CN103011297B - 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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- CN103011297B CN103011297B CN201210519842.9A CN201210519842A CN103011297B CN 103011297 B CN103011297 B CN 103011297B CN 201210519842 A CN201210519842 A CN 201210519842A CN 103011297 B CN103011297 B CN 103011297B
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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 49
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 35
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 35
- 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 13
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 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
- 238000005406 washing Methods 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
- 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
- 150000007513 acids Chemical class 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
- 238000006460 hydrolysis reaction Methods 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
- 239000000126 substance Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 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 the method that manganese sulfate monohydrate content more than 99.8%, calcium magnesium potassium sodium impurity are all less than 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, minute carbon fire reduction and wet reducing reductive agents such as () sulfurous iron ore, ferrous sulfate or titanium white waste acids two kinds of reduction extract technology technology of acidleach, and then be simply oxidized-be hydrolyzed deironing, sulfuration removing heavy metals, and to filter, staticly settle, solution crystallization, centrifuge dehydration are dried, obtain technical grade, feed grade or three kinds of other manganese sulfate products of level of fine work level, for fields such as chemical fertilizer, feed, paint, agricultural chemicals.In recent years, along with the development of New Energy Sources lithium manganate battery technology, the high purity manganese sulfate of take more and more comes into one's own as raw material production lithium manganate, and Technology is also more and more ripe.And abroad for the various reasons such as environment protection, cost consumption, consider, particularly the developed country such as America and Europe, Japan and Korea S, does not almost have manganous sulfate production; China has become in the world main manganous sulfate producing country and supply country, approximately 150,000 tons of annual outputs.Therefore, abroad lithium manganate battery manufacturer wishes to find high-purity manganous sulfate material in China, for the lithium cell that taps a new source of energy.
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, purification and impurity removal technology all only rests on oxidation-hydrolysis deironing, sulfuration removing heavy metals simple process stage, the low (MnSO of the main content of product
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), cannot 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, be mainly to purify calcium magnesium and potassium sodium is technical makes a breakthrough and improve.
Summary of the invention
The production method that the object of this invention is to provide a kind of high-purity manganese sulphate, the Manganous sulfate monohydrate content of producing is greater than 99.6%, and the content of calcium, magnesium, sodium, potassium impurity is all lower than 30ppm.
Take pyrolusite as raw material, add after 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, with Neutral ammonium fluoride, remove calcium-magnesium removing, the manganese sulfate solution that the 3rd step obtains after filtering adds bicarbonate of ammonia and generates manganous carbonate precipitation with separating potassium sodium, and filter liquor reclaims to obtain ammonium sulfate byproduct, the molten high-purity sulphuric acid manganese solution that obtains of filter residue manganous carbonate washing acid, obtains high-purity sulphuric acid manganese product by solution crystallization.For achieving the above object, technical scheme of the present invention is:
The production method of 99.6% high-purity manganese sulphate, comprises the following steps:
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of 100:18, drop in reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.05～1.1 times of theoretical acid, stirring reaction time 1～2h at 60～90 ℃, 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, add vulcanizing agent, the add-on of vulcanizing agent is 1% of reduced ore dry weight, normal-temperature reaction 30～60min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds fluorochemical, add-on is 4～6 times of theoretical molar quality, at 80～90 ℃, reacts 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, add-on is theoretical amount 1.1～1.3 times, generate manganous carbonate precipitation, filter, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnSO
4concentration is the manganese sulfate solution of 350～500g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration.
Above-mentioned vulcanizing agent is a kind of in manganese sulfide, Iron sulfuret, barium sulphide, ammonium sulfide, zinc sulphide and hydrogen sulfide or their composition.
Above-mentioned fluorochemical is a kind of in manganous fluoride, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride and 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, easy to operate, and controllability and the circulation ratio of quality are high, and quality is guaranteed.
2. the additive that the recyclable ammonium sulfate byproduct of the present invention is produced as manganese metal, can obtain high-purity sulphuric acid manganese product by primary crystallization, therefore simple to operate, easily allows producers grasp.
Embodiment
embodiment 1
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of 100:18, drop in reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.05 times of theoretical acid, stirring reaction time 2h at 60 ℃, then add 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, normal-temperature reaction 60min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds barium fluoride, add-on is 4 times of theoretical molar quality, at 80 ℃, reacts 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, add-on is theoretical amount 1.1 times, generate manganous carbonate precipitation, filter, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnSO
4concentration is the manganese sulfate solution of 350g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration.
embodiment 2
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of 100:18, drop in reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.07 times of theoretical acid, stirring reaction time 1.5h at 70 ℃, then add deironing manganese powder iron removal by oxidation 0.7h, the add-on of manganese powder is 1.06 times of theoretical requirement, add manganese sulfide, the add-on of manganese sulfide is 1% of reduced ore dry weight, normal-temperature reaction 40min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds manganous fluoride, add-on is 5 times of theoretical molar quality, at 85 ℃, reacts 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, add-on is theoretical amount 1.2 times, generate manganous carbonate precipitation, filter, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnSO
4concentration is the manganese sulfate solution of 400g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration.
embodiment 3
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of 100:18, drop in reduction furnace, 800～900 ℃ of maturing temperatures, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.08 times of theoretical acid, stirring reaction time 2h at 80 ℃, then add deironing manganese powder iron removal by oxidation 1h, the add-on of manganese powder is 1.1 times of theoretical requirement, add hydrogen sulfide, the add-on of hydrogen sulfide is 1% of reduced ore dry weight, normal-temperature reaction 45min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds barium fluoride, add-on is 6 times of theoretical molar quality, at 90 ℃, reacts 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, add-on is theoretical amount 1.3 times, generate manganous carbonate precipitation, filter, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnSO
4concentration is the manganese sulfate solution of 450g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration.
embodiment 4
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of 100:18, drop in reduction furnace, 850～900 ℃ of maturing temperatures, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.1 times of theoretical acid, stirring reaction time 1.5h at 60～90 ℃, then add deironing manganese powder iron removal by oxidation 1h, the add-on of manganese powder is 1.06 times of theoretical requirement, add Iron sulfuret, the add-on of Iron sulfuret is 1% of reduced ore dry weight, normal-temperature reaction 50min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds Potassium monofluoride, add-on is 4.5 times of theoretical molar quality, at 90 ℃, reacts 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, add-on is theoretical amount 1.25 times, generate manganous carbonate precipitation, filter, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnSO
4concentration is the manganese sulfate solution of 460g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration.
embodiment 5
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of 100:18, drop in reduction furnace, 880～900 ℃ of maturing temperatures, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.1 times of theoretical acid, stirring reaction time 2h at 75 ℃, then add deironing manganese powder iron removal by oxidation 0.5h, the add-on of manganese powder is 1.1 times of theoretical requirement, add barium sulphide, the add-on of barium sulphide is 1% of reduced ore dry weight, normal-temperature reaction 60min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds Sodium Fluoride, add-on is 5 times of theoretical molar quality, at 90 ℃, reacts 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, add-on is theoretical amount 1.15 times, generate manganous carbonate precipitation, filter, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnSO
4concentration is the manganese sulfate solution of 380g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration.
embodiment 6
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of 100:18, drop in reduction furnace, 800～850 ℃ of maturing temperatures, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.08 times of theoretical acid, stirring reaction time 2h at 70 ℃, then add deironing manganese powder iron removal by oxidation 1h, the add-on of manganese powder is 1.08 times of theoretical requirement, add zinc sulphide, the add-on of zinc sulphide is 1% of reduced ore dry weight, normal-temperature reaction 30min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds Neutral ammonium fluoride, add-on is 5 times of theoretical molar quality, at 90 ℃, reacts 1h, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, add-on is theoretical amount 1.3 times, generate manganous carbonate precipitation, filter, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnSO
4concentration is the manganese sulfate solution of 420g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration.
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 purity that the present invention produces the manganous sulfate that the method for high-purity manganese sulphate produces is all greater than more than 99.8%, and the content of the impurity such as calcium magnesium potassium sodium is all less than 30ppm.
Claims (1)
1. a production method for high-purity manganese sulphate, is characterized in that: comprise the following steps:
A. the carbon fire reduction-leaching of pyrolusite: by pyrolusite powder, reduction coal dust is pressed after the quality proportioning mixing of l00:18, drop in reduction furnace, maturing temperature 800-900 ℃, roasting time 2h, after discharging is cooling, reducing material and deionized water are pressed after the solid-to-liquid ratio pulp of 1:4, adding weight concentration is 98% sulfuric acid, sulphuric acid is 1.05-1.1 times of theoretical acid, stirring reaction time l-2h at 60-90 ℃, then add deironing manganese powder iron removal by oxidation 0.5-lh, the add-on of manganese powder is 1.05-1.1 times of theoretical requirement, add vulcanizing agent, the add-on of vulcanizing agent is 1% of reduced ore dry weight, normal-temperature reaction 30-60min, filter,
B. remove calcium, magnesium addition: the filtrate obtaining to step a adds fluorochemical, add-on is 4-6 times of theoretical molar quality, at 80-90 ℃, reacts lh, generates Calcium Fluoride (Fluorspan) and magnesium fluoride precipitation, filters;
C. the separation of potassium sodium impurity: the filtrate obtaining to step b adds bicarbonate of ammonia or volatile salt, the 1.1-1.3 that add-on is theoretical amount doubly, generates manganous carbonate precipitation, filters, by 60 ℃ of deionized water wash manganous carbonate throw outs for liquid-solid ratio 3:1;
D. dissolve and crystallization: the manganous carbonate after the sulfuric acid dissolution step c that is 50% by weight concentration washing, makes MnS0
4concentration is the manganese sulfate solution of 350-500g/L, standing, and solution carries out normal pressure crystallization manganous sulfate crystal, dry, then drying obtains high-purity manganese sulphate with whizzer centrifuge dehydration;
Described vulcanizing agent is a kind of in manganese sulfide, Iron sulfuret, barium sulphide, ammonium sulfide, zinc sulphide and hydrogen sulfide or their composition;
Described fluorochemical is a kind of in manganous fluoride, Neutral ammonium fluoride, Sodium Fluoride, Potassium monofluoride and barium fluoride or their composition.
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| CN103667747B (en) * | 2013-12-11 | 2015-03-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Process for producing manganese sulfate from low-grade manganese ores |
| CN103771525B (en) * | 2013-12-30 | 2015-09-30 | 中信大锰矿业有限责任公司大新锰矿分公司 | A kind of pyrogenic process is in conjunction with the novel process of wet production manganous sulfate |
| CN104195331A (en) * | 2014-09-02 | 2014-12-10 | 湖南科技大学 | Method for preparing high-purity manganese sulfate through extracting low-grade pyrolusite by using rice straw |
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| CN108314086A (en) * | 2018-04-28 | 2018-07-24 | 戴建军 | The method for producing LITHIUM BATTERY high purity manganese sulfate as raw material using ferric manganese ore |
| CN109097578A (en) * | 2018-07-17 | 2018-12-28 | 重庆上甲电子股份有限公司 | A method of manganese carbonate is produced using aniline reduction electrolytic manganese anode mud |
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| CN113387391B (en) * | 2021-07-30 | 2022-05-24 | 广西埃索凯新材料科技有限公司 | Manganese sulfate production system based on manganese oxide ore |
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| CN114671467A (en) * | 2022-04-11 | 2022-06-28 | 中南大学 | Method for preparing manganese sulfate from pyrolusite |
| CN114772648B (en) * | 2022-04-17 | 2023-12-01 | 张响 | Method for producing battery-grade manganese sulfate by purifying industrial-grade manganese sulfate |
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