CN1210893A - Process for extracting manganese ore with sulfuric acid at ordinary temperature - Google Patents
Process for extracting manganese ore with sulfuric acid at ordinary temperature Download PDFInfo
- Publication number
- CN1210893A CN1210893A CN 97108214 CN97108214A CN1210893A CN 1210893 A CN1210893 A CN 1210893A CN 97108214 CN97108214 CN 97108214 CN 97108214 A CN97108214 A CN 97108214A CN 1210893 A CN1210893 A CN 1210893A
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- CN
- China
- Prior art keywords
- manganese
- manganese ore
- add
- sulfuric acid
- hour
- 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.)
- Granted
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 74
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 72
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 31
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 9
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004537 pulping Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention has no demerits of low extraction rate and high cost, which exist in available steam heating process. Manganese ore powder after pulping by adding waste manganese containing electrolyte, waste MnO2 electrolyte or water is reacted first with excessive sulfuric acid; and during the reaction, industrial pyrolusite powder, waste manganese containing electrolyte, sulfite as additive and more industrial pyrolusite powder are added successively for further reaction, with the manganese sulfate solution as reaction product being collected from the reaction solution. The process issuitable for various manganese product producer using manganese ore powder and sulfuric acid as raw material.
Description
The present invention relates to a kind of method of using the method, particularly a kind of extracting manganese ore with sulfuric acid at ordinary temperature of sulfuric acid to leach manganese ore.
At present, useful sulfuric acid of institute and manganese ore powder are the raw material production manganous sulfate, electrolytic metal Mn, electrolytic manganese dioxide, the manufacturer of manganese goods such as manganous carbonate, all be to adopt heat the down method abbreviation steam heat method of sulfuric acid and manganese ore reaction leaching generation manganese sulfate solution of steam, this method is not only wanted facilities such as steam boiler, pipeline, and the leaching rate of energy consumption height and manganese ore is not high yet, generally about 85%, the production cost height.
The object of the present invention is to provide a kind of technology simple, with low cost, the method for the extracting manganese ore with sulfuric acid at ordinary temperature that leaching rate is high.
The present invention finishes with following mode: the method for extracting manganese ore with sulfuric acid at ordinary temperature is to adopt following step successively:
1). will be fed in the retort according to the manganese ore powder that calculating takes by weighing, the useless electrolytic manganese solution of adding retort volume 25%-50% or useless electrolytic manganese dioxide solution or water mixing break into pulpous state liquid, add again by industrial strong sulfuric acid response 0.5-1.5 hour that tests out the excessive 5%-15% of the actual acid consumption of manganese ore powder
2). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 3%-4% and reacted 0.5-1.5 hour,
3). add useless electrolytic manganese solution or useless electrolytic manganese dioxide solution or water to the predetermined reaction volume of retort, reacted 0.5-1.5 hour,
4). added additive reaction 2-4 hour that is mainly sulphite, the sulphite add-on is the 0.5%-5% of manganese ore grain weight amount.
5). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 5%-15% and reacted 0.5-1.5 hour, from reaction soln, collect the resultant manganese sulfate solution.
Additive is: ammonium sulphite or ammonium bisulfite or sulfurous gas or S-WAT or sodium bisulfite or potassium sulfite, supplementary additive are formaldehyde or methyl alcohol or hydrogen peroxide.Adding additive sulphite is that liquid state contains SO
2During 25-300g/L, its add-on is the 1.6%-5% of manganese ore grain weight amount, when sulphite when being solid-state its add-on be the 0.5%-2% of manganese ore grain weight amount.
The technical process of extracting manganese ore with sulfuric acid at ordinary temperature method of the present invention is not only simple to operate, and leaching rate height, oxidation of divalent is complete, adopt and add contained a small amount of high oxidation state manganese in the additive sulphite reduction manganese ore powder, activate the reaction of manganese carbonate ore and vitriolic simultaneously, make the manganese in the manganese ore powder be changed into manganese sulfate solution by sulfuric acid to leach dramatically, supplementary additive suppresses ferric iron and is not reduced into ferrous iron by sulfurous acid, adopt excessive sulfuric acid can guarantee that sulphite and high oxidation state manganese react smoothly, this method manganese leaching rate reaches and surpasses the steam heat law technology, additive is with low cost, and without any detrimentally affect, it produces stable to the production of back operation.It and steam heat method are relatively, steam and province have been saved except equipment such as boiler and steam-pipes, reduced production cost widely, this method be applicable to useful sulfuric acid and manganese ore powder be that the producer of raw material production manganous sulfate, manganous carbonate, electrolytic metal Mn, electrolytic manganese dioxide and all manganese goods uses.
The present invention is further detailed explanation with embodiment below:
Technical process of the present invention is:
The manganese ore powder adds the useless electrolytic manganese liquid (or useless electrolytic manganese dioxide solution or water) of part and mixes and break into pulpous state liquid → add strong sulfuric acid response → add part industry pyrolusite powder reaction → fill it up with the industrial pyrolusite powder reaction → liming of retort → addings sulphite additive reaction → adding with useless electrolytic manganese liquid to neutralize and add cleaner and additive, filtration collection resultant of reaction manganese sulfate solution.
Now contain manganese 20% with the manganese ore powder, wherein the manganese that exists with the manganous carbonate form is 19%, and the actual acid consumption that tests out the manganese ore powder is 0.55 ton of/ton ore deposit, contains manganese 12.5g/L in sulfuric acid concentration 93%, the electrolytic manganese waste liquid, contains H
2SO
4, the 20.0g/L starting material are implemented the inventive method:
Embodiment one: at 22m
3Add useless electrolytic manganese liquid total amount 20m in the volume retort
3, all leaching concentration by manganese is 2.75 tons of the charging capacitys that 40g/L calculates the manganese ore powder, calculating the vitriolic add-on by excessive 10% is 1.36 tons, can react smoothly to guarantee sulphite and high oxidation state manganese.
With 2.75 tons of manganese ore powder and 7m
3Useless electrolytic manganese liquid drops in the retort, stirs into pulpous state liquid, adds 1.36 ton 93% industrial sulphuric acid then, stirs reaction down after 1 hour, adds 100 kilograms of reactions of industrial pyrolusite powder 1 hour, adds 13m then
3Useless electrolytic manganese liquid reaction 1 hour adds the additive ammonium sulfite solution and (contains SO
2280g/L) 80 kilograms, add a small amount of high oxidation state manganese contained in the ammonium sulphite reduction manganese ore powder (as MnO
2), activate the reaction of manganous carbonate and vitriolic simultaneously, make the manganese in the manganese ore powder be changed into manganese sulfate solution by sulfuric acid to leach dramatically, supplementary additive is content 10% methyl alcohol 200ml, reacted 2.5 hours, supplementary additive suppresses ferric iron and is not reduced into ferrous iron by sulfurous acid, and some ore deposit can not add supplementary additive, and the supplementary additive add-on is every retort (22m
3) 200-500ml adds 250 kilograms of industrial pyrolusite powders again, after reacting half an hour, detect manganese and ferrous content in the solution, ferrous content reaches≤0.01% requirement after, adding liming (calcium hydroxide) is neutralized to PH6.5-7.0 and gets final product, and this moment, the manganese sulfate solution leaching rate was generally about 95%.
Embodiment two: at 22m
3Retort in add useless electrolytic manganese liquid total amount 21m
3, all leaching concentration by manganese is that the charging capacity that 40g/L calculates the manganese ore powder is 2.89 tons, is 1.39 tons by the add-on of excessive 8% calculating industrial sulphuric acid (93%).With 2.89 tons of manganese ore powder and 7m
3After waste electrolyte drops into and stirs pulping in the retort, 1.39 tons in the sulfuric acid of adding 93%, reaction 1 hour stirs.Add 100 kilograms of industrial pyrolusite powders again, reacted 1 hour.Add useless electrolytic manganese solution 14m
3, reacted 1 hour, add ammonium sulfite solution and (contain SO
2280g/L) 100 kilograms, and add 10% methyl alcohol 200ml simultaneously, reacted 2.5 hours.Add 250 kilograms of industrial pyrolusite powders, the reaction half an hour after, manganese and ferrous content in the detection reaction resultant solution, when ferrous amount reach≤0.01% requirement after, add liming and be neutralized to PH:6.5-7.0, at this moment, the manganese sulfate solution leaching rate can reach about 95%.
Claims (3)
1. the method for an extracting manganese ore with sulfuric acid at ordinary temperature is characterized in that adopting successively following step:
1). will be fed in the retort according to the manganese ore powder that calculating takes by weighing, the useless electrolytic manganese solution of adding retort volume 25%-50% or useless electrolytic manganese dioxide solution or water mixing break into pulpous state liquid, add by industrial strong sulfuric acid response 0.5-1.5 hour that tests out the excessive 5%-15% of the actual acid consumption of manganese ore powder again;
2). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 3%-4% and reacted 0.5-1.5 hour;
3). add useless electrolytic manganese solution or useless electrolytic manganese dioxide solution or water to the retort pre-determined volume, reacted 0.5-1.5 hour;
4). added additive reaction 2-4 hour that is mainly sulphite, the sulphite add-on is the 0.5%-5% of manganese ore grain weight amount;
5). add the industrial pyrolusite powder of pressing manganese ore grain weight amount 5%-15% and reacted 0.5-1.5 hour, from reaction soln, collect the resultant manganese sulfate solution.
2. according to the method for the described extracting manganese ore with sulfuric acid at ordinary temperature of claim 1, it is characterized in that additive is: ammonium sulphite or ammonium bisulfite or sulfurous gas or S-WAT or sodium thionyl or potassium sulfite, supplementary additive are formaldehyde or methyl alcohol or hydrogen peroxide.
3. according to the method for the described extracting manganese ore with sulfuric acid at ordinary temperature of claim 1, it is characterized in that adding additive sulphite is that liquid state contains SO
2During 250-300g/L, its add-on is the 1.6%-5% of manganese ore grain weight amount, when sulphite when being solid-state its add-on be the 0.5%-2% of manganese ore grain weight amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108214A CN1075120C (en) | 1997-09-09 | 1997-09-09 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108214A CN1075120C (en) | 1997-09-09 | 1997-09-09 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1210893A true CN1210893A (en) | 1999-03-17 |
| CN1075120C CN1075120C (en) | 2001-11-21 |
Family
ID=5170233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97108214A Expired - Fee Related CN1075120C (en) | 1997-09-09 | 1997-09-09 | Process for extracting manganese ore with sulfuric acid at ordinary temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1075120C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260471B (en) * | 2008-04-28 | 2010-06-02 | 中国环境科学研究院 | Complete set of cleaning producing technique for extracting soluble manganese from manganese residue by using anode liquor |
| CN101880767A (en) * | 2010-06-07 | 2010-11-10 | 姚茂君 | Process for reducing leached pyrolusite ore by iron powder |
| CN103757247A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757249A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757444A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103937973A (en) * | 2014-04-16 | 2014-07-23 | 广西民族大学 | Organic-inorganic combined pyrolusite reduction method |
| CN113088999A (en) * | 2021-03-31 | 2021-07-09 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide for mercury-free alkaline zinc-manganese battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295355C (en) * | 2004-07-19 | 2007-01-17 | 中南大学 | Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034517C (en) * | 1992-11-02 | 1997-04-09 | 冶金工业部长沙冶研究院 | Preparation of highly pure manganese sulfate with high yield rate |
-
1997
- 1997-09-09 CN CN97108214A patent/CN1075120C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260471B (en) * | 2008-04-28 | 2010-06-02 | 中国环境科学研究院 | Complete set of cleaning producing technique for extracting soluble manganese from manganese residue by using anode liquor |
| CN101880767A (en) * | 2010-06-07 | 2010-11-10 | 姚茂君 | Process for reducing leached pyrolusite ore by iron powder |
| CN103757247A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757249A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103757444A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103937973A (en) * | 2014-04-16 | 2014-07-23 | 广西民族大学 | Organic-inorganic combined pyrolusite reduction method |
| CN113088999A (en) * | 2021-03-31 | 2021-07-09 | 广西桂柳化工有限责任公司 | Preparation method of electrolytic manganese dioxide for mercury-free alkaline zinc-manganese battery |
| CN113088999B (en) * | 2021-03-31 | 2021-12-31 | 广西桂柳新材料股份有限公司 | Preparation method of electrolytic manganese dioxide for mercury-free alkaline zinc-manganese battery |
| WO2022205534A1 (en) * | 2021-03-31 | 2022-10-06 | 广西桂柳化工有限责任公司 | Preparation method for electrolytic manganese dioxide for mercury-free alkaline zinc-manganese battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1075120C (en) | 2001-11-21 |
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