CN1058201A - The novel process of wet producing manganese sulfate from two kinds of mine - Google Patents
The novel process of wet producing manganese sulfate from two kinds of mine Download PDFInfo
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- CN1058201A CN1058201A CN 91102845 CN91102845A CN1058201A CN 1058201 A CN1058201 A CN 1058201A CN 91102845 CN91102845 CN 91102845 CN 91102845 A CN91102845 A CN 91102845A CN 1058201 A CN1058201 A CN 1058201A
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- solution
- manganese sulfate
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- manganese
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- 238000000034 method Methods 0.000 title claims abstract description 22
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 10
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 10
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- -1 iron ion Chemical class 0.000 claims abstract description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 5
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 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 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 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 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000384 rearing effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The novel process of wet producing manganese sulfate from two kinds of mine is the novel method that manganous sulfate is produced, and this method is with poor, bad, the useless MnO that contains
2Manganese ore powder and troilite powder add sulphuric acid soln, generate manganese sulfate solution after the reacting by heating, remove iron ion in the solution with feeding compressed-air actuated method again.Use this method manufacture manganous sulfate, compared with prior art, have that energy consumption is low, equipment is simple, invest that low, raw material is general, product yield height, cost is low, the advantage of good product quality, particularly the Fe% in the product requires also low ten percentage points less than 0.0005 than GB.
Description
The invention belongs to the production method of manganous sulfate in the domain of inorganic chemistry.
Industrial manganic sulfate (MnSo
4H
2O) belong to the inorganic salts Chemicals, it is one of important trace element fertilizer, also is the raw materials for production of industries such as fodder additives in the livestock rearing industry and papermaking, pottery, electrolytic manganese, printing and dyeing.
The traditional method of producing manganous sulfate with pyrolusite is to utilize the manganese ore powder to mix with a certain proportion of coal dust, carries out making through sulfuric acid to leach after the reducing roasting in the high-temperature roasting stove again.This method, equipment is huge, complex process, investment is many, the energy consumption height, and high-temperature dust is many, work under bad environment, and labor strength is big.Existing in recent years report: with pyrolusite add sulfurous iron ore with sulphuric acid soln leach the method for manganous sulfate, example: 1988 the 6th phases of " inorganic chemicals industry " magazine report: " pyrolusite directly leaches the system manganous sulfate ".Owing to added sulfurous iron ore in this method, under the vitriolic effect, contain the existence of iron ion, had a strong impact on the quality of manganese sulfate product, make to reach GB (iron Fe%＜0.004).
The objective of the invention is to improve the quality of products in order to reduce the content of iron in the manganese sulfate product.
The present invention has adopted such method: to contain MnO
2Pyrolusite powder and contain FeS
2Troilite powder be raw material, add sulphuric acid soln, heating, reaction, generate the reaction solution of sulfur acid manganese, carry out the separation of slag liquid after adjusting PH, the filtrate heating with sulfur acid manganese concentrates again, feeds pressurized air to this hot concentrated solution simultaneously, making oxidation of divalent is the ferric iron throw out, and from reaction solution, separate, its reaction principle is: in acidic solution, airborne oxygen also can be Fe
+ 2Be oxidized to Fe
+ 3
The main flow process of this method as shown in Figure 1.
In order to strengthen de-ferrous effect, pressurized air can feed by secondary in whole flow process.Promptly for the first time be in the reaction solution that after adjusting PH, separates first before removing slag, to feed; For the second time be after reaction solution after separation is removed slag enters concentration tank, to feed pressurized air simultaneously in heating, concentration process, the solution after concentrating is again through separating de-iron, crystallization then, dewater manganous sulfate (MnSo
4H
2O) finished product.
Above-mentioned technology, because the iron ion in the reaction solution has been removed in the feeding of air, particularly blowing air for the second time is and remaining iron ion reaction, thereby greatly reduces the content of iron ion in the manganous sulfate finished product.Improved quality product.Secondly, at the air that enriching stage feeds, also play a part to stir and take away moisture, thereby helped shortening concentration time.
Flow process of the invention process as shown in the figure.
The vitriol oil is made into dilute sulphuric acid (15%-20%), go into reaction tank, by about steam heating to 90 °, under agitation condition, add raw material manganese ore powder and troilite powder, about thermal reacting for two hours, transfer PH=5 with manganese carbonate ore, enter pressure-filtering tank, feed pressurized air, enter the pressure filter press filtration again and remove slag, (owing to the manganous sulfate that also contains in the slag about 10%, so the flow process of washery slag and recovery is arranged in addition.) filtrate press filtration for the second time behind standing sedimentation removes slag.Filtrate is advanced concentration tank (circuit shown among the figure 1), is heated to indirect steam and boils, and the while is bubbling air again, and air is come out by the air-distributor that is installed in the concentration tank bottom, further makes Fe
++Be oxidized to Fe
2O
3And precipitate, utilize air to play stirring action on the other hand and also help to have taken away the moisture in the solution, shortened concentration time, concentrated solution after concentrating enters and leaves standstill the pond after sedimentation, press filtration, filtrate enters crystallizer (circuit shown among the figure 2), make the crystallization of manganous sulfate reconcentration, enter the whizzer centrifuge dehydration again, the drying room oven dry gets product.Owing to still contain the manganous sulfate about 38% in the mother liquor that whizzer is deviate from, thereby as shown in the figure mother liquor is returned concentration tank, adjust PH, with back operations such as subsequent solution concentrate.
By above-mentioned technology, get manganese sulfate product, measure through quality supervision and test, the content of iron has reduced by ten percentage points than GB, promptly reaches Fe%=0.0005(and sees Appendix 1).
If heavy metal content is higher in the sulfurous iron ore, can in concentration process, in solution, add a small amount of BaS, can remove reaction formula:
Claims (2)
1, wet producing manganese sulfate from two kinds of mine technology is to contain MnO
2Pyrolusite powder and contain FeS
2Troilite powder add sulphuric acid soln, reacting by heating generates the solution of sulfur acid manganese, adjust pH value after separating for several times removes slag, concentrates, crystallization, dehydration, manganese sulfate product, it is characterized in that: the method that the removal of the iron ion that exists in the reacted solution is adopted the deironing of feeding pressurized air.
2, by the described technology of claim 1, it is characterized in that: pressurized air can enter solution at enriching stage; Perhaps dividing secondary to feed respectively, carry out the secondary air deironing, for the first time is after finishing in reaction, adjusting PH, to enter and separate the preceding feeding of removing slag, and is for the second time that manganese sulfate solution after separation is removed slag enters when heating enriching stage and feeds once more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102845 CN1058201A (en) | 1991-04-22 | 1991-04-22 | The novel process of wet producing manganese sulfate from two kinds of mine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91102845 CN1058201A (en) | 1991-04-22 | 1991-04-22 | The novel process of wet producing manganese sulfate from two kinds of mine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1058201A true CN1058201A (en) | 1992-01-29 |
Family
ID=4905777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91102845 Pending CN1058201A (en) | 1991-04-22 | 1991-04-22 | The novel process of wet producing manganese sulfate from two kinds of mine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1058201A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325670C (en) * | 2006-03-03 | 2007-07-11 | 郝鹏飞 | Method for removing ferrous-iron from manganese sulfate |
| CN101845562A (en) * | 2010-06-22 | 2010-09-29 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN101988153A (en) * | 2010-10-30 | 2011-03-23 | 湖南科技大学 | Novel process for efficiently and fast removing iron in manganese ore wet process reduction method |
| CN103757228A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757440A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757430A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757234A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757433A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103771525A (en) * | 2013-12-30 | 2014-05-07 | 中信大锰矿业有限责任公司大新锰矿分公司 | Novel process for producing manganese sulfate by combination of pyrogenic process and wet process |
| CN108300854A (en) * | 2018-04-10 | 2018-07-20 | 铜仁学院 | A kind of microwave reaction device and application process leaching pyrolusite |
-
1991
- 1991-04-22 CN CN 91102845 patent/CN1058201A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325670C (en) * | 2006-03-03 | 2007-07-11 | 郝鹏飞 | Method for removing ferrous-iron from manganese sulfate |
| CN101845562A (en) * | 2010-06-22 | 2010-09-29 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| WO2011160578A1 (en) * | 2010-06-22 | 2011-12-29 | Chen Banglong | Method for producing electrolytic manganese metal by using two ores and apparatus thereof |
| CN101845562B (en) * | 2010-06-22 | 2013-03-20 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN101988153A (en) * | 2010-10-30 | 2011-03-23 | 湖南科技大学 | Novel process for efficiently and fast removing iron in manganese ore wet process reduction method |
| CN101988153B (en) * | 2010-10-30 | 2013-07-31 | 湖南科技大学 | Novel process for efficiently and fast removing iron in manganese ore wet process reduction method |
| CN103757430A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757440A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757228A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757234A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757433A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757440B (en) * | 2013-12-29 | 2015-05-13 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757228B (en) * | 2013-12-29 | 2016-01-20 | 四川师范大学 | The leaching method of pyrolusite |
| CN103757234B (en) * | 2013-12-29 | 2016-01-20 | 四川师范大学 | The leaching method of pyrolusite |
| CN103771525A (en) * | 2013-12-30 | 2014-05-07 | 中信大锰矿业有限责任公司大新锰矿分公司 | Novel process for producing manganese sulfate by combination of pyrogenic process and wet process |
| 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 |
| CN108300854A (en) * | 2018-04-10 | 2018-07-20 | 铜仁学院 | A kind of microwave reaction device and application process leaching pyrolusite |
| CN108300854B (en) * | 2018-04-10 | 2023-09-22 | 铜仁学院 | Microwave reaction device for leaching pyrolusite and application method |
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