CN103435103A - High-purity manganous nitrate and preparation method thereof - Google Patents
High-purity manganous nitrate and preparation method thereof Download PDFInfo
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- CN103435103A CN103435103A CN2013103558301A CN201310355830A CN103435103A CN 103435103 A CN103435103 A CN 103435103A CN 2013103558301 A CN2013103558301 A CN 2013103558301A CN 201310355830 A CN201310355830 A CN 201310355830A CN 103435103 A CN103435103 A CN 103435103A
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- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000012065 filter cake Substances 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 18
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 15
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 15
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000004073 vulcanization Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 17
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 7
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052745 lead Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- BEUZULQWJZXWLA-UHFFFAOYSA-N [N+](=O)(O)[O-].[S-2].[Mn+2] Chemical compound [N+](=O)(O)[O-].[S-2].[Mn+2] BEUZULQWJZXWLA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention provides a high-purity manganous nitrate and a preparation method thereof. The method comprises the following steps: (1) sulfuration, adding the mixed gas containing ammonia gas and hydrogen sulfide into a manganese sulfate solution of 150-300g/L to conduct a sulfuration reaction until the concentration of Mn<2+> in the solution is less than 500ppm, then stopping the reaction, conducting solid-liquid separation, and then washing an obtained manganese sulfate filter cake for later use; (2) acidification, adding nitric acid into the manganese sulfate filter cake obtained in the sulfuration step (1) at the nitrogen atmosphere, keeping the temperature of a reaction system to be less than 50 DEG C, and using hydrogen sulfide produced in a nitrogen displacement reaction in the reaction process; stirring, reacting until the pH value is 3.5-4.0, stopping adding acid, then conducting solid-liquid separation, and the obtained filtrate is a manganous nitrate product. The preparation method adopts a manganese sulfide-nitric acid process route to obtain the high-purity manganous nitrate product with low content of heavy metals, and the process cost is lowered.
Description
Technical field
The present invention relates to domain of inorganic chemistry, concrete, relate to a kind of high pure nitric acid manganese and preparation method thereof.
Background technology
High pure nitric acid manganese is mainly used in the preparation of lithium-ion secondary cell tertiary cathode material presoma, and the production of high-purity manganese oxide.The production method of tradition manganous nitrate is mainly manganese metal-nitrate method, and the defect of the method is that in products obtained therefrom, heavy metal content is high, and production energy consumption is large, cost is high.
Summary of the invention
Technical problem to be solved by this invention is: overcome the high defect of heavy metal content in existing high pure nitric acid manganese, a kind of high pure nitric acid manganese and preparation method thereof is provided, adopt manganese sulfide-nitric acid process route, obtained the high purity liquid manganous nitrate product of low-heavy metal content, reduced process costs.
In order to solve the problems of the technologies described above, the first technical scheme provided by the invention is, a kind of preparation method of manganous nitrate, and the method comprises:
(1) sulfuration
To contain the mixed gas of ammonia and hydrogen sulfide and the manganese sulfate solution of 150～300g/L, carry out vulcanization reaction, until Mn in solution
2+stopped reaction when concentration is less than 500ppm, solid-liquid separation, then that the manganese sulfide filter cake washing obtained is stand-by;
(2) acidifying
Under nitrogen atmosphere, nitric acid is joined in (1) vulcanisation step gained manganese sulfide filter cake, maintain temperature of reaction system and be less than 50 ℃, the hydrogen sulfide that adopts the nitrogen replacement reaction to produce in reaction process; Stirring reaction to pH value 3.5～4.0 o'clock stop acid adding; Then solid-liquid separation, gained filtrate is the manganous nitrate product.
The preparation method of aforesaid manganous nitrate, in step (1), the concentration of described manganese sulfate solution is 200-250g/L.
Preferably, in step (1), ammonia and hydrogen sulfide (preferred reaction mol ratio) are passed in absorption tower, manganese sulfate solution sprays the absorption above-mentioned gas and carries out vulcanization reaction.The jet velocity of solution and product quality relation are little.
The preparation method of aforesaid manganous nitrate, in step (1), solid-liquid separation gained filter cake is pressed material-water ratio 1:4 washing secondary with 60～65 ℃ of deionized waters, and each 3 hours, then press filtration separated, and obtains the filter cake that moisture content is less than 25%.
The preparation method of aforesaid manganous nitrate, in step (2), reaction gained hydrogen sulfide is for the vulcanization reaction of step (1).
The preparation method of aforesaid manganous nitrate, in step (2), before solid-liquid separation, the molar ratio according to MnS/Fe=2/1 in reaction soln adds the manganese sulfide filter cake, stirs 4～5 hours; Then according to molar ratio [SO
4 2-]: [Ba
2+]=1:1, join barium hydroxide solution in reaction soln, stirring reaction 1.5～2 hours.
The preparation method of aforesaid manganous nitrate, the method further comprises (3) purifying step, this step comprises: according to the ratio of 1.0～1.5 liters of every cubic metre of solution, add superoxol in the filtrate obtained in step (2), 45～50 ℃ are stirred 0.5-1.5 hour, filter, cooling.
The invention provides the second technical scheme is that a kind of manganous nitrate, made by aforesaid method.
Aforesaid manganous nitrate, Fe content<0.34ppm, containing Cu, Co, Ni, Pb, As, Cr and Cd.
Adopt technical scheme of the present invention, at least there is following beneficial effect:
The low heavy metal high pure nitric acid manganese product that adopted manganese sulfide-preparation of nitric acid, its Fe content<0.34ppm, containing Cu, Co, Ni, Pb, As, Cr and Cd.
The accompanying drawing explanation
The process flow sheet that Fig. 1 the present invention is main.
Embodiment
For fully understanding the present invention's purpose, feature and effect, by following concrete embodiment, the present invention is elaborated.
A kind of preparation method of manganous nitrate, the method comprises:
(1) sulfuration
Mixed gas and the preferred 200-250g/L of 150～300g/L(that will contain ammonia and hydrogen sulfide) manganese sulfate solution, carry out vulcanization reaction, until Mn in solution
2+stopped reaction when concentration is less than 500ppm, solid-liquid separation (preferably press filtration separates), then that the manganese sulfide filter cake washing obtained is stand-by.Solid-liquid separation gained filtrate is for the reclaim(ed) sulfuric acid ammonium.
Above-mentioned manganese sulfate solution can be made by commercial manganous sulfate, also can be made by flue gas desulfurization.
In an embodiment, ammonia and hydrogen sulfide (preferred reaction mol ratio) are passed in absorption tower, manganese sulfate solution sprays the absorption above-mentioned gas and carries out vulcanization reaction.The jet velocity of solution and product quality relation are little.Conventional absorption tower all can be applied to the present invention.
The preferred mode of above-mentioned washing is: solid-liquid separation gained filter cake is pressed material-water ratio (weight) 1:4 washing secondary with 60～65 ℃ of deionized waters, and each 3 hours, then press filtration separated, and obtains the filter cake that moisture content is less than 25%.
The reaction equation of this step is:
MnSO
4+H
2S+NH
3→MnS↓+(NH
4)
2SO
4
(2) acidifying
(1) vulcanisation step gained manganese sulfide filter cake is placed in to reactor (preferably lass lining reactor), with the air in the nitrogen replacement reactor, add nitric acid under air tight condition, the cooling temperature of reaction system that maintains of chuck is less than 50 ℃, and stirring reaction to pH value 3.5～4.0 o'clock stop acid adding.The hydrogen sulfide that adopts the nitrogen replacement reaction to produce in reaction process, reaction gained hydrogen sulfide is for the vulcanization reaction of step (1).
The reaction equation of this step is:
MnS+2HNO
3→Mn(NO
3)
2+H
2S↑
Nitric acid has stronger oxidisability, has a small amount of sulfide oxidation and generates sulfate radical.In order to address the above problem, the content of iron and sulfate radical in assaying reaction solution, add the manganese sulfide filter cake according to the molar ratio of MnS/Fe=2/1, maintains and stir 4～5 hours, then according to molar ratio [SO
4 2-]: [Ba
2+]=1:1, join barium hydroxide solution in reaction soln, stirring reaction 1.5～2 hours, and then solid-liquid separation (press filtration separation), obtain filtrate, and filter residue is abandoned.
The reaction equation of this step is:
SO
4 2-+Ba
2+→BaSO
4↓
M+MnS→MS↓+Mn
2+
M---Fe, Cu, Co, Zn, Ni, As, Pb, Cr, Cd etc.
(3) purifying step
Ratio according to 1.0～1.5 liters of every cubic metre of solution, add superoxol in the filtrate obtained in step (2), 45～50 ℃ are stirred 0.5-1.5 hour, filter, filter residue is abandoned, the filtrate of clarification is added deionized water according to concentration requirement and is mixed, and cooling rear packing obtains the high pure nitric acid manganese product.
The manganous nitrate prepared by aforesaid method, its Fe content<0.34ppm, containing Cu, Co, Ni, Pb, As, Cr and Cd.
Set forth the enforcement of method of the present invention below by specific embodiment, one skilled in the art will appreciate that this should not be understood to the restriction to the claims in the present invention scope.
Embodiment
At first, determinator and measuring method used is described as follows when in following embodiment, manganous nitrate preparation process and product are analyzed:
Mn, K, Na, Ca, Mg, Fe, Cu, Co, Ni, Pb, As, Cd, Cr, Cu and Ba content elemental analysis method: inductively coupled plasma (ICP) atomic emission spectrometry;
Atomic Absorption SpectrophotometerICP: IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, U.S. power & light company system.
PH value determinator: PHS-3C type precision acidity meter, Shanghai precision instrumentation company system.
Embodiment 1
(1) sulfuration
To react mol ratio ammonia and hydrogen sulfide and pass in absorption tower, then spray the manganese sulfate solution of concentration 150g/L, and absorb above-mentioned gas and carry out vulcanization reaction.Work as Mn
2+stopped reaction when concentration is less than 500ppm, press filtration separates, the treated recovery (NH of filtrate
4)
2sO
4, filter cake (manganese sulfide) is with 60 ℃ of deionized waters by material water weight ratio 1:4 washing secondary, and each 3 hours, the squeezing press filtration separated, and controlled filter cake moisture and was less than 25% stand-by.
(2) acidifying
Above-mentioned filter cake is placed in the lass lining reactor, and air in the nitrogen replacement pot, then add 98% technical grade nitric acid under air tight condition, and the cooling temperature of reaction system that maintains of chuck is less than 50 ℃, and stirring reaction to pH value is 3.5, stops acid adding.The hydrogen sulfide produced with the nitrogen replacement reaction, this hydrogen sulfide is for (1) vulcanisation step.
The content of iron and sulfate radical in assaying reaction solution, add the manganese sulfide filter cake according to the molar ratio of MnS/Fe=2/1, maintains and stir 4 hours, then according to molar ratio [SO
4 2-]=[Ba
2+] add barium hydroxide solution, stirring reaction 1.5 hours, press filtration separates, and filter residue is abandoned.
(3) purifying step
Suddenly the filtrate that (2) obtain is placed in the stirring reaction pot, according to the ratio of 1.0 liters of every cubic metre of solution, adds the industrial hydrogen peroxide solution of 27.5wt%, and 45 ℃ are stirred 0.5 hour, secondary filter, and filter residue is abandoned, and the filtrate of clarification is according to Mn (NO
3)
2concentration 50.4wt% adds deionized water and mixes, and cooling rear packing obtains high pure nitric acid manganese product 1#.
To react mol ratio ammonia and hydrogen sulfide and pass in absorption tower, then spray the manganese sulfate solution of concentration 214g/L, and absorb above-mentioned gas and carry out vulcanization reaction.Work as Mn
2+stopped reaction when concentration is less than 500ppm, press filtration separates, the treated recovery (NH of filtrate
4)
2sO
4, filter cake (manganese sulfide) is with 62 ℃ of deionized waters by material water weight ratio 1:4 washing secondary, and each 3 hours, the squeezing press filtration separated, and controlled filter cake moisture and was less than 25% stand-by.
(2) acidifying
Above-mentioned filter cake is placed in the lass lining reactor, and air in the nitrogen replacement pot, then add 98% technical grade nitric acid under air tight condition, and the cooling temperature of reaction system that maintains of chuck is less than 50 ℃, and stirring reaction to pH value is 3.7, stops acid adding.The hydrogen sulfide produced with the nitrogen replacement reaction, this hydrogen sulfide is for (1) vulcanisation step.
The content of iron and sulfate radical in assaying reaction solution, add the manganese sulfide filter cake according to the molar ratio of MnS/Fe=2/1, maintains and stir 4.2 hours, then according to molar ratio [SO
4 2-]=[Ba
2+] add barium hydroxide solution, stirring reaction 1.6 hours, press filtration separates, and filter residue is abandoned.
(3) purifying step
Suddenly the filtrate that (2) obtain is placed in the stirring reaction pot, according to the ratio of 1.2 liters of every cubic metre of solution, adds the industrial hydrogen peroxide solution of 27.5wt%, and 46 ℃ are stirred 1 hour, secondary filter, and filter residue is abandoned, and the filtrate of clarification is according to Mn (NO
3)
2concentration 50.4wt% adds deionized water and mixes, and cooling rear packing obtains high pure nitric acid manganese product 2#.
Embodiment 3
To react mol ratio ammonia and hydrogen sulfide and pass in absorption tower, then spray the manganese sulfate solution of concentration 247g/L, and absorb above-mentioned gas and carry out vulcanization reaction.Work as Mn
2+stopped reaction when concentration is less than 500ppm, press filtration separates, the treated recovery (NH of filtrate
4)
2sO
4, filter cake (manganese sulfide) is with 64 ℃ of deionized waters by material water weight ratio 1:4 washing secondary, and each 3 hours, the squeezing press filtration separated, and controlled filter cake moisture and was less than 25% stand-by.
(2) acidifying
Above-mentioned filter cake is placed in the lass lining reactor, and air in the nitrogen replacement pot, then add 98% technical grade nitric acid under air tight condition, and the cooling temperature of reaction system that maintains of chuck is less than 50 ℃, and stirring reaction to pH value is 3.8, stops acid adding.The hydrogen sulfide produced with the nitrogen replacement reaction, this hydrogen sulfide is for (1) vulcanisation step.
The content of iron and sulfate radical in assaying reaction solution, add the manganese sulfide filter cake according to the molar ratio of MnS/Fe=2/1, maintains and stir 4.6 hours, then according to molar ratio [SO
4 2-]=[Ba
2+] add barium hydroxide solution, stirring reaction 1.8 hours, press filtration separates, and filter residue is abandoned.
(3) purifying step
Suddenly the filtrate that (2) obtain is placed in the stirring reaction pot, according to the ratio of 1.4 liters of every cubic metre of solution, adds the industrial hydrogen peroxide solution of 27.5wt%, and 48 ℃ are stirred 1 hour, secondary filter, and filter residue is abandoned, and the filtrate of clarification is according to Mn (NO
3)
2concentration 50.4wt% adds deionized water and mixes, and cooling rear packing obtains high pure nitric acid manganese product 3#.
Embodiment 4
To react mol ratio ammonia and hydrogen sulfide and pass in absorption tower, then spray the manganese sulfate solution of concentration 300g/L, and absorb above-mentioned gas and carry out vulcanization reaction.Work as Mn
2+stopped reaction when concentration is less than 500ppm, press filtration separates, the treated recovery (NH of filtrate
4)
2sO
4, filter cake (manganese sulfide) is with 65 ℃ of deionized waters by material water weight ratio 1:4 washing secondary, and each 3 hours, the squeezing press filtration separated, and controlled filter cake moisture and was less than 25% stand-by.
(2) acidifying
Above-mentioned filter cake is placed in the lass lining reactor, and air in the nitrogen replacement pot, then add 98% technical grade nitric acid under air tight condition, and the cooling temperature of reaction system that maintains of chuck is less than 50 ℃, and stirring reaction to pH value is 4.0, stops acid adding.The hydrogen sulfide produced with the nitrogen replacement reaction, this hydrogen sulfide is for (1) vulcanisation step.
The content of iron and sulfate radical in assaying reaction solution, add the manganese sulfide filter cake according to the molar ratio of MnS/Fe=2/1, maintains and stir 5 hours, then according to molar ratio [SO
4 2-]=[Ba
2+] add barium hydroxide solution, stirring reaction 2 hours, press filtration separates, and filter residue is abandoned.
(3) purifying step
Suddenly the filtrate that (2) obtain is placed in the stirring reaction pot, according to the ratio of 1.5 liters of every cubic metre of solution, adds the industrial hydrogen peroxide solution of 27.5wt%, and 50 ℃ are stirred 1.5 hours, secondary filter, and filter residue is abandoned, and the filtrate of clarification is according to Mn (NO
3)
2concentration 50.4wt% adds deionized water and mixes, and cooling rear packing obtains high pure nitric acid manganese product 4#.
Through ultimate analysis, the results are shown in Table 1.
Table 1
| Project | 1 # | 2 # | 3 # | 4 # |
| Mn(NO 3) 2wt% | 50.40 | 50.42 | 50.40 | 50.44 |
| K?ppm | <5 | <5 | <5 | <5 |
| Na?ppm | <5 | <5 | <5 | <5 |
| Ca?ppm | 9.7 | 4.7 | 4.5 | 12.1 |
| Mg?ppm | <5 | <5 | <5 | <5 |
| Fe?ppm | 0.33 | 0.31 | 0.30 | 0.34 |
| Cu?ppm | ND | ND | ND | ND |
| Co?ppm | ND | ND | ND | ND |
| Ni?ppm | ND | ND | ND | ND |
| Pb?ppm | ND | ND | ND | ND |
| As?ppm | ND | ND | ND | ND |
| Cr?ppm | ND | ND | ND | ND |
| Cd?ppm | ND | ND | ND | ND |
ND means not detect.
The manganous nitrate that the present invention prepares, its Fe content<0.34ppm,, containing Cu, Co, Ni, Pb, As, Cr and Cd, not can be used in the preparation of lithium-ion secondary cell tertiary cathode material presoma.
Claims (8)
1. the preparation method of a manganous nitrate, the method comprises:
(1) sulfuration
To contain the mixed gas of ammonia and hydrogen sulfide and the manganese sulfate solution of 150～300g/L, carry out vulcanization reaction, until Mn in solution
2+stopped reaction when concentration is less than 500ppm, solid-liquid separation, then that the manganese sulfide filter cake washing obtained is stand-by;
(2) acidifying
Under nitrogen atmosphere, nitric acid is joined in (1) vulcanisation step gained manganese sulfide filter cake, maintain temperature of reaction system and be less than 50 ℃, the hydrogen sulfide that adopts the nitrogen replacement reaction to produce in reaction process; Stirring reaction to pH value 3.5～4.0 o'clock stop acid adding; Then solid-liquid separation, gained filtrate is the manganous nitrate product.
2. the preparation method of manganous nitrate according to claim 1, is characterized in that, in step (1), the concentration of described manganese sulfate solution is 200-250g/L.
3. the preparation method of manganous nitrate according to claim 1 and 2, is characterized in that, in step (1), solid-liquid separation gained filter cake is pressed material-water ratio 1:4 washing secondary with 60～65 ℃ of deionized waters, each 3 hours, then press filtration separated, and obtains the filter cake that moisture content is less than 25%.
4. according to the preparation method of the described manganous nitrate of claim 1-3 any one, it is characterized in that, in step (2), reaction gained hydrogen sulfide is for the vulcanization reaction of step (1).
5. according to the preparation method of the described manganous nitrate of claim 1-4 any one, it is characterized in that, in step (2), before solid-liquid separation, the molar ratio according to MnS/Fe=2/1 in reaction soln adds the manganese sulfide filter cake, stirs 4～5 hours; Then according to molar ratio [SO
4 2-]: [Ba
2+]=1:1, join barium hydroxide solution in reaction soln, stirring reaction 1.5～2 hours.
6. according to the preparation method of the described manganous nitrate of claim 1-5 any one, it is characterized in that, the method further comprises (3) purifying step, this step comprises: according to the ratio of 1.0～1.5 liters of every cubic metre of solution, add superoxol in the filtrate obtained in step (2), 45～50 ℃ are stirred 0.5-1.5 hour, filter, cooling.
7. a manganous nitrate, made by the described method of claim 1-6 any one.
8. according to manganous nitrate claimed in claim 8, it is characterized in that, Fe content<0.34ppm in described manganous nitrate, containing Cu, Co, Ni, Pb, As, Cr and Cd.
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104229897A (en) * | 2014-09-28 | 2014-12-24 | 北京晶晶星科技有限公司 | Preparing method for manganese nitrate solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO87251B1 (en) * | 1983-09-14 | 1985-07-31 | Institutul De Cercetare | Process for preparing manganese nitrate |
| CN101982419A (en) * | 2010-10-25 | 2011-03-02 | 四川大学 | Method for preparing manganous nitrate solution by utilizing oxynitride gas to leach pyrolusite |
| CN102583564A (en) * | 2012-03-23 | 2012-07-18 | 宁夏东方钽业股份有限公司 | Preparation method of electronic grade manganous nitrate for tantalum capacitor |
| CN102660756A (en) * | 2012-05-28 | 2012-09-12 | 贵州红星发展股份有限公司 | High-purity manganese metal and preparation method thereof |
| CN102674467A (en) * | 2012-05-23 | 2012-09-19 | 贵州红星发展股份有限公司 | Preparation method of manganese sulfate and manganese sulfate product prepared by same |
| CN102795670A (en) * | 2012-09-10 | 2012-11-28 | 深圳市新昊青科技有限公司 | High-purity manganese sulfide and method for preparing the same |
-
2013
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO87251B1 (en) * | 1983-09-14 | 1985-07-31 | Institutul De Cercetare | Process for preparing manganese nitrate |
| CN101982419A (en) * | 2010-10-25 | 2011-03-02 | 四川大学 | Method for preparing manganous nitrate solution by utilizing oxynitride gas to leach pyrolusite |
| CN102583564A (en) * | 2012-03-23 | 2012-07-18 | 宁夏东方钽业股份有限公司 | Preparation method of electronic grade manganous nitrate for tantalum capacitor |
| CN102674467A (en) * | 2012-05-23 | 2012-09-19 | 贵州红星发展股份有限公司 | Preparation method of manganese sulfate and manganese sulfate product prepared by same |
| CN102660756A (en) * | 2012-05-28 | 2012-09-12 | 贵州红星发展股份有限公司 | High-purity manganese metal and preparation method thereof |
| CN102795670A (en) * | 2012-09-10 | 2012-11-28 | 深圳市新昊青科技有限公司 | High-purity manganese sulfide and method for preparing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229897A (en) * | 2014-09-28 | 2014-12-24 | 北京晶晶星科技有限公司 | Preparing method for manganese nitrate solution |
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