CN103361669B - High-performance electrolytic manganese dioxide and preparation method thereof and application - Google Patents
High-performance electrolytic manganese dioxide and preparation method thereof and application Download PDFInfo
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Abstract
A kind of preparation method of electrolytic manganese dioxide, including: (1) manganous oxide preparation section: by [Ba2+] be the BaS solution of 0.70～1.5mol/L it being manganese by the ratio of mole: sulfur=1:1～1.1 add manganese oxide powder and react, and control temperature of reaction system 60～90 DEG C of scopes, and the response time controls at 1～2.5 hour, and reaction carries out solid-liquid separation after terminating；(2) liquid operation processed: wash the manganous oxide that (1) obtains with water rear solid-liquid separation, carrying out acidolysis to manganese sulfate concentration in solution to filter cake addition sulphuric acid is 110-120g/L, solid-liquid separation, hydrogen peroxide or Barium dioxide is added to filtrate, make Fe < 0.15ppm in solution, separate manganese sulfate filtrate；(3) electrowinning process: the manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide.Present invention also offers the electrolytic manganese dioxide product prepared by the method.The electrolytic manganese dioxide of the present invention can be used for preparing alkali manganese one-shot battery and lithium rechargeable battery manganate cathode material for lithium.
Description
Technical field
The high-performance electrolytic manganese dioxide product the present invention relates to the preparation method of a kind of high-performance electrolytic manganese dioxide, being obtained by the method and the application of this product.
Background technology
Electrolytic manganese dioxide (EMD) is mainly used in alkali manganese one-shot battery and prepared by lithium rechargeable battery manganate cathode material for lithium, and traditional electrolytic manganese dioxide preparation technology is broadly divided into two classes: a class is to adopt manganese carbonate ore to prepare through acidolysis, remove impurity, refining, electrolysis and powder process operation；Another kind of is adopt dioxide ore for manganese to prepare through carbon reduction, acidleach, remove impurity, refining, electrolysis and powder process operation.In both traditional handicrafts, except the alkali metal in raw material, alkaline-earth metal have separation circuit except potassium, all the other all enter electrolytic solution, cause multiple objectionable impurities in product to increase, have influence on product serviceability.
Summary of the invention
The present invention is directed to the problem that electrolytic manganese dioxide impurity content prepared by traditional handicraft is high, it is provided that the application of the preparation method of a kind of high-performance electrolytic manganese dioxide, the high-performance electrolytic manganese dioxide product obtained by the method and this product.
On the one hand, the preparation method that the invention provides a kind of electrolytic manganese dioxide, including following operation:
(1) manganous oxide preparation section
By [Ba2+] be the BaS solution of 0.70～1.5mol/L it being manganese by the ratio of mole: sulfur=1:1～1.1 add manganese oxide powder and react, control temperature of reaction system 60～90 DEG C of scopes, response time controls at 1～2.5 hour, and reaction carries out solid-liquid separation after terminating, and gained solid phase is manganous oxide；
(2) liquid operation processed
First time solid-liquid separation is carried out after being washed with water by the manganous oxide that (1) obtains, it is 110-120g/L that the filter cake addition sulphuric acid obtained after first time solid-liquid separation carries out acidolysis to manganese sulfate concentration in solution, carry out second time solid-liquid separation, the filtrate obtained after second time solid-liquid separation adds hydrogen peroxide or Barium dioxide, make Fe < 0.15ppm in solution, separate manganese sulfate filtrate；
(3) electrowinning process
The manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide.
In the preparation method of aforesaid electrolytic manganese dioxide, in operation (2), it is 1:4～6 at 40～60 DEG C to described manganous oxide agitator treating 1.5～2 hours according to the mass ratio of manganous oxide Yu water.
In the preparation method of aforesaid electrolytic manganese dioxide, in operation (2), after acidolysis, solution ph maintains in 5.5～6.5 scopes, carries out insulation filter pressing at 80～90 DEG C and separates.
In the preparation method of aforesaid electrolytic manganese dioxide, in operation (3), electric current density 60 pacifies/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95～97 DEG C.
On the other hand, the invention provides a kind of electrolytic manganese dioxide, it is to be obtained by the preparation method of aforesaid electrolytic manganese dioxide.Wherein, by weight percentage, content >=92.30% of manganese dioxide, iron content≤7.4ppm, potassium content≤14.2ppm.
The electrolytic manganese dioxide of the present invention can be used for preparing alkali manganese one-shot battery and lithium rechargeable battery manganate cathode material for lithium.
Compared with traditional handicraft, advantages of the present invention is as follows:
(1) raw material cannot be carried out pretreatment remove impurity by traditional handicraft, and the impurity such as K, Na, Ca, Mg enters electrolytic solution, particularly uses MnCO3Breeze, it is necessary to high Acid leaching, CaCO3、MgCO3MnO prepared by dissolving, manganese oxide ore carbon reducting roast is also required to the high acidity guarantee Mn response rate.And the MnO of the present invention is from liquid phase oxidation reduction reaction, K, Na dissolution, add and can dissolve by weakly acidic pH, the carbonate of Ca, Mg seldom dissolves.
(2) traditional handicraft needs, at low ph values by forming ferric potassium alum except K, then to need larger amount of CaO to neutralize, and the present invention need not this operation.
(3) heavy metal sulfide formed in the present invention is insoluble when technique pH, can remove directly as filtering residue, because of without removing heavy metals operation.
(4) the full manganese recovery ratio of the present invention reaches 90.4%, adds remove impurity operation, it is possible to electrolytic manganese dioxide cost is greatly reduced.
Accompanying drawing explanation
Fig. 1 is the process chart of the preparation method of the present invention.
Detailed description of the invention
The present invention adopts manganese oxide ore and sulfide to carry out redox reaction to obtain manganous oxide, comparatively pure manganese sulfate solution is obtained then through the operation such as magazins' layout, liquid processed, obtain high-performance electrolytic manganese dioxide product through conventional electrolysis, solve the problem that traditional electrolyte manganese dioxide impurity content is high.
Referring to Fig. 1, the process of the present invention is described in detail, except the description below, all the other conventional methods all adopting this area or device.
(1) manganous oxide preparation section
By [Ba2+] be the BaS solution of 0.70～1.5mol/L it being manganese by the ratio of mole: sulfur=1:1～1.1 add manganese oxide powder and react, control temperature of reaction system 60～90 DEG C of scopes, response time controls at 1～2.5 hour, reaction carries out solid-liquid separation after terminating, the sulfide (BaS of the barium in filtratex+1), it is used for preparing Ba (OH)2·8H2O；
The main chemical reactions that manganous oxide preparation section relates to is:
xMnO2+(x+1)BaS+xH2O→xMnO+xBa(OH)2+BaSx+1
(M represents Fe, K, Na, Ca, Mg, Cu, Co, Ni, Pb and Cr)
(2) liquid operation processed
The manganous oxide (1) obtained is 1:4～6 40～60 DEG C of agitator treatings 1.5～2 hours according to the mass ratio of manganous oxide Yu water, filter pressing separates, washing mother solution is back to barium sulfide and leaches workshop section, filter cake is placed in stirred tank, add sulphuric acid and carry out acidolysis, it is preferably added to 98% industrial sulphuric acid and carries out acidolysis, by manganese sulfate concentration in filter cake inventory and sulphuric acid adjustment solution at 110～120g/L；
Containing H in the gas that acid hemolysis process produces2S gas, can pass through claus oven to H2S carries out absorbing process for producing industrial sulphur, and specifically, gas acidolysis produced by vacuum pump sends into claus oven, in the burner that claus oven is anterior, and the H in gas2The 1/3(volume ratio of S) generate SO with air burning2, all the other 2/3(volume ratios) H2The SO of S and production2Reaction, generates elementary sulfur；
Solution ph maintains in 5.5～6.5 scopes, 80～90 DEG C of insulation filter pressings separate, and filtering residue is abandoned after reclaiming manganese sulfate, and filtrate is placed in stirred tank, adding hydrogen peroxide or Barium dioxide carries out oxidation reaction, middle control checks Fe < 0.15ppm in solution；Adding barium hydroxide solution and be about 7 to neutralize sulphuric acid excessive in acid hemolysis process to pH value, filter pressing separates, and filtering residue is abandoned, thus obtaining the manganese sulfate filtrate of clarification；Wherein, any commercially available Barium dioxide is used equally in the method for the present invention, it addition, the Barium dioxide used in the present invention can also obtain by the following method: add industrial grade hydrogen peroxide in the barium hydroxide solution of 1.5～2.0mol/L, the solid fully obtained after reaction is Barium dioxide.Compared to hydrogen peroxide, the thermostability of Barium dioxide is better, can play the effect of nertralizer simultaneously.
The main chemical reactions that liquid operation processed relates to is:
MnO+H2SO4→MnSO4+H2O
H2SO4+H2S+BaO2→S+BaSO4+2H2O
8Fe2++6BaO2+12H2O+6SO4 2-→8Fe(OH)3↓+6BaSO4↓
(3) electrowinning process
The manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide, wherein electric current density 60 pacify/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95～97 DEG C.Electrolysis terminate after electrolysis mother solution in containing sulphuric acid, therefore the electrolysis mother solution of this step and 98% industrial sulphuric acid together can be added in (2) liquid operation processed and filter cake carry out acidolysis to reduce cost.
The main chemical reactions that electrowinning process relates to is:
(4) finished product process
The thick product of electrolytic manganese dioxide that (3) are obtained rinses, pulverizes, powder process, blending, packaging, thus obtaining electrolytic manganese dioxide product, wherein, described rinsing, pulverizing, powder process, blending, packaging all adopt conventional equipment to carry out.
Set forth the enforcement of the method for the present invention below by specific embodiment, it will be apparent to a skilled person that this is understood not to the restriction to the claims in the present invention scope.
Embodiment
The purity of related chemistry reagent used in embodiments of the invention and the assay method related to are as described below:
Sulphuric acid, manganese sulfate is analytical pure；
Fe, K, Na, Ca, Mg, Cu, Co, Ni, Pb and Cr content elemental analysis method: inductively coupled plasma (ICP) atomic emission spectrometry；
Fe ion concentration assay method: inductively coupled plasma (ICP) atomic emission spectrometry；
MnO2Analysis method: Disodium oxalate. reduction-potassium permanganate back titration method；
Hydrochloric acid insoluble substance analyzes method: gravimetric method, accurately weighs 10g sample, is accurate to 0.0002g, adds 1+1 hydrochloric acid and is completely dissolved to sample, and heating by electric cooker, to gentle boil, filters with No. 4 sand core funnels, and washing is to drying without after chloride ion 105 DEG C × 4h, weighing；
Fe ion concentration measures, each Atomic Absorption SpectrophotometerICP: IRISIntrepidIIXSP type inductively coupled plasma atomic emission spectrometer, power & light company of U.S. system.
Embodiment 1
(1) manganous oxide preparation section
By [Ba2+] for the BaS solution 100m of 0.70mol/L3Being manganese by the ratio of mole: sulfur=1:1 adds Low grade manganese ore powder and reacts, control temperature of reaction system at 60 DEG C, the response time controls at 1 hour, and reaction carries out solid-liquid separation after terminating；
(2) liquid operation processed
The manganous oxide (1) obtained is 1:4 40 DEG C of agitator treatings 1.5 hours according to the mass ratio of manganous oxide Yu water, filter pressing separates, washing mother solution is back to barium sulfide and leaches workshop section, filter cake is placed in stirred tank, add 98% industrial sulphuric acid and carry out acidolysis, by manganese sulfate concentration in filter cake inventory and sulphuric acid adjustment solution at 110g/L；
Containing H in the gas that acid hemolysis process produces2S gas, by claus oven to H2S carries out absorbing process for producing industrial sulphur；
Solution ph maintains in 5.5～6.5 scopes, 80 DEG C of insulation filter pressings separate, and filtering residue is abandoned after reclaiming manganese sulfate, and filtrate is placed in stirred tank, add self-control Barium dioxide and carry out oxidation reaction, the stopped reaction when checking to Fe < 0.15ppm in solution；Adding barium hydroxide solution and be about 7 to neutralize sulphuric acid excessive in acid hemolysis process to pH value, filter pressing separates, and filtering residue is abandoned, thus obtaining the manganese sulfate filtrate of clarification；
(3) electrowinning process
The manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide, and wherein, electric current density 60 pacifies/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95 DEG C；
(4) finished product process
The thick product of electrolytic manganese dioxide that (3) are obtained rinses, pulverizes, powder process, blending, packaging, thus obtaining electrolytic manganese dioxide product 1#.
MnO to product 1#2, hydrochloric acid insoluble substance and various constituent content be analyzed, result is in Table 1.Embodiment 2
(1) manganous oxide preparation section
By [Ba2+] for the BaS solution 100m of 1.5mol/L3Being manganese by the ratio of mole: sulfur=1:1.1 adds Low grade manganese ore powder and reacts, control temperature of reaction system at 90 DEG C, the response time controls at 2.5 hours, and reaction carries out solid-liquid separation after terminating；
(2) liquid operation processed
The manganous oxide (1) obtained is 1:6 60 DEG C of agitator treatings 2 hours according to the mass ratio of manganous oxide Yu water, filter pressing separates, washing mother solution is back to barium sulfide and leaches workshop section, filter cake is placed in stirred tank, add 98% industrial sulphuric acid and carry out acidolysis, by manganese sulfate concentration in filter cake inventory and sulphuric acid adjustment solution at 120g/L；
Containing H in the gas that acid hemolysis process produces2S gas, by claus oven to H2S carries out absorbing process for producing industrial sulphur；
Solution ph maintains in 5.5～6.5 scopes, 90 DEG C of insulation filter pressings separate, and filtering residue is abandoned after reclaiming manganese sulfate, and filtrate is placed in stirred tank, add self-control Barium dioxide and carry out oxidation reaction, the stopped reaction when checking to Fe < 0.15ppm in solution；Adding barium hydroxide solution and be about 7 to neutralize sulphuric acid excessive in acid hemolysis process to pH value, filter pressing separates, and filtering residue is abandoned, thus obtaining the manganese sulfate filtrate of clarification；
(3) electrowinning process
The manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide, and wherein, electric current density 60 pacifies/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95 DEG C；
(4) finished product process
The thick product of electrolytic manganese dioxide that (3) are obtained rinses, pulverizes, powder process, blending, packaging, thus obtaining electrolytic manganese dioxide product 2#.
MnO to product 2#2, hydrochloric acid insoluble substance and various constituent content be analyzed, result is in Table 1.
Embodiment 3
(1) manganous oxide preparation section
By [Ba2+] for the BaS solution 100m of 0.9mol/L3Being manganese by the ratio of mole: sulfur=1:1 adds Low grade manganese ore powder and reacts, control temperature of reaction system at 80 DEG C, the response time controls at 1.8 hours, and reaction carries out solid-liquid separation after terminating；
(2) liquid operation processed
The manganous oxide (1) obtained is 1:5 48 DEG C of agitator treatings 1.8 hours according to the mass ratio of manganous oxide Yu water, filter pressing separates, washing mother solution is back to barium sulfide and leaches workshop section, filter cake is placed in stirred tank, add 98% industrial sulphuric acid and carry out acidolysis, by manganese sulfate concentration in filter cake inventory and sulphuric acid adjustment solution at 115g/L；
Containing H in the gas that acid hemolysis process produces2S gas, by claus oven to H2S carries out absorbing process for producing industrial sulphur；
Solution ph maintains in 5.5～6.5 scopes, 85 DEG C of insulation filter pressings separate, and filtering residue is abandoned after reclaiming manganese sulfate, and filtrate is placed in stirred tank, add hydrogen peroxide and carry out oxidation reaction, the stopped reaction when checking to Fe < 0.15ppm in solution；Adding barium hydroxide solution and be about 7 to neutralize sulphuric acid excessive in acid hemolysis process to pH value, filter pressing separates, and filtering residue is abandoned, thus obtaining the manganese sulfate filtrate of clarification；
(3) electrowinning process
The manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide, and wherein, electric current density 60 pacifies/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95 DEG C；
(4) finished product process
The thick product of electrolytic manganese dioxide that (3) are obtained rinses, pulverizes, powder process, blending, packaging, thus obtaining electrolytic manganese dioxide product 3#.
MnO to product 3#2, hydrochloric acid insoluble substance and various constituent content be analyzed, result is in Table 1.
Embodiment 4
(1) manganous oxide preparation section
By [Ba2+] for the BaS solution 100m of 1.2mol/L3Being manganese by the ratio of mole: sulfur=1:1.1 adds Low grade manganese ore powder and reacts, control temperature of reaction system at 70 DEG C, the response time controls at 2 hours, and reaction carries out solid-liquid separation after terminating；
(2) liquid operation processed
The manganous oxide (1) obtained is 1:5 55 DEG C of agitator treatings 1.6 hours according to the mass ratio of manganous oxide Yu water, filter pressing separates, washing mother solution is back to barium sulfide and leaches workshop section, filter cake is placed in stirred tank, add 98% industrial sulphuric acid and carry out acidolysis, by manganese sulfate concentration in filter cake inventory and sulphuric acid adjustment solution at 117g/L；
Containing H in the gas that acid hemolysis process produces2S gas, by claus oven to H2S carries out absorbing process for producing industrial sulphur；
Solution ph maintains in 5.5～6.5 scopes, 88 DEG C of insulation filter pressings separate, and filtering residue is abandoned after reclaiming manganese sulfate, and filtrate is placed in stirred tank, add hydrogen peroxide and carry out oxidation reaction, the stopped reaction when checking to Fe < 0.15ppm in solution；Adding barium hydroxide solution and be about 7 to neutralize sulphuric acid excessive in acid hemolysis process to pH value, filter pressing separates, and filtering residue is abandoned, thus obtaining the manganese sulfate filtrate of clarification；
(3) electrowinning process
The manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide, and wherein, electric current density 60 pacifies/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95 DEG C；
(4) finished product process
The thick product of electrolytic manganese dioxide that (3) are obtained rinses, pulverizes, powder process, blending, packaging, thus obtaining electrolytic manganese dioxide product 4#.
MnO to product 4#2, hydrochloric acid insoluble substance and various constituent content be analyzed, result is in Table 1.
Reference examples
(1) manganese carbonate ore acidolysis: Mn weight percent content is the manganese carbonate breeze 10kg of 15%, and electricity consumption hydrolysis mother liquor is added sulphuric acid and made MnSO4Concentration is the slurry of 100g/L；
(2) remove impurity: with the H of mass concentration 98%2SO4The manganese sulfate slurry pH that solution adjustment is derived is 1.5, adopts steam heating to make slurry be warming up to 80 DEG C, maintains 15 minutes under the stirring condition of 100 revs/min, and when 0.5 MPa, filter pressing separates afterwards；
(3) electrolysis: it is 105g/L that filtrate is diluted to manganese sulfate concentration, carries out electrolysis and obtains the thick product of electrolytic manganese dioxide, and wherein, electric current density 60 pacifies/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95 DEG C；
(4) the thick product of electrolytic manganese dioxide (3) obtained rinses, pulverizes, powder process, blending, packaging, thus obtaining electrolytic manganese dioxide product 5#.
MnO to product 5#2, hydrochloric acid insoluble substance and various constituent content be analyzed, result is in Table 1.
The various physical property measurement results of table 1 electrolytic manganese dioxide product 1#-5#
| Project | 1# | 2# | 3# | 4# | 5# |
| MnO2% | 92.32 | 92.30 | 92.32 | 92.32 | 91.47 |
| Hydrochloric acid insoluble substance % | 0.004 | 0.004 | 0.004 | 0.004 | 0.015 |
| Fe ppm | 7.4 | 7.3 | 7.4 | 7.4 | 51.0 |
| K ppm | 14.2 | 15.4 | 14.9 | 14.4 | 156.0 |
| Na ppm | 55.7 | 58.1 | 57.0 | 57.0 | 3320 |
| Ca ppm | 17.0 | 23.0 | 19.7 | 21.4 | 302.0 |
| Mg ppm | 9.3 | 12.7 | 10.1 | 12.0 | 557 |
| Cu ppm | 0.3 | 0.3 | 0.3 | 0.3 | 1.1 |
| Co ppm | ND | ND | ND | ND | 2.0 |
| Ni ppm | ND | ND | ND | ND | 0.7 |
| Pb ppm | ND | ND | ND | ND | 0.6 |
| Cr ppm | ND | ND | ND | ND | 1.4 |
From the data of table 1 it can be seen that adopt the electrolytic manganese dioxide product that the method for the present invention obtains, its MnO2The electrolytic manganese dioxide that content obtains higher than traditional method, and the electrolytic manganese dioxide that Fe, K, Na, Ca, Mg, Cu impurity content obtains far below traditional method, and do not contain Co, Ni, Pb and Cr impurity.
Claims (3)
1. the preparation method of an electrolytic manganese dioxide, it is characterised in that include following operation:
(1) manganous oxide preparation section
By [Ba2+] be the BaS solution of 0.70～1.5mol/L it being manganese by the ratio of mole: sulfur=1:1～1.1 add manganese oxide powder and react, control temperature of reaction system 60～90 DEG C of scopes, response time controls at 1～2.5 hour, and reaction carries out solid-liquid separation after terminating, and gained solid phase is manganous oxide；
(2) liquid operation processed
First time solid-liquid separation is carried out after being washed with water by the manganous oxide that (1) obtains, it is 110-120g/L that the filter cake addition sulphuric acid obtained after first time solid-liquid separation carries out acidolysis to manganese sulfate concentration in solution, carry out second time solid-liquid separation, the filtrate obtained after second time solid-liquid separation adds Barium dioxide, make Fe < 0.15ppm in solution, separate manganese sulfate filtrate；
(3) electrowinning process
The manganese sulfate filtrate that (2) are obtained carries out electrolysis and obtains the thick product of electrolytic manganese dioxide；
Wherein, step (3) electrolysis terminate after electrolysis mother solution be back to step (2), together add in the filter cake obtained after first time solid-liquid separation in step (2) with sulphuric acid；
Wherein, in operation (2), after acidolysis, solution ph maintains in 5.5～6.5 scopes, carries out insulation filter pressing at 80～90 DEG C and separates.
2. the preparation method of electrolytic manganese dioxide as claimed in claim 1, it is characterised in that in operation (2), is 1:4～6 at 40～60 DEG C to described manganous oxide agitator treating 1.5～2 hours according to the mass ratio of manganous oxide Yu water.
3. the preparation method of electrolytic manganese dioxide as claimed in claim 1 or 2, it is characterised in that in operation (3), electric current density 60 pacifies/square metre, sulphuric acid 50g/L, manganese sulfate 45g/L, temperature 95～97 DEG C.
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