CN102674467A - Preparation method of manganese sulfate and manganese sulfate product prepared by same - Google Patents
Preparation method of manganese sulfate and manganese sulfate product prepared by same Download PDFInfo
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- CN102674467A CN102674467A CN2012101631793A CN201210163179A CN102674467A CN 102674467 A CN102674467 A CN 102674467A CN 2012101631793 A CN2012101631793 A CN 2012101631793A CN 201210163179 A CN201210163179 A CN 201210163179A CN 102674467 A CN102674467 A CN 102674467A
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Abstract
The invention relates to a preparation method of manganese sulfate and a manganese sulfate product prepared by the same. The method comprises the following steps: A. adding metal manganese into deionized water, and slowly adding sulfuric acid into the mixture to react until the pH value reaches 3.5-4.0, thereby obtaining a solution; B. adding excessive manganese sulfide relative to impurity content into the solution obtained in the step A, stirring to react at 70-100 DEG C for 4-6 hours, and carrying out solid-liquid separation; C. adding excessive hydrogen peroxide into the solution obtained by the solid-liquid separation in the step B, uniformly stirring, heating to a boiling state, and carrying out solid-liquid separation; and D. evaporating the solution obtained by solid-liquid separation in the step C to obtain the manganese sulfate. The preparation method provided by the invention optimizes and simplifies the preparation technique of high-purity manganese sulfate. The high-purity manganese sulfate product prepared by the method provided by the invention contains fewer impurities, and especially the content of potassium, sodium and other impurities which are difficult to remove is nearly down to 10ppm.
Description
Technical field
The present invention relates to the preparation method of the preparation field of inorganic fine chemical product, particularly a kind of manganous sulfate and the manganese sulfate product that this method makes.
Background technology
High purity manganese sulfate can prepare the lithium ion battery manganese cathode material; It is one of raw material of positive electrode material ternary presoma (nickel Co-Mn compound); The quality of high purity manganese sulfate directly has influence on the performance of lithium ion battery, and seek becomes industrial hot spot with low technology cost mass preparation high purity manganese sulfate for this reason.
At present, the preparation method of high purity manganese sulfate mainly is to be the preparation were established of starting raw material with the ore.
CN101704554A; Taked to utilize sulfide and dioxide ore for manganese to react with reductibility, press filtration separating obtained solid phase again with sulfuric acid reaction to pH=3～5, control manganous sulfate concentration 300～400g/L scope; Solid-liquid separation gained solution uses sulfuric acid acidation to pH value to be 2-3; And add hydrogen peroxide and heating, and the secondary filter removal of impurities, filtrating carries out evaporating, concentrating and crystallizing and dehydration obtains manganous sulfate.This method utilizes ore to be raw material, because impurity component is more in the ore, therefore needs the control strength of solution; The removal of impurities processing is carried out in secondary filter, steps such as crystallization, yet even through these steps; The foreign matter content of the product that obtains still can not ignore; Calcium contents can reach 200ppm sometimes, and the content of potassium and sodium is approximately 50ppm, and the content of nickel and zinc still can be surveyed.
CN101723466A discloses low-grade MnO in a kind of utilization
2The ore deposit is carried out flue gas desulfurization and is prepared MnSO
4H
2The method of O, low-grade MnO in the utilization
2Breeze is mixed with slip, in absorption unit, feeds earlier sulfur-containing smoke gas, the gentle liquid proportional of control gas speed, and the back adds MnO
2Slip, and control it and do countercurrent flow with respect to sulfur-containing smoke gas, and the flue gas self-absorption device after the desulfurization is discharged, press filtration separates the slip of being discharged by absorption unit, mother liquor is led being back to absorption unit, continues this and leads back operations [MnSO in this mother liquor
4]>=200g/L, with the gained filter cake under 60-70 ℃, agitator treating, settled solution that press filtration is separating obtained is regulated pH value=2-4; At 25 ℃-95 ℃, stir adding manganese sulfide down, and filtering and impurity removing, continue to stir; Press filtration separates, and evaporation gained clear filtrate can get MnSO behind the airflow drying
4H
2O.Though take to add the manganese sulfide filtering and impurity removing in this technology, make manganous sulfate, yet its be with in low-grade MnO
2Breeze and sulfur-containing smoke gas are the reaction of raw material, and complex process, the MnSO that obtains
4H
2O purity also only has and at most only has 98.77%.
There is the shortcoming of technical process length, complex process in above-mentioned these preparation routes.
Summary of the invention
It is starting raw material that the present invention adopts with the electrolytic metal Mn, produces the high-purity sulphuric acid manganese product through removal of impurities, cleaning section, has solved the long technical problem of technical process.
The basic chemical reaction that the present invention relates to:
Mn+H
2S?O
4→MnSO
4+H
2↑
MSO
4+MnS→MS↓+MnSO
4
(wherein M:Cd, Cr, Cu, Co, Ni, Pb, As, Zn, Se etc.)
Fe
2++H
2O
2→Fe(OH)
3↓+H
2O
A kind of method for preparing manganous sulfate is characterized in that, may further comprise the steps:
A puts into manganese metal earlier in deionized water, in this mixture, slowly add sulfuric acid reaction to pH value=3.5～4.0, obtains solution;
B adds excessive manganese sulfide in steps A gained solution, in 70～100 ℃ of stirring reactions 4～6 hours, and solid-liquid separation;
C adds hydrogen peroxide in the solution of step B solid-liquid separation gained, the post-heating that stirs is to boiling solid-liquid separation;
D obtains manganese sulfate product with the solution evaporation of step C solid-liquid separation gained.
Preferably, the manganese metal of said steps A is the electrolytic metal Mn of weight percentage more than 99%.
Preferably, the manganese metal of said steps A and the ratio of deionized water are 75～175g/L water, preferred 125～163g/L water.
Preferably, pH value=3.5 of said steps A.
Preferably, the reaction of said step B adds 3 times the manganese sulfide of the mole number of sulphur more than or equal to mole number plumbous in the solution.
Preferably, the temperature of reaction of said step B is 85～90 ℃.
Preferably, the temperature of reaction of said step B is 87 ℃.
Preferably, the reaction times of said step B is 4.5～5.5 hours, preferred 5 hours.
Preferably, the add-on of the hydrogen peroxide of said step B is 1.0～3.6L/m
3, preferred 1.7～3.4L/m
3
The invention still further relates to a kind of high-purity sulphuric acid manganese product that utilizes preceding method to prepare.
Preferably, the heavy metal content of said manganese sulfate product is all less than 0.1ppm, and K, Na, Mg content are lower than 10ppm, and Fe content is lower than 1ppm, and Ca content is lower than 20ppm.
Preparing method's optimization of the present invention has also been simplified the preparation technology of high purity manganese sulfate.The prepared high-purity sulphuric acid manganese product of the present invention, product purity is high, and various impurity are few, especially are difficult for the K of removal, and impurity such as Na have almost reached and have been lower than 10ppm.
Description of drawings
Fig. 1 is a main schema of the present invention.
Embodiment
About raw material:
Electrolytic metal Mn: use the electrolytic metal Mn more than 99%.
Sulfuric acid: choose the industrial sulphuric acid of any concentration, for example mass concentration is 98% the industrial vitriol oil.
MnS: be generally self-control, make through manganous sulfate and ammonium sulfide.Because equipment, the add-on of manganese sulfide is mainly seen the amount of the metallic impurity that it will be handled, and its add-on is generally got more than 3 times of Pb mole number in the solution (comprising 3 times), and the available inductively coupled plasma atomic emission spectrometry method of the amount of Pb is measured.
Hydrogen peroxide: the industrial hydrogen peroxide of optional any concentration, for example mass percentage concentration is 27.5%, 60% hydrogen peroxide.The add-on of hydrogen peroxide is generally according to MnSO
4Strength of solution and deciding, according to situation of the present invention, preferred 1～3.6L/m
3, more preferably 1.7～3.4L/m
3
Concrete technology:
In conjunction with Fig. 1, main technique flow process of the present invention is described below:
A sulfuric acid reaction step:
In uncovered reactor, add deionized water earlier, stir adding electrolytic metal Mn (purity 99%) down, wherein the ratio of manganese metal and deionized water can be 75～175g/L water; Consider the influence of evaporation energy consumption factor, when the manganous sulfate concentration that promptly obtains was hanged down, it was bigger to evaporate used energy consumption; But manganous sulfate is during greater than 450g/L; Viscosity significantly increases, and filters to begin to become difficulty so the preferred 125～163g/L water of manganese metal.Slowly add industrial sulphuric acid (mass concentration 98%) then and react to pH value 3～5, preferred 3.5～4.0, most preferably 3.5.
This step mainly is that manganese is dissolved as manganese sulfate solution, wherein controls pH value 3 ~ 5th, reaches reaction ratio in order to control, and guarantees the impurity-eliminating effect of MnS simultaneously.Because the purity of manganese is higher, need carry out removal of impurities and handle.
B MnS removal of impurities is handled
In the solution that the steps A reaction obtains, add MnS; A large amount of Pb have been brought into owing to produce the pole plate equipment of electrolytic metal Mn; So it is plumbous as topmost impurity in the plain metal manganese; The Pb content estimation capable of using of foreign matter content in the solution, wherein the mol ratio of MnS and impurity Pb so just can guarantee that more than or equal to 3: 1 all heavy metal ion all are removed.Plumbous content can be measured through the inductively coupled plasma emission spectrography method.Removing miscellaneous operation can be 70～100 ℃ of stirring reaction 4～6 hours, preferred 85～90 ℃ of stirring reactions 4.5～5.5 hours, and most preferably 87 ℃ of stirring reactions are 5 hours, and press filtration separates, the recyclable valuable element of filter cake, Cu for example, Zn etc., clear filtrate gets into next-step operation.
This step mainly be with wherein mostly impurity metallic elements form sulfide precipitation, especially produce the higher Pb heavy metal of content that the lead-containing alloy pole plate equipment of electrolytic metal Mn is brought into, thus with these metals as impurity and MnSO
4Separate, and remove impurity such as Strontium Sulphate, finally reach the effect of removing impurity.The element that wherein is removed comprises Cd, Cr, Cu, Co, Ni, Pb, As, Zn, Se etc.And also have Ca in the solution, and Mg, Fe, elements such as Na, K because above-mentioned several kinds of elements are own less in electrolytic metal Mn, have only tens ppm, therefore can not influence the grade of the finished product.
C hydrogen peroxide purifying treatment
The filtrating of step B solid-liquid separation gained is added industrial hydrogen peroxide, and the amount that wherein adds hydrogen peroxide is 2～3L/m when preferably being controlled at manganese sulfate solution for 400g/L
3, because preferred manganese sulfate solution concentration is generally 206～481g/L, preferred 344～450g/L (concentration by manganese metal is that 75～175g/L calculates), the hydrogen peroxide flow that therefore feeds is preferably 1.0～3.6L/m
3, more preferably 1.7～3.4L/m
3Stir 15 minutes post-heating to boiling after adding hydrogen peroxide, preferably kept gentle boil 30 minutes, stop heating, solid-liquid separation, filter residue is abandoned.
The most of Fe that will exist during this step will be filtrated
2+Oxidation and deposition are removed, and also oxidable a spot of sulfide is not introduced new impurity simultaneously again.
D is with the clear filtrate of step C solid-liquid separation gained, and evaporative crystallization obtains the high-purity manganese sulfate monohydrate product.
The manganese sulfate product of gained; Heavy metal content is all less than the minimum value of the detecting 0.1ppm of detecting instrument inductively coupled plasma atomic emission spectrometer (ICP-AES can guarantee less than 0.1ppm under strong background interference the detection of these several kinds of elements); K, Na, Mg content are lower than 10ppm; Fe content is lower than 1ppm, and Ca content is lower than 20ppm.
Instance with following is described in detail as follows, yet, one skilled in the art will appreciate that protection scope of the present invention should not be confined to this.
The used instrument and equipment of following examples is conventional equipment, and those skilled in the art can be easy to buy or obtain.
The raw materials used source of following examples is as shown in table 2 below:
Embodiment (preparation test and performance evaluation experiment):
Embodiment 1
In 5000 liters of uncovered lass lining reactors, add 4000 liters of deionized waters earlier, 500 kilograms of purity of adding are 99% manganese metal under stirring, and slowly adding 98% industrial sulphuric acid reacts to pH value 3.5; The mensuration lead content is 14.76kg; The MnS that adds 40 kilogram 60%, 87 ℃ of stirring reactions 5 hours, press filtration separates; Filter cake reclaims valuable element, and clear filtrate gets into next-step operation.
Above-mentioned filtrating is added 27.5% industrial hydrogen peroxide in the ratio of every cubic metre of 2.5L, stir 15 minutes post-heating to boiling, and kept gentle boil 30 minutes, stop heating, solid-liquid separation, filter residue is abandoned, and the clear filtrate evaporation obtains high purity manganese sulfate sample 1
#
Embodiment 2
In 5000 liters of uncovered lass lining reactors, add 4000 liters of deionized waters earlier, 600 kilograms of purity of adding are 99% manganese metal under stirring, and slowly adding 98% industrial sulphuric acid reacts to pH value 4.0; The mensuration lead content is 17.20kg; The MnS that adds 40 kilogram 60%, 85 ℃ of stirring reactions 5.5 hours, press filtration separates; Filter cake reclaims valuable element, and clear filtrate gets into next-step operation.
Above-mentioned filtrating is added 27.5% industrial hydrogen peroxide in the ratio of every cubic metre of 2.5L, stir 15 minutes post-heating to boiling, and kept gentle boil 30 minutes, stop heating, solid-liquid separation, filter residue is abandoned, and the clear filtrate evaporation obtains high purity manganese sulfate sample 2
#
Embodiment 3
In 5000 liters of uncovered lass lining reactors, add 4000 liters of deionized waters earlier, 650 kilograms of purity of adding are 99% manganese metal under stirring, and slowly adding 98% industrial sulphuric acid reacts to pH value 3.5; The mensuration lead content is 18.59kg; The MnS that adds 40 kilogram 60%, 87 ℃ of stirring reactions 5 hours, press filtration separates; Filter cake reclaims valuable element, and clear filtrate gets into next-step operation.
Above-mentioned filtrating is added 27.5% industrial hydrogen peroxide in the ratio of every cubic metre of 2.5L, stir 15 minutes post-heating to boiling, and kept gentle boil 30 minutes, stop heating, solid-liquid separation, filter residue is abandoned, and the clear filtrate evaporation obtains high purity manganese sulfate sample 3
#
Embodiment 4
In 5000 liters of uncovered lass lining reactors, add 4000 liters of deionized waters earlier, 700 kilograms of purity of adding are 99% manganese metal under stirring, and slowly adding 98% industrial sulphuric acid reacts to pH value 3.5; The mensuration lead content is 19.04kg; The MnS that adds 40 kilogram 60%, 100 ℃ of stirring reactions 6 hours, press filtration separates; Filter cake reclaims valuable element, and clear filtrate gets into next-step operation.
Above-mentioned filtrating is added 27.5% industrial hydrogen peroxide in the ratio of every cubic metre of 2.5L, stir 15 minutes post-heating to boiling, and kept gentle boil 30 minutes, stop heating, solid-liquid separation, filter residue is abandoned, and the clear filtrate evaporation obtains high purity manganese sulfate sample 4
#
Embodiment 5
In 5000 liters of uncovered lass lining reactors, add 4000 liters of deionized waters earlier, 300 kilograms of purity of adding are 99% manganese metal under stirring, and slowly adding 98% industrial sulphuric acid reacts to pH value 4.0; The mensuration lead content is 8.68kg; The MnS that adds 40 kilogram 60%, 70 ℃ of stirring reactions 4 hours, press filtration separates; Filter cake reclaims valuable element, and clear filtrate gets into next-step operation.
Above-mentioned filtrating is added 27.5% industrial hydrogen peroxide in the ratio of every cubic metre of 2.5L, stir 15 minutes post-heating to boiling, and kept gentle boil 30 minutes, stop heating, solid-liquid separation, filter residue is abandoned, and the clear filtrate evaporation obtains high purity manganese sulfate sample 5
#
Effect assessment
The result of embodiment and prior art relatively sees the following form shown in 3.
Embodiment gained sample result is analyzed like following table:
| Project | 1 # | 2 # | 3 # | 4 # | 5 # |
| Mn % | 32.24 | 32.18 | 32.27 | 32.15 | 32.10 |
| K ppm | 4.3 | 3.9 | 3.4 | 5.1 | 5.3 |
| Na ppm | 5.8 | 6.1 | 6.0 | 7.3 | 7.8 |
| Ca?ppm | 17.2 | 18.4 | 17.2 | 19.9 | 20.4 |
| Mg ppm | 8.6 | 9.1 | 9.4 | 10.0 | 10.7 |
| Fe ppm | 0.72 | 0.61 | 0.47 | 0.78 | 0.88 |
| Cu?ppm | ND (not detecting) | ND | ND | ND | ND |
| Co?ppm | ND | ND | ND | ND | ND |
| Ni ppm | ND | ND | ND | ND | ND |
| Pb ppm | ND | ND | ND | ND | ND |
| As ppm | ND | ND | ND | ND | ND |
| Zn?ppm | ND | ND | ND | ND | ND |
| Cd ppm | ND | ND | ND | ND | ND |
| Sr?ppm | ND | ND | ND | ND | ND |
| Se ppm | ND | ND | ND | ND | ND |
| Cr?ppm | ND | ND | ND | ND | ND |
Measuring method:
What the present invention detected that the content of above-mentioned impurity all selects for use is the ordinary method of this area, and those skilled in the art are easy to from standard, find.
The method that detects lead content in the solution is: inductively coupled plasma atomic emission spectrometry, and measure and use instrument to be IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, U.S. power & light company system.
Interpretation of result:
Can be drawn by above comparison, the foreign matter content of high-purity sulphuric acid manganese product is all very low in the various embodiments of the present invention, Cu, Co, Ni; Pb, As, Zn, Cd; Sr, Se, the content of Cr all is lower than the value of detecting, K; Na, the content of Mg are all less than 10ppm, and the content of Ca is all less than 20ppm, and the content of Fe all is lower than 1ppm.Though purity of the present invention is not very high, water-content is the principal element that influences its purity, and this can not impact its application as the lithium ion battery manganese cathode material.And wherein, preferred prescription is embodiment 1,2,3,4, and preferred prescription is embodiment 1,2; 3, most preferred prescription is 1, and its K content has reached 4.3ppm, and Na reaches 5.8ppm, and Ca reaches 17.2ppm, and Mg reaches 8.6ppm; Fe reaches 0.72ppm, Cu, Co, Ni, Pb, As; Zn, Cd, Sr, Se, metal contents such as Cr all are lower than the minimum value of the detecting 0.1ppm of detecting instrument inductively coupled plasma atomic emission spectrum (ICP-AES), are trace.
Claims (10)
1. a method for preparing manganous sulfate is characterized in that, may further comprise the steps:
A puts into manganese metal earlier in deionized water, in this mixture, slowly add sulfuric acid reaction to pH value=3.5～4.0, obtains solution; PH value preferred 3.5;
B adds excessive manganese sulfide in steps A gained solution, in 70～100 ℃ of stirring reactions 4～6 hours, and solid-liquid separation;
C adds hydrogen peroxide in the solution of step B solid-liquid separation gained, the post-heating that stirs is to boiling solid-liquid separation;
D obtains manganese sulfate product with the solution evaporation of step C solid-liquid separation gained.
2. the method for claim 1 is characterized in that, the manganese metal of said steps A is the electrolytic metal Mn of weight percentage more than 99%.
3. according to claim 1 or claim 2 method is characterized in that the manganese metal of said steps A and the ratio of deionized water are 75～175g/L water, preferred 125～163g/L water.
4. like each described method of claim 1～3, it is characterized in that the reaction of said step B adds 3 times the manganese sulfide of the mole number of sulphur more than or equal to mole number plumbous in the solution.
5. like each described method of claim 1～4, it is characterized in that the temperature of reaction of said step B is 85～90 ℃.
6. like each described method of claim 1～5, it is characterized in that the temperature of reaction of said step B is 87 ℃.
7. like each described method of claim 1～6, it is characterized in that the reaction times of said step B is 4.5～5.5 hours, preferred 5 hours.
8. like each described method of claim 1～7, it is characterized in that the add-on of the hydrogen peroxide of said step B is 1.0～3.6L/m
3, preferred 1.7～3.4L/m
3
9. the manganese sulfate product for preparing of a utilization such as each described method of claim 1～8.
10. high-purity sulphuric acid manganese product as claimed in claim 9 is characterized in that, the heavy metal content of said manganese sulfate product is all less than 0.1ppm, and K, Na, Mg content are lower than 10ppm, and Fe content is lower than 1ppm, and Ca content is lower than 20ppm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011298A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for production of high purity manganese sulfate by using metal manganese sheet as raw material |
| CN103435103A (en) * | 2013-08-15 | 2013-12-11 | 贵州红星发展股份有限公司 | High-purity manganous nitrate and preparation method thereof |
| CN105110300A (en) * | 2015-07-24 | 2015-12-02 | 长沙矿冶研究院有限责任公司 | Method for extracting manganese and sulfur from composite manganese mine containing manganese sulfide |
| CN110316760A (en) * | 2019-07-29 | 2019-10-11 | 佛山西陇化工有限公司 | A kind of preparation method of ultra-fine manganese carbonate |
| CN114835167A (en) * | 2022-04-13 | 2022-08-02 | 贵州大龙汇成新材料有限公司 | Process for producing manganese sulfate by using poor manganese ore |
| CN114855220A (en) * | 2022-04-13 | 2022-08-05 | 贵州大龙汇成新材料有限公司 | Method for preparing high-purity manganese by using poor manganese ore |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103011298A (en) * | 2012-12-07 | 2013-04-03 | 中信大锰矿业有限责任公司 | Method for production of high purity manganese sulfate by using metal manganese sheet as raw material |
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| CN103435103B (en) * | 2013-08-15 | 2016-01-20 | 贵州红星发展股份有限公司 | High pure nitric acid manganese and preparation method thereof |
| CN105110300A (en) * | 2015-07-24 | 2015-12-02 | 长沙矿冶研究院有限责任公司 | Method for extracting manganese and sulfur from composite manganese mine containing manganese sulfide |
| CN105110300B (en) * | 2015-07-24 | 2017-07-07 | 长沙矿冶研究院有限责任公司 | The method that a kind of compound manganese ore of Containing Sulfur manganese extracts manganese and sulphur |
| CN110316760A (en) * | 2019-07-29 | 2019-10-11 | 佛山西陇化工有限公司 | A kind of preparation method of ultra-fine manganese carbonate |
| CN114835167A (en) * | 2022-04-13 | 2022-08-02 | 贵州大龙汇成新材料有限公司 | Process for producing manganese sulfate by using poor manganese ore |
| CN114855220A (en) * | 2022-04-13 | 2022-08-05 | 贵州大龙汇成新材料有限公司 | Method for preparing high-purity manganese by using poor manganese ore |
| CN114855220B (en) * | 2022-04-13 | 2024-02-13 | 贵州大龙汇成新材料有限公司 | Method for preparing high-purity manganese from lean manganese ores |
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