CN109319843A - A method of high purity manganese sulfate is prepared from poor manganese spar - Google Patents
A method of high purity manganese sulfate is prepared from poor manganese spar Download PDFInfo
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Abstract
The invention discloses a kind of methods that high purity manganese sulfate is prepared from poor manganese spar.It comprises the following steps that and is crushed poor manganese ore material, obtain A product；By A product magnetic separation, B product are obtained；B product acidleach, obtains C product；C product filters pressing, takes filtrate to obtain D product；Add Fe into D product2(SO4)3、KMnO4, stir, filtered after standing, filtrate is taken to obtain E product；E product are taken, after adjusting PH, activated carbon of sorbent is added, stirs, filtered after standing, filtrate is taken to obtain F product；Add MnF into F product2, it is aided with ultrasonic treatment, stirs, is filtered after standing, filtrate is taken to obtain G product；Add MnS into G product, be aided with ultrasonic treatment, stir, is filtered after standing, filtrate is taken to obtain H product；By H product condensing crystallizing, high-purity LITHIUM BATTERY manganese sulfate is obtained.The present invention, which has, prepares high purity manganese sulfate using poor manganese spar, and the utilization efficiency of poor manganese spar is high, for impurity such as calcium and magnesiums in manganese sulfate, separates simpler, to obtain manganese sulfate purity is high, the low feature of manganese sulfate production cost.
Description
Technical field
The present invention relates to a kind of method that poor manganese spar prepares manganese sulfate, especially a kind of poor manganese spar obtains high-purity electricity
The preparation method of pond grade manganese sulfate.
Background technique
For China's manganese resource although very abundant, grade is lower.Such as Guizhou Province's Song Taoxian discovered in recent years
In ultra-large type manganese ore deposit, the taste of Mn is lower than 20% in about half reserves, efficiently utilizes these low so finding effective method
Sampling mineral (poor manganese spar) resource is critical issue urgently to be resolved.In addition, in recent years with lithium ion secondary battery industry
It grows rapidly, such as lithium nickel cobalt manganese oxygen tertiary cathode material and a series of high-quality electronic chemical products of manganate cathode material for lithium
It rises, as the manganese sulfate of primary raw material, purity is also increasingly valued by people.
At present in method of purification, common flocculent precipitation, extraction, physisorphtion, multiple steps of crystallization method, manganese metal
The methods of displacement method, electrolysis method, there is low yield, energy consumption is high, at high cost, especially impurity-eliminating effect is incomplete.Use chemistry
The precipitation method carry out purification and impurity removal to manganese sulfate solution and for foreign ion present in solution, corresponding precipitating theoretically are added
Agent can substantially remove it clean.But in the manganese spar of Guizhou province, the impurity such as the higher calcium and magnesium of content are often associated with,
Separation is more difficult, will have a direct impact on MnSO4The quality of product.At present common carbonate, oxalates, phosphate, fluoride with
And composite fluoride etc. removes calcium ions and magnesium ions as precipitating reagent, first three is more serious to manganese consumption, meanwhile, experiment shows
MnF2In 2.5 times of theoretical amounts, impurity-eliminating effect just reaches preferable level.Therefore above method cost is higher.
Now currently, the utilization technology for poor manganese spar is few, the utilization efficiency of poor manganese spar is low, for the calcium in manganese sulfate
The technical issues of impurity such as magnesium, separation is more difficult, and obtained manganese sulfate purity is low, the high production cost of manganese sulfate.
Summary of the invention
The object of the present invention is to provide a kind of methods that high purity manganese sulfate is prepared from poor manganese spar.The present invention has
Preparing high purity manganese sulfate using poor manganese spar, the utilization efficiency of poor manganese spar is high, for impurity such as calcium and magnesiums in manganese sulfate,
Separate simpler, to obtain manganese sulfate purity is high, the low feature of the production cost of manganese sulfate.
Technical solution of the present invention: a method of high purity manganese sulfate being prepared from poor manganese spar, is comprised the following steps that
(a) poor manganese ore material is crushed, obtains A product；
(b) A product are sent into magnetic separator and carry out magnetic separation, obtain B product；
(c) put product B is put in impregnating in sulfuric acid solution, manganese sulfate concentration is 300-600g/L in soak, obtains C product；
(d) C product are subjected to filters pressing, take filtrate, obtains D product；
(e) Fe is added into D product2(SO4)3And KMnO4, while solution PH is adjusted to 2-4, and it is stirred at 80-90 DEG C, it is quiet
Filtering is postponed, filtrate is taken, obtains E product；
(f) E product are taken, solution PH is adjusted to 4-5, adds activated carbon of sorbent, stirred evenly at 60-70 DEG C, after standing
Filtering, takes filtrate, obtains F product；
(g) MnF is added into F product2Slurry, while solution PH is adjusted to 4-6, ultrasonic treatment is aided at 80-90 DEG C, is stirred
It mixes, is filtered after standing, take filtrate, obtain G product；
(h) MnS is added into G product, while adjusting solution PH to 4-6.5, and ultrasonic treatment is aided at 85-95 DEG C, is stirred
Uniformly, it is filtered after standing, takes filtrate, obtain H product；
(i) by after H product normal temperature and pressure condensing crystallizing, final products are filtered to obtain.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, the step e, step f, step g and step h
In, it is all made of Mn (OH)2The H that powder or concentration are 40-60%2SO4To adjust solution pH value.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step a, the particle size of A product is
400-600 mesh.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step c, the concentration of sulfuric acid solution is
40-60%.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step e, D product KMnO4And Fe2
(SO4)3Usage ratio be, in the D product of 1L be added 1.5-5g KMnO4With 7-38g Fe2(SO4)3。
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step e, stirred at 80-90 DEG C
1-2h is filtered after then standing 2-3h.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step f, stirred at 60-70 DEG C
0.5-1h is filtered after then standing 1-2h.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step g, F product and MnF2Dosage
Ratio is that the MnF of 3-6g is first added in the F product of 1L2After slurry, after stirring 0.5-1h, then the MnF of 3-6g is added2Slurry continues
Stir 0.5-1h；Under conditions of adjusting solution PH to 4-6.5 simultaneously in whole process, and be aided at 80-90 DEG C ultrasonic treatment into
Row filters after then standing 9-11h, takes filtrate, obtain G product；The MnF2The concentration of slurry is 0.8-2mol/L.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step h, the amount ratio of G product and MnS
Example is that the MnS of 1-4.2g is added in the G product of 1L.
It is above-mentioned from the method for preparing high purity manganese sulfate in poor manganese spar, in the step h, be aided at 85-95 DEG C
Ultrasonic treatment stirs 0.5-1h, filters after then standing 3-6h.
Advantage is as follows in technical solution of the present invention compared with prior art:
It is broken to reduce feedstock Particle size in step a, mineral effecting reaction contact area is improved, reaction efficiency is increased,
The impurity in the poor manganese ore material of part is rejected simultaneously.
In step b, raw material grade can be significantly improved by carrying out pre- purification using magnetic separator, reduced sour dosage, reduced to equipment
Corruption effect, effectively reduce cost；
In step c, after acidleach, manganese sulfate concentration is 300-600g/L；
In step d, filters pressing can be effectively except insoluble matters such as impurity elimination stone and soil；
In step e, Fe2(SO4)3Remove K+、Na+Shown in principle following equation, while KMnO4By Fe in solution2+Oxidation
At Fe3+Facilitate removal, and step e PH environment is lower, the first step removes K+、Na+Afterwards, remaining operation avoids strong acid environment, prevents
The generation of HF.
3Fe2(SO4)3+6H2O=6Fe (OH) SO4+3H2SO4
4Fe(OH)SO4+4H2O=2Fe2(OH)4SO4+2H2SO4
2Fe(OH)SO4+2Fe2(OH)4SO4+K2SO4+2H2O=K2Fe6(SO4)4(OH)12+H2SO4
2Fe(OH)SO4+2Fe2(OH)4SO4+Na2SO4+2H2O=Na2Fe6(SO4)4(OH)12+H2SO4
MnO4 -+5Fe2++8H+→5Fe3++Mn2++4H2O
In step f, Fe is removed3+Shown in reaction principle following equation, while using Mn (OH)2It will not be introduced by adjusting PH
His impurity element, is effectively ensured product purity；
In step g, Ca is removed2+、Mg2+Shown in reaction principle following equation, due to Mn2F is insoluble in water, so first will
Mn2F stirs into slurry, according to F product and MnF2Usage ratio be that the MnF of 3-6g is first added in the F product of 1L2After slurry, stirring
After 0.5-1h, then add the MnF of 3-6g2Slurry continues to stir 0.5-1h；MnF is added into F product2Slurry, and in whole process
It uses Mn (OH)2The H that powder or concentration are 40-60%2SO4, to adjust solution PH to 4-6, and it is aided with ultrasonic place at 80-90 DEG C
It is carried out under conditions of reason, increases F-With Ca2+、Mg2+Reaction efficiency, make reaction it is more complete, dust removal rate is higher, and use
Mn2F will not introduce other impurities element as precipitating reagent, and product purity is effectively ensured；
Ca2++2F-→CaF2↓
Mg2++2F-→MgF2↓
In step h, the following equation of heavy metal ion Me (Fe, Cu, Pb, Zn, Cd, Co, Ni) reaction principle is removed using MnS
Shown in formula, and when stirring, it is aided with ultrasonic treatment, increases S2-With Men+Reaction efficiency, make reaction it is more complete, dust removal rate is more
Height, and other impurities element will not be introduced as precipitating reagent using MnS, product purity is effectively ensured；
MnS+Me2+=MeS+Mn2+
In step i, H product purity is sufficiently high, and normal temperature and pressure condensing crystallizing cost is minimum, can obtain high-purity LITHIUM BATTERY sulfuric acid
Manganese.
Experiments have shown that:
Applicant distinguishes high-purity LITHIUM BATTERY manganese sulfate progress constituent analysis obtained, analysis in 1-3 of the embodiment of the present invention
The results are shown in Table 1:
1 interpretation of result of table
From the foregoing, it will be observed that the manganese sulfate impurity content that patented method is prepared through the invention meets the People's Republic of China (PRC)
Chemical industry standard, battery manganese sulfate (HG/T 4823-2015) indices, so manganese sulfate prepared by the present invention reaches
High-purity LITHIUM BATTERY.
In conclusion the present invention, which has, prepares high purity manganese sulfate using poor manganese spar, the utilization efficiency of poor manganese spar is high,
For impurity such as calcium and magnesiums in manganese sulfate, simpler, to obtain manganese sulfate purity is high is separated, the production cost of manganese sulfate is low
Beneficial effect.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
Embodiment 1.A kind of method preparing high purity manganese sulfate from poor manganese spar comprises the following steps that
(a) poor manganese ore material is broken into 400 mesh, obtains A product；
(b) A product are sent into magnetic separator and carry out magnetic separation, obtain B product；
(c) it is impregnated in the sulfuric acid solution for being 40% put product B is put in concentration, manganese sulfate concentration is 300g/L in soak, obtains C
Product；
(d) by C product filters pressing, filtrate is taken, obtains D product；
(e) according to D product, Fe2(SO4)3And KMnO4Usage ratio be, in the D product of 1L be added 7g Fe2(SO4)3With
1.5g KMnO4；Fe is added into D product2(SO4)3And KMnO4, while using Mn (OH)2The H that powder or concentration are 40%2SO4Come
Solution PH is adjusted to 2-4,1h is stirred at 80 DEG C, is filtered after then standing 2h；
(f) E product are taken, using Mn (OH)2The H that powder or concentration are 40%2SO4To adjust solution PH to 4-5, addition absorption
Agent active carbon stirs evenly 0.5h at 60 DEG C, filters after then standing 1h, takes filtrate, obtain F product；
(g) according to F product and MnF2Usage ratio be that the MnF of 3g is first added in the F product of 1L2After slurry, after stirring 0.5h,
The MnF of 3g is added again2Slurry continues to stir 0.5h；MnF is added into F product2Slurry, and Mn (OH) is used in whole process2Powder
The H that end or concentration are 40%2SO4It is carried out under conditions of solution PH is adjusted to 4-6, and is aided at 80 DEG C ultrasonic treatment, it is then quiet
It is filtered after setting 9h, takes filtrate, obtain G product；The MnF2The concentration of slurry is 0.8mol/L；
It (h) is that the MnS of 1g is added in the G product of 1L according to the usage ratio of G product and MnS；MnS is added into G product, is used
Mn(OH)2The H that powder or concentration are 40%2SO4Solution PH is adjusted to 4-6.5, ultrasonic treatment is aided at 85 DEG C, stirs
0.5h is filtered after then standing 3h, is taken filtrate, obtain H product；
(i) by after H product normal temperature and pressure condensing crystallizing, final products are filtered to obtain.
Embodiment 2.A kind of method preparing high purity manganese sulfate from poor manganese spar comprises the following steps that
(a) poor manganese ore material is broken into 500 mesh, obtains A product；
(b) A product are sent into magnetic separator and carry out magnetic separation, obtain B product；
(c) it is impregnated in the sulfuric acid solution for being 50% put product B is put in concentration, manganese sulfate concentration is 400g/L in soak, obtains C
Product；
(d) by C product filters pressing, filtrate is taken, obtains D product；
(e) according to D product, Fe2(SO4)3And KMnO4Usage ratio be, in the D product of 1L be added 20g Fe2(SO4)3And 3g
KMnO4；Fe is added into D product2(SO4)3And KMnO4, while using Mn (OH)2The H that powder or concentration are 50%2SO4It is molten to adjust
Liquid PH to 2-4 stirs 1.5h at 85 DEG C, filters after then standing 2.5h；
(f) E product are taken, using Mn (OH)2The H that powder or concentration are 50%2SO4To adjust solution PH to 4-5, addition absorption
Agent active carbon stirs evenly 1h at 65 DEG C, filters after then standing 1.5h, takes filtrate, obtain F product；
(g) according to F product and MnF2Usage ratio be that the MnF of 4g is first added in the F product of 1L2After slurry, after stirring 0.8h,
The MnF of 4g is added again2Slurry continues to stir 0.8h；MnF is added into F product2Slurry, and Mn (OH) is used in whole process2Powder
The H that end or concentration are 50%2SO4It is carried out under conditions of solution PH is adjusted to 4-6, and is aided at 90 DEG C ultrasonic treatment, it is then quiet
It is filtered after setting 10h, takes filtrate, obtain G product；The MnF2The concentration of slurry is 1.2mol/L；
It (h) is that the MnS of 2.5g is added in the G product of 1L according to the usage ratio of G product and MnS；MnS is added into G product, is adopted
With Mn (OH)2The H that powder or concentration are 50%2SO4Solution PH is adjusted to 4-6.5, ultrasonic treatment is aided at 90 DEG C, stirs
1h is filtered after then standing 4h, is taken filtrate, obtain H product；
(i) by after H product normal temperature and pressure condensing crystallizing, final products are filtered to obtain.
Embodiment 3.A kind of method preparing high purity manganese sulfate from poor manganese spar comprises the following steps that
(a) poor manganese ore material is broken into 500 mesh, obtains A product；
(b) A product are sent into magnetic separator and carry out magnetic separation, obtain B product；
(c) it is impregnated in the sulfuric acid solution for being 50% put product B is put in concentration, manganese sulfate concentration is 500g/L in soak, obtains C
Product；
(d) by C product filters pressing, filtrate is taken, obtains D product；
(e) according to D product, Fe2(SO4)3And KMnO4Usage ratio be, in the D product of 1L be added 30g Fe2(SO4)3And 4g
KMnO4；Fe is added into D product2(SO4)3And KMnO4, while using Mn (OH)2The H that powder or concentration are 50%2SO4It is molten to adjust
Liquid PH to 2-4 stirs 2h at 85 DEG C, filters after then standing 3h；
(f) E product are taken, using Mn (OH)2The H that powder or concentration are 50%2SO4To adjust solution PH to 4-5, addition absorption
Agent active carbon stirs evenly 1h at 65 DEG C, filters after then standing 1.5h, takes filtrate, obtain F product；
(g) according to F product and MnF2Usage ratio be that the MnF of 5g is first added in the F product of 1L2After slurry, after stirring 1h, then
Add the MnF of 5g2Slurry continues to stir 1h；MnF is added into F product2Slurry, and Mn (OH) is used in whole process2Powder or
The H that concentration is 50%2SO4It carries out under conditions of solution PH is adjusted to 4-6, and is aided at 85 DEG C ultrasonic treatment, then stands
It is filtered after 10h, takes filtrate, obtain G product；The MnF2The concentration of slurry is 1.4mol/L；
It (h) is that the MnS of 3g is added in the G product of 1L according to the usage ratio of G product and MnS；MnS is added into G product, is used
Mn(OH)2The H that powder or concentration are 50%2SO4Solution PH is adjusted to 4-6.5, ultrasonic treatment is aided at 90 DEG C, stirs
0.8h is filtered after then standing 4h, is taken filtrate, obtain H product；
(i) by after H product normal temperature and pressure condensing crystallizing, final products are filtered to obtain.
Embodiment 4.A kind of method preparing high purity manganese sulfate from poor manganese spar comprises the following steps that
(a) poor manganese ore material is broken into 600 mesh, obtains A product；
(b) A product are sent into magnetic separator and carry out magnetic separation, obtain B product；
(c) it is impregnated in the sulfuric acid solution for being 60% put product B is put in concentration, manganese sulfate concentration is 600g/L in soak, obtains C
Product；
(d) by C product filters pressing, filtrate is taken, obtains D product；
(e) according to D product, Fe2(SO4)3And KMnO4Usage ratio be, in the D product of 1L be added 38g Fe2(SO4)3And 5g
KMnO4；Fe is added into D product2(SO4)3And KMnO4, while using Mn (OH)2The H that powder or concentration are 60%2SO4It is molten to adjust
Liquid PH to 2-4 stirs 2h at 90 DEG C, filters after then standing 3h；
(f) E product are taken, using Mn (OH)2The H that powder or concentration are 60%2SO4To adjust solution PH to 4-5, addition absorption
Agent active carbon stirs evenly 1h at 70 DEG C, filters after then standing 2h, takes filtrate, obtain F product；
(g) according to F product and MnF2Usage ratio be that the MnF of 6g is first added in the F product of 1L2After slurry, after stirring 1h, then
Add the MnF of 6g2Slurry continues to stir 1h；MnF is added into F product2Slurry, and Mn (OH) is used in whole process2Powder or
The H that concentration is 60%2SO4It carries out under conditions of solution PH is adjusted to 4-6, and is aided at 90 DEG C ultrasonic treatment, then stands
It is filtered after 11h, takes filtrate, obtain G product；The MnF2The concentration of slurry is 2.0mol/L；
It (h) is that the MnS of 4.2g is added in the G product of 1L according to the usage ratio of G product and MnS；MnS is added into G product, is adopted
With Mn (OH)2The H that powder or concentration are 60%2SO4Solution PH is adjusted to 4-6.5, ultrasonic treatment is aided at 95 DEG C, stirs
1h is filtered after then standing 6h, is taken filtrate, obtain H product；
(i) by after H product normal temperature and pressure condensing crystallizing, final products are filtered to obtain.
In above step, in the adjustment process of pH value, whether measurement PH first if it is within range, is then not required in range
It adjusts；If being used Mn (OH) not in range2The H that powder or concentration are 40-60%2SO4To adjust solution PH to range
It is interior.
Such as: if the pH value of step e solution is 1.5, use Mn (OH)2Powder is by the pH value adjustment of step e solution
To 2-4；If the solution pH value of step f is 4.8, which meets the pH value requirement of step f, then does not need to adjust；
If the pH value of g step solution is 6.5, the H of 40-60% is used2SO4To adjust solution PH to 4-6；If the solution pH value of step h
It is 5, which meets the pH value requirement of step h, then does not have to adjust pH value.
Claims (10)
1. a kind of method for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: comprise the following steps that
(a) poor manganese ore material is crushed, obtains A product；
(b) A product are sent into magnetic separator and carry out magnetic separation, obtain B product；
(c) put product B is put in impregnating in sulfuric acid solution, manganese sulfate concentration is 300-600g/L in soak, obtains C product；
(d) C product are subjected to filters pressing, take filtrate, obtains D product；
(e) Fe is added into D product2(SO4)3And KMnO4, while solution PH is adjusted to 2-4, it is stirred at 80-90 DEG C, mistake after standing
Filter, takes filtrate, obtains E product；
(f) E product are taken, adjust solution PH to 4-5, addition activated carbon of sorbent is stirred evenly at 60-70 DEG C, is filtered after standing,
Filtrate is taken, F product are obtained；
(g) MnF is added into F product2Slurry, while solution PH is adjusted to 4-6, ultrasonic treatment is aided at 80-90 DEG C, stirring is quiet
Filtering is postponed, filtrate is taken, obtains G product；
(h) MnS is added into G product, while adjusting solution PH to 4-6.5, and ultrasonic treatment is aided at 85-95 DEG C, is stirred evenly,
It is filtered after standing, takes filtrate, obtain H product；
(i) by after H product normal temperature and pressure condensing crystallizing, final products are filtered to obtain.
2. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
E, in step f, step g and step h, it is all made of Mn (OH)2The H that powder or concentration are 40-60%2SO4To adjust solution pH value.
3. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In a, the particle size of A product is 400-600 mesh.
4. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In c, the concentration of sulfuric acid solution is 40-60%.
5. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In e, D product KMnO4And Fe2(SO4)3Usage ratio be, in the D product of 1L be added 1.5-5g KMnO4With 7-38g Fe2(SO4)3。
6. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In e, 1-2h is stirred at 80-90 DEG C, is filtered after then standing 2-3h.
7. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In f, 0.5-1h is stirred at 60-70 DEG C, is filtered after then standing 1-2h.
8. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In g, F product and MnF2Usage ratio be that the MnF of 3-6g is first added in the F product of 1L2After slurry, after stirring 0.5-1h, then add
The MnF of 3-6g2Slurry continues to stir 0.5-1h；Solution PH is adjusted to 4-6.5 simultaneously in whole process, and is aided at 80-90 DEG C
It is carried out under conditions of ultrasonic treatment, is filtered after then standing 9-11h, take filtrate, obtain G product；The MnF2The concentration of slurry is
0.8-2mol/L。
9. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In h, the usage ratio of G product and MnS are that the MnS of 1-4.2g is added in the G product of 1L.
10. the method according to claim 1 for preparing high purity manganese sulfate from poor manganese spar, it is characterised in that: the step
In rapid h, ultrasonic treatment is aided at 85-95 DEG C, 0.5-1h is stirred, is filtered after then standing 3-6h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110357164A (en) * | 2019-07-08 | 2019-10-22 | 四川大学 | The method that manganese oxide ore pulp recycles high-efficiency flue gas desulfurization coupling manganese sulfate green purifying |
| CN110668502A (en) * | 2019-10-31 | 2020-01-10 | 青川县青云上锰业有限公司 | Method for preparing manganese sulfate by purification |
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| CN110668502A (en) * | 2019-10-31 | 2020-01-10 | 青川县青云上锰业有限公司 | Method for preparing manganese sulfate by purification |
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