sulfuret, barium sulphide, ammonium sulfide, zinc sulphide and the hydrogen sulfide or their composition.
3. the production method of high-purity manganese sulphate as claimed in claim 1 is characterized in that: described fluorochemical is a kind of in manganous fluoride, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride and the barium fluoride or their composition.
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