CN1122640C - Process for preparing manganor manganic oxide used for soft magnetic ferrite - Google Patents
Process for preparing manganor manganic oxide used for soft magnetic ferrite Download PDFInfo
- Publication number
- CN1122640C CN1122640C CN 00136211 CN00136211A CN1122640C CN 1122640 C CN1122640 C CN 1122640C CN 00136211 CN00136211 CN 00136211 CN 00136211 A CN00136211 A CN 00136211A CN 1122640 C CN1122640 C CN 1122640C
- Authority
- CN
- China
- Prior art keywords
- manganese sulfate
- manganese
- sulfate solution
- carbonate
- pyrolusite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910000859 α-Fe Inorganic materials 0.000 title claims description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims description 3
- 238000004519 manufacturing process Methods 0.000 title description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 24
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 17
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 17
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 17
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- -1 phosphine carboxylic acid Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims 2
- 235000006748 manganese carbonate Nutrition 0.000 abstract description 5
- 239000011656 manganese carbonate Substances 0.000 abstract description 5
- 229940093474 manganese carbonate Drugs 0.000 abstract description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 abstract 2
- 239000008204 material by function Substances 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to the technical field of functional materials. Pyrolusite or manganese sulfate is used as a raw material and is carbonized into manganese carbonate, and trimanganese tetraoxide with the specific surface area greater than 20m<2>/g is obtained after the manganese carbonate is calcined. Expensive manganese metal obtained by electrolysis is not needed, and cheap pyrolusite or cheap manganese sulfate is directly prepared into the trimanganese tetraoxide by a chemical treatment method; thereby, the present invention has the advantages of easy operation, low cost, and large specific surface area, good activity and high purity of a product.
Description
The present invention relates to technical field of function materials, specifically be the preparation method of soft magnetic materials with chemical.
Trimanganese tetroxide is a kind of inorganic functional material.Main raw material trimanganese tetroxide as soft magnetic ferrite not only requires high-purity chemical index, also good physical index will be arranged, and wherein specific surface is important physical index, and it directly influences the activity and the ferritic quality of trimanganese tetroxide.At present, domestic production technology is raw material with the electrolytic metal manganese powder of costliness all, adopts liquid phase oxidation to produce trimanganese tetroxide.Its shortcoming is the production cost height, the product poor activity, and specific surface is little (all at 5～7m
2/ g).Once reported this method as Chinese patent CN96116905.In order to reduce cost, improve the quality of products, be raw material with manganous sulfate or pyrolusite, be an effective means through carbonization, baked for producing trimanganese tetroxide.Chinese patent CN98112437 proposes, and is raw material with the manganous sulfate, prepares the method for trimanganese tetroxide through carbonization, roasting, but does not relate to technical parameters such as concrete impurity removal process and synthesis technique, more undeclared product index and specific surface size.
The object of the present invention is to provide a kind of is raw material with pyrolusite or manganous sulfate, does not use expensive manganese metal, directly produces the method for large specific surface trimanganese tetroxide with chemical treatment method.It focuses on foreign matter content and specific surface by removal of impurities, synthetic, sinter process control product.
Main technical schemes of the present invention: at first the pH value with manganese sulfate solution transfers to 5～6, add organic polymer coargulator, filtering and impurity removing, secondly ammonium bicarbonate soln is added in the purified manganese sulfate solution, the throw out that obtains makes high-purity manganese carbonate through washing, oven dry, manganous carbonate can obtain specific surface greater than 20m in 950 ℃～1050 ℃ following roastings 1～2 hour
2The trimanganese tetroxide of/g.
Above-mentioned manganese sulfate solution is made by pyrolusite.
Above-mentioned organic polymer coargulator can make silicon dioxide microparticle and other suspended substances in the manganese sulfate solution form big floc sedimentation, removes by filter.
Above-mentioned organic polymer coargulator is the polymkeric substance of vinylformic acid or acrylate.
Above-mentioned manganous carbonate is synthetic to be that unsaturated carbonate hydrogen ammonium solution is joined in the finite concentration purified manganese sulfate solution, adds inhibitor simultaneously metal ions such as calcium, magnesium are retained in the mother liquor, and mn ion then is precipitated as manganous carbonate.
Above-mentioned inhibitor is the multipolymer of organic phosphine carboxylic acid or its salt.
Above-mentioned manganese sulfate solution concentration is 100～400g/l.
Above-mentioned manganous carbonate roasting time is 1-2 hour, and maturing temperature is 950 ℃～1050 ℃.
Technological process division of the present invention is as follows:
1, is in the manganese sulfate solution of 100～400g/l in concentration, under 20～80 ℃, transfers pH value, add 100～200ppm organic polymer coargulator again, after fully stirring evenly, filter, obtain the purified manganese sulfate solution to 5-6.
2, be that the ammonium bicarbonate soln of 200g/l is added in the POV manganese solution that concentration is 100～400g/l with concentration, add the 50-200ppm inhibitor simultaneously, control reaction temperature is 20～900 ℃, pH value 5～9, the throw out that obtains obtains high-purity manganese carbonate through washing, oven dry.
3, high-purity manganese carbonate makes trimanganese tetroxide 950 ℃～1050 ℃ following roastings 1～2 hour.Its product index is:
Mn：70～71％ SiO
2≤0.01％
Ca≤0.01％ Mg≤0.005％
Pb≤0.001% specific surface 〉=20m
2/ g
Advantage of the present invention: the present invention is to be raw material with pyrolusite or manganous sulfate, directly adopts chemical treatment method to produce high-purity mangano-manganic oxide without electrolysis.Used starting material are cheap and easy to get, and production cost is low; Used technology advanced person, simple to operate, easy to control; The products obtained therefrom specific surface is big, activity is good, purity is high.
The present invention will be further described below in conjunction with embodiment, but be not limited to present embodiment.
Embodiment
Concentration is the manganese sulfate solution 3000ml of 200g/l, to 5-6, adds the 150ppm sodium polyacrylate in 40 ℃ of downward modulation pH values again, fully stirs evenly, and filters, and gets the purified manganese sulfate solution.With concentration is the ammonium bicarbonate soln 3140ml of 200g/l, is added under 40 ℃ in the purified manganese sulfate solution, adds the poly-phosphine carboxylic acid sodium of 100ppm simultaneously, after precipitated product washing, the oven dry, in 1000 ℃ of following roasting 1.5h, finally makes high-purity mangano-manganic oxide.Its product index is (weight percentage):
Mn：71％ SiO
2：0.005％
Ca：0.006％ Mg：0.004％
Pb:0.001% specific surface: 22m
2/ g
Claims (5)
1, a kind of preparation method of manganor manganic oxide used for soft magnetic ferrite, with pyrolusite or manganous sulfate is raw material, it is characterized in that: at first the pH value with manganese sulfate solution transfers to 5～6, add the organic polymer coargulator acrylate polymer, secondly filtering and impurity removing adds ammonium bicarbonate soln and POV manganese solution in the reactor, add inhibitor simultaneously and contain the polymkeric substance of phosphine carboxylic acid or its salt, reaction generates manganous carbonate, then through washing, oven dry, roasting, obtains specific surface greater than 20m
2The trimanganese tetroxide of/g.
2, according to the method for claim 1, it is characterized in that: manganese sulfate solution is to be made by pyrolusite.
3, according to the method for claim 1, it is characterized in that: make silicon dioxide microparticle and other suspended substances in the manganese sulfate solution form big floc sedimentation with the organic polymer coargulator acrylate polymer, remove by filter.
4, according to the method for claim 1, it is characterized in that: manganous carbonate synthetic is that unsaturated carbonate hydrogen ammonium solution is joined concentration is in 100～400g/l purified manganese sulfate solution, add inhibitor simultaneously and contain the polymkeric substance of phosphine carboxylic acid or its salt, calcium, magnesium metal ion are retained in the mother liquor, and mn ion then is precipitated as manganous carbonate.
5, according to the method for claim 1, it is characterized in that: the manganous carbonate roasting time is 1～2 hour, and maturing temperature is 950～1050 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00136211 CN1122640C (en) | 2000-12-25 | 2000-12-25 | Process for preparing manganor manganic oxide used for soft magnetic ferrite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00136211 CN1122640C (en) | 2000-12-25 | 2000-12-25 | Process for preparing manganor manganic oxide used for soft magnetic ferrite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1295978A CN1295978A (en) | 2001-05-23 |
| CN1122640C true CN1122640C (en) | 2003-10-01 |
Family
ID=4597138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00136211 Expired - Fee Related CN1122640C (en) | 2000-12-25 | 2000-12-25 | Process for preparing manganor manganic oxide used for soft magnetic ferrite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1122640C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134101A (en) * | 2011-04-29 | 2011-07-27 | 金瑞新材料科技股份有限公司 | Method for preparing trimanganese tetroxide by using rhodochrosite |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1677579B (en) * | 2004-03-31 | 2012-10-10 | 广东肇庆微硕电子有限公司 | Wide-band manganese-zinc series high-magnetic-conductivity soft magnet oxysome material |
| CN101219809B (en) * | 2007-12-12 | 2010-06-09 | 中国科学院长春应用化学研究所 | Preparation method of manganese tetraoxide nanocrystals with controllable size and shape |
| CN101704553B (en) * | 2009-07-20 | 2012-11-07 | 贵州红星发展股份有限公司 | Method for preparing manganese carbonate |
| CN103011295B (en) * | 2012-12-17 | 2014-08-13 | 攀枝花市立宇矿业有限公司 | Reduction method for producing manganese tetroxide |
| CN104211122B (en) * | 2014-08-14 | 2016-01-20 | 重庆上甲电子股份有限公司 | With the decomposition precipitation circulation technology of preparing manganous-manganic oxide by manganese sulphate solution |
| CN108910957A (en) * | 2018-07-18 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of soft magnetism mangano-manganic oxide is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN114702075A (en) * | 2022-04-11 | 2022-07-05 | 中南大学 | Purification preparation method of manganese sulfate |
-
2000
- 2000-12-25 CN CN 00136211 patent/CN1122640C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134101A (en) * | 2011-04-29 | 2011-07-27 | 金瑞新材料科技股份有限公司 | Method for preparing trimanganese tetroxide by using rhodochrosite |
| CN102134101B (en) * | 2011-04-29 | 2012-08-29 | 金瑞新材料科技股份有限公司 | Method for preparing trimanganese tetroxide by using rhodochrosite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1295978A (en) | 2001-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100396733C (en) | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN1122640C (en) | Process for preparing manganor manganic oxide used for soft magnetic ferrite | |
| CN1077546C (en) | Method for producing mixed rare-earth chloride | |
| CN112978805A (en) | Comprehensive recovery method of titanium, iron and sulfate radicals in titanium white waste acid | |
| CN102337409A (en) | Method for recovering vanadium from dephosphorization bottom flow residues | |
| CN108754186A (en) | The method for preparing vfanadium compound containing vanadium solution | |
| CN102167400A (en) | Method for preparing vanadium pentoxide from vanadium-containing solution | |
| CN1415666A (en) | Method for producing the yellow pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white | |
| CN114134344B (en) | Method for precipitating vanadium by using ammonium metavanadate | |
| CN1927727A (en) | Method of preparing high-purity manganomanganic oxide by pyrolyzing manganese sulfate at high temperature | |
| CN1020273C (en) | Method for producing barium carbonate | |
| CN116283552B (en) | Refining method of oxalic acid | |
| CN116119710B (en) | Preparation method of potassium fluotitanate | |
| CN112390295A (en) | Method for utilizing artificial rutile mother liquor | |
| CN103103351A (en) | Method for preparing high-purity calcium carbonate for saponifying rare earth extraction agent | |
| CN103011295B (en) | Reduction method for producing manganese tetroxide | |
| CN102416315A (en) | Magnesium-containing rare earth oxygen storage material and preparation method thereof | |
| CN113912130B (en) | Iron oxide red and preparation method thereof | |
| CN1172027C (en) | Process for removing Si and Al from solution of ferrous chloride | |
| CN1031459C (en) | Iron-removing method used in course of aluminum sulfate production | |
| CN1133702C (en) | Process for preparing iron oxide red for soft-magnetic ferrite | |
| CN110407241B (en) | Preparation method of high-activity calcium oxide | |
| JPS62235221A (en) | Production of high-purity iron oxide | |
| CN112479334A (en) | Purification treatment method of silver electrolyte | |
| CN110306063A (en) | A method of organic matter in the heavy germanium solution of removing wet zinc-making system tannic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| C10 | Entry into substantive examination | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20031001 Termination date: 20131225 |