CN101891254A - Method for preparing heavy manganese carbonate - Google Patents
Method for preparing heavy manganese carbonate Download PDFInfo
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- CN101891254A CN101891254A CN 201010236245 CN201010236245A CN101891254A CN 101891254 A CN101891254 A CN 101891254A CN 201010236245 CN201010236245 CN 201010236245 CN 201010236245 A CN201010236245 A CN 201010236245A CN 101891254 A CN101891254 A CN 101891254A
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- Prior art keywords
- manganese
- sulfate solution
- pure
- manganese sulfate
- ammonium bicarbonate
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- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 27
- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 27
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 27
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 53
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 52
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 52
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 52
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 31
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 30
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 30
- 238000001556 precipitation Methods 0.000 claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- PAVJEQIFHXNOSM-UHFFFAOYSA-H manganese(3+);trisulfate Chemical compound [Mn+3].[Mn+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PAVJEQIFHXNOSM-UHFFFAOYSA-H 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 3
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 150000002696 manganese Chemical class 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000002966 varnish Substances 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract 1
- 229910002096 lithium permanganate Inorganic materials 0.000 abstract 1
- 239000000696 magnetic material Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000029219 regulation of pH Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 45
- 238000005303 weighing Methods 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing heavy manganese carbonate. In the method, solid industrial manganese sulfate or metal manganese powder are used as raw materials to form pure solution of manganese sulfate by dissolution, purification and pH regulation; and the pure solution of the manganese sulfate is reacted with pure solution of ammonium bicarbonate and a heavy manganese carbonate product which contains over 45 percent of manganese and has a tap density of more than 2.4g/cm<3> is obtained by regulating the pH value of the solution and controlling the precipitation reaction time. The method can be widely used for manufacturing magnetic materials, ceramic, glass, desulfuration catalysts, porcelain glaze pigments, varnish drier and other manganese salts and for preparing novel battery materials. Particularly, the method can be used for producing chemical manganese dioxide and lithium permanganate for anode materials of lithium ion batteries.
Description
Technical field: the preparation method who the present invention relates to the preparing technical field of manganous carbonate, particularly heavy manganese carbonate.
Background technology: manganous carbonate is a kind of important chemical product, is widely used as catalyzer, enamel pigment, the varnish siccative of desulfurization, is the raw material of preparation cell positive material chemical manganese bioxide, lithium manganate and other manganese salt.Also be used for aspects such as medicine, mechanical component and bonderizing.Domestic existing production method all is the reactor internal reaction that adopts manganese salt solution and carbonate solution to stir at normal tape, and the product manganous carbonate tap density that obtains is low, and the jolt ramming volume density has only 1.5g/cm
3About, manganese purity is low, and content is lower than 45%, can not satisfy the production requirement of lithium cell anode material lithium manganate, also is not suitable for preparing high-quality chemical manganese bioxide.Document announcement has and adopts the aminoquinoxaline method to produce heavy manganese carbonate, namely uses natural manganese ore, and ammonification and carbon dioxide leach and also be hydrolyzed to manganese carbonate, though the more common manganese carbonate of manganese carbonate tap density that this method is produced is improved largely, but still does not reach 2.4g/cm
3, and ammonia to soak in the process Material control strict, severe reaction conditions requires airtight pressurization, equipment material is required high, production cost is corresponding higher.
The reaction of manganous sulfate and bicarbonate of ammonia is a double decomposition precipitation reaction, and speed of response is exceedingly fast.When manganese sulfate solution pH value was higher, crystallization nucleation speed was fast, and crystal nucleation speed easily generates open-textured low-gravity manganese carbonate product greater than the speed of growth; When the pH of manganese sulfate solution value was low, the nucleation rate of precipitin reaction reduced, and helps crystal growth, easily generates the heavy manganese carbonate product of quality densification.The manganese carbonate precipitation reaction time is also very big to the impact of manganese carbonate tap density, the fine particle that reacts newly-generated constantly is deposited on the surface of nucleus or is filled in the internal void of nucleus, therefore prolonging the reaction time is conducive to growing up of crystal, generates fine and close manganese carbonate crystallization.The present invention has done a large amount of research experiments in order to overcome above-mentioned shortcoming on reaction process, obtained heavy manganese carbonate and preparation method.
Summary of the invention: the preparation method of heavy manganese carbonate provided by the invention, its technical characterictic is as raw material take solid industrial manganic sulfate or manganese powder, with pure water the solid industrial manganic sulfate is dissolved into the manganese sulfate solution that concentration is 0.5～1.5mol/L, or with sulfuric acid manganese powder is dissolved into the manganese sulfate solution that concentration is 0.5～1.5mol/L; In above-mentioned manganese sulfate solution, add cleaner H under 70～95 ℃ of stirring conditions
2O
2, cleaner H
2O
2Addition is 0.1%～0.5% (percetage by weight) of solid industrial manganic sulfate weight, insulation reaction 30～60 minutes, regulate pH to 5.0 with carbonic hydroammonium again, remove by filter metal ion and mechanical admixture in the reactant liquor, filtrate after the filtration obtains pure manganese sulfate solution with sulphur acid for adjusting pH to 1.5～4.0; With pure water carbonic hydroammonium is dissolved, be configured to the ammonium bicarbonate soln that concentration is 0.5～1.0mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; In precipitation reactor, add a small amount of pure water and make end liquid, stir, be warming up to 30～60 ℃, the pure manganese sulfate solution and the pure ammonium bicarbonate soln that prepare are dripped in reactor simultaneously, the amount of ammonium bicarbonate soln is 100%～110% of manganese sulfate solution amount, and the precipitation reaction time is 12～20 hours.After precipitin reaction is finished, centrifugal, wash, dry manganese content greater than 45%, tap density is greater than 2.4g/cm
3The heavy manganese carbonate product.
Above-mentioned cleaner H
2O
2Refer to the H of 27.5% (percetage by weight)
2O
2Solution, pure water conductivity is less than 10 μ s/cm.
Embodiment:
Embodiment 1:
Take by weighing solid industrial manganic sulfate 2070g, be dissolved into the manganese sulfate solution that concentration is 1mol/L with pure water; Under being 70 ℃, stirring condition, temperature in above-mentioned manganese sulfate solution, adds 10.5gH
2O
2, insulation reaction is regulated pH to 5.0 with carbonic hydroammonium after 60 minutes again, removes by filter metal ion and mechanical admixture in the manganese sulfate solution, filters rear filtrate with sulphur acid for adjusting pH to 1.5, obtains pure manganese sulfate solution; Take by weighing 2085g carbonic hydroammonium and dissolve with pure water, be configured to the ammonium bicarbonate soln that concentration is 1mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; Add a small amount of pure water and make end liquid in precipitation reactor, stir, be warming up to 30 ℃, pure manganese sulfate solution and pure ammonium bicarbonate soln are dripped in reactor simultaneously, the precipitation reaction time is 12 hours.After precipitation reaction is finished, centrifugal, wash, dry the heavy manganese carbonate product, product Mn content is 45.51%, tap density is 2.42g/cm
3
Embodiment 2:
Take by weighing solid industrial manganic sulfate 2586g, be dissolved into the manganese sulfate solution that concentration is 1.5mol/L with pure water; Under being 85 ℃, stirring condition, temperature in above-mentioned manganese sulfate solution, adds 5.5gH
2O
2, insulation reaction is regulated pH to 5.0 with carbonic hydroammonium after 30 minutes again, removes by filter metal ion and mechanical admixture in the manganese sulfate solution, with sulphur acid for adjusting pH to 3.0, obtains pure manganese sulfate solution after filtering; Take by weighing 2607g carbonic hydroammonium and dissolve with pure water, be configured to the ammonium bicarbonate soln that concentration is 1mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; Add a small amount of pure water and make end liquid in precipitation reactor, stir, be warming up to 45 ℃, pure manganese sulfate solution and the pure ammonium bicarbonate soln for preparing dripped in reactor simultaneously, the precipitation reaction time is 15 hours.After precipitation reaction is finished, centrifugal, wash, dry the heavy manganese carbonate product.Product Mn content is 45.32%, and tap density is 2.46g/cm
3
Embodiment 3:
Take by weighing solid industrial manganic sulfate 3450g, be dissolved into the manganese sulfate solution that concentration is 0.5mol/L with pure water; Under being 95 ℃, stirring condition, temperature in above-mentioned manganese sulfate solution, adds 3.5gH
2O
2, insulation reaction is regulated pH to 5.0 with carbonic hydroammonium after 40 minutes again, removes by filter metal ion and mechanical admixture in the manganese sulfate solution, with sulphur acid for adjusting pH to 4.0, obtains pure manganese sulfate solution after filtering; Take by weighing 3476g carbonic hydroammonium and dissolve with pure water, be configured to the ammonium bicarbonate soln that concentration is 1mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; Add a small amount of pure water and make end liquid in precipitation reactor, stir, be warming up to 60 ℃, pure manganese sulfate solution and pure ammonium bicarbonate soln are dripped in reactor simultaneously, the precipitation reaction time is 20 hours.After precipitation reaction is finished, centrifugal, wash, dry the heavy manganese carbonate product.Product Mn content is 45.43%, and tap density is 2.40g/cm
3
Embodiment 4:
Take by weighing solid electrolytic manganese metal 990g, becoming concentration with sulfuric acid dissolution with pure water is the manganese sulfate solution of 1.5mol/L; Under being 90 ℃, stirring condition, temperature in above-mentioned manganese sulfate solution, adds 15.50gH
2O
2, insulation reaction is regulated pH to 5.0 with carbonic hydroammonium after 40 minutes again, removes by filter metal ion and mechanical admixture in the manganese sulfate solution, with sulphur acid for adjusting pH to 2.0, obtains pure manganese sulfate solution after filtering; Take by weighing 3128g carbonic hydroammonium and dissolve with pure water, be configured to the ammonium bicarbonate soln that concentration is 0.5mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; Add a small amount of pure water and make end liquid in precipitation reactor, stir, be warming up to 40 ℃, pure manganese sulfate solution and pure ammonium bicarbonate soln are dripped in reactor simultaneously, the precipitation reaction time is 18 hours.After precipitation reaction is finished, centrifugal, wash, dry the heavy manganese carbonate product.Product Mn content is 45.70%, and tap density is 2.45g/cm
3
Embodiment 5:
Take by weighing solid electrolytic manganese metal 550g, becoming concentration with sulfuric acid dissolution with pure water is the manganese sulfate solution of 1mol/L; Under being 85 ℃, stirring condition, temperature in above-mentioned manganese sulfate solution, adds 3.0gH
2O
2, insulation reaction is regulated pH to 5.0 with carbonic hydroammonium after 50 minutes again, removes by filter metal ion and mechanical admixture in the manganese sulfate solution, with sulphur acid for adjusting pH to 4.5, obtains pure manganese sulfate solution after filtering; Take by weighing 1738g carbonic hydroammonium and dissolve with pure water, be configured to the ammonium bicarbonate soln that concentration is 0.8mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; Add a small amount of pure water and make end liquid in precipitation reactor, stir, be warming up to 40 ℃, pure manganese sulfate solution and pure ammonium bicarbonate soln are dripped in reactor simultaneously, the precipitation reaction time is 10 hours.After precipitation reaction is finished, centrifugal, wash, dry the heavy manganese carbonate product.Product Mn content is 45.46%, and tap density is 2.33g/cm
3
Embodiment 6:
Take by weighing solid electrolytic manganese metal 1100g, becoming concentration with sulfuric acid dissolution with pure water is the manganese sulfate solution of 0.5mol/L; Under being 75 ℃, stirring condition, temperature in above-mentioned manganese sulfate solution, adds 7.0gH
2O
2, insulation reaction is regulated pH to 5.0 with carbonic hydroammonium after 40 minutes again, removes by filter metal ion and mechanical admixture in the manganese sulfate solution, with sulphur acid for adjusting pH to 2.0, obtains pure manganese sulfate solution after filtering; Take by weighing 3476g carbonic hydroammonium and dissolve with pure water, be configured to the ammonium bicarbonate soln that concentration is 1mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; Add a small amount of pure water and make end liquid in precipitation reactor, stir, be warming up to 45 ℃, pure manganese sulfate solution and pure ammonium bicarbonate soln are dripped in reactor simultaneously, the precipitation reaction time is 20 hours.After precipitation reaction is finished, centrifugal, wash, dry the heavy manganese carbonate product.Product Mn content is 45.8%, and tap density is 2.47g/cm
3
Embodiment 7
Take by weighing solid electrolytic manganese metal 880g, becoming concentration with sulfuric acid dissolution with pure water is the manganese sulfate solution of 1.2mol/L; Under being 80 ℃, stirring condition, temperature in above-mentioned manganese sulfate solution, adds 5.5gH
2O
2, insulation reaction is regulated pH to 5.0 with carbonic hydroammonium after 45 minutes again, removes by filter metal ion and mechanical admixture in the manganese sulfate solution, with sulphur acid for adjusting pH to 2.5, obtains pure manganese sulfate solution after filtering; Take by weighing 2781g carbonic hydroammonium and dissolve with pure water, be configured to the ammonium bicarbonate soln that concentration is 1mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; Add a small amount of pure water and make end liquid in precipitation reactor, stir, be warming up to 50 ℃, pure manganese sulfate solution and pure ammonium bicarbonate soln are dripped in reactor simultaneously, the precipitation reaction time is 16 hours.After precipitation reaction is finished, centrifugal, wash, dry the heavy manganese carbonate product.Product Mn content is 45.77%, and tap density is 2.43g/cm
3
Claims (2)
1. the preparation method of a heavy manganese carbonate, it is characterized in that: take solid industrial manganic sulfate or manganese powder as raw material, with pure water the solid industrial manganic sulfate is dissolved into the manganese sulfate solution that concentration is 0.5～1.5mol/L, or with sulfuric acid manganese powder is dissolved into the manganese sulfate solution that concentration is 0.5～1.5mol/L; In above-mentioned manganese sulfate solution, add cleaner H under 70～95 ℃ of stirring conditions
2O
2, cleaner H
2O
2Addition be 0.1%～0.5% (percetage by weight) of solid industrial manganic sulfate weight, insulation reaction 30～60 minutes, regulate pH to 5.0 with carbonic hydroammonium again, remove by filter metal ion and mechanical admixture in the reactant liquor, filtrate after the filtration obtains pure manganese sulfate solution with sulphur acid for adjusting pH to 1.5～4.0; With pure water carbonic hydroammonium is dissolved, be configured to the ammonium bicarbonate soln that concentration is 0.5～1.0mol/L, leave standstill, sedimentation, filtration, get pure ammonium bicarbonate soln; In precipitation reactor, add a small amount of pure water and make end liquid, stir, be warming up to 30～60 ℃, the pure manganese sulfate solution and the pure ammonium bicarbonate soln that prepare are dripped in reactor simultaneously, the amount of ammonium bicarbonate soln is 100%～110% of manganese sulfate solution amount, the precipitation reaction time is 12～20 hours, after precipitation reaction is finished, centrifugal, wash, dry manganese content greater than 45%, tap density is greater than 2.4g/cm
3The heavy manganese carbonate product.
2. according to the preparation method of the described heavy manganese carbonate of claim 1, it is characterized in that cleaner H
2O
2Be the H of 27.5% (percetage by weight)
2O
2Solution, pure water conductivity is less than 10 μ s/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010236245 CN101891254A (en) | 2010-07-26 | 2010-07-26 | Method for preparing heavy manganese carbonate |
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| CN 201010236245 CN101891254A (en) | 2010-07-26 | 2010-07-26 | Method for preparing heavy manganese carbonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795669A (en) * | 2011-05-23 | 2012-11-28 | 湖北开元化工科技股份有限公司 | Process method for producing high-pure spherical heavy manganese carbonate |
| CN104740987A (en) * | 2015-03-20 | 2015-07-01 | 凯天环保科技股份有限公司 | Recycling ammonia desulphurization process |
| CN105778566A (en) * | 2016-02-29 | 2016-07-20 | 三祥新材股份有限公司 | Method for preparing pigment with manganese carbonate |
| CN110316760A (en) * | 2019-07-29 | 2019-10-11 | 佛山西陇化工有限公司 | A kind of preparation method of ultra-fine manganese carbonate |
| CN113582234A (en) * | 2021-08-11 | 2021-11-02 | 南方锰业集团有限责任公司 | Preparation method of battery-grade spheroidal manganese carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101704553A (en) * | 2009-07-20 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese carbonate |
-
2010
- 2010-07-26 CN CN 201010236245 patent/CN101891254A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704553A (en) * | 2009-07-20 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese carbonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795669A (en) * | 2011-05-23 | 2012-11-28 | 湖北开元化工科技股份有限公司 | Process method for producing high-pure spherical heavy manganese carbonate |
| CN104740987A (en) * | 2015-03-20 | 2015-07-01 | 凯天环保科技股份有限公司 | Recycling ammonia desulphurization process |
| CN105778566A (en) * | 2016-02-29 | 2016-07-20 | 三祥新材股份有限公司 | Method for preparing pigment with manganese carbonate |
| CN110316760A (en) * | 2019-07-29 | 2019-10-11 | 佛山西陇化工有限公司 | A kind of preparation method of ultra-fine manganese carbonate |
| CN113582234A (en) * | 2021-08-11 | 2021-11-02 | 南方锰业集团有限责任公司 | Preparation method of battery-grade spheroidal manganese carbonate |
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