CN115571919A - Method for removing calcium and magnesium ions in production of high-purity manganese sulfate - Google Patents
Method for removing calcium and magnesium ions in production of high-purity manganese sulfate Download PDFInfo
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- CN115571919A CN115571919A CN202211202775.8A CN202211202775A CN115571919A CN 115571919 A CN115571919 A CN 115571919A CN 202211202775 A CN202211202775 A CN 202211202775A CN 115571919 A CN115571919 A CN 115571919A
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 116
- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 115
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 115
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000011575 calcium Substances 0.000 title claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001424 calcium ion Inorganic materials 0.000 title claims abstract description 22
- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 20
- 238000003825 pressing Methods 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000012066 reaction slurry Substances 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 230000002035 prolonged effect Effects 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- OKVGBKABWITJQA-UHFFFAOYSA-L manganese dithionate Chemical compound [Mn+2].[O-]S(=O)(=O)S([O-])(=O)=O OKVGBKABWITJQA-UHFFFAOYSA-L 0.000 abstract description 4
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 3
- 239000002918 waste heat Substances 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 208000005903 Manganese Poisoning Diseases 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 208000007443 Neurasthenia Diseases 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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Abstract
The invention belongs to the technical field of high-purity manganese sulfate production, and discloses a method for removing calcium and magnesium ions in the production of high-purity manganese sulfate, which adopts the preparation of crude manganese sulfate; dispersing crude manganese sulfate in water to obtain a manganese sulfate solution; the crude manganese sulfate comprises calcium and magnesium elements; and filtering and separating the precipitated manganese sulfate crystals from the solution, reserving the filtrate, and drying the manganese sulfate crystals by using an oven to obtain the high-purity manganese sulfate crystals. According to the invention, the crude manganese sulfate preparation method adopts a desulfurization-vulcanization-circulation process, so that manganese forms a solid and is separated from a system, the problem of influence of manganese dithionate in a manganese sulfate solution is solved, and the process cost is reduced; meanwhile, the stirrer control method avoids the problems that vibration and noise are easy to generate due to synchronous rotation of the motor and the fan, abrasion of the fan is accelerated, and the service life of the fan is seriously influenced.
Description
Technical Field
The invention belongs to the technical field of high-purity manganese sulfate production, and particularly relates to a method for removing calcium and magnesium ions in the production of high-purity manganese sulfate.
Background
Manganese sulfate, an inorganic compound of the formula MnSO4, is commonly used as a microanalytical reagent, a mordant, and a paint drier. Inhalation, ingestion or percutaneous absorption are harmful and have an irritant effect. The long-term inhalation of the product can cause chronic manganese poisoning, and early stage mainly comprises neurasthenia syndrome and nerve dysfunction, and late stage paralysis agitans syndrome. Is harmful to the environment and can cause pollution to water. The product is non-inflammable and irritant; however, the existing method for removing calcium and magnesium ions in the production of high-purity manganese sulfate has the defects of high cost of the manganese sulfate preparation process; meanwhile, the fan in the adopted stirrer stops rotating along with the motor, the internal temperature of the motor is high at the moment, the internal coil of the motor is easy to damage, the rotating speed of the fan is always synchronous with that of the motor, when the motor runs at a high speed, the fan is easy to vibrate, and the generated noise is large; reducing the service life of the motor.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) The method for removing calcium and magnesium ions in the existing high-purity manganese sulfate production has the advantage of higher cost of the manganese sulfate preparation process.
(2) The fan in the adopted stirrer stops rotating along with the motor, the internal temperature of the motor is high at the moment, the coil in the motor is easy to damage, the rotating speed of the fan is always synchronous with the motor, when the motor runs at a high speed, the fan is easy to vibrate, and the generated noise is large; reducing the service life of the motor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for removing calcium and magnesium ions in the production of high-purity manganese sulfate.
The invention is realized in such a way that the method for removing calcium and magnesium ions in the production of high-purity manganese sulfate comprises the following steps:
step one, preparing crude manganese sulfate; dispersing the crude manganese sulfate in water to obtain a manganese sulfate solution; the crude manganese sulfate comprises calcium and magnesium elements;
adding an organic solvent into the manganese sulfate solution, continuously mechanically stirring the mixed solution at the temperature of 31 ℃ by using a stirrer to quickly separate manganese sulfate crystals, and standing at room temperature after the manganese sulfate crystals are separated; the organic solvent is any one of propanol, butanol, acetone and propiophenone; the volume ratio of the manganese sulfate solution to the organic solvent is 1.3-6;
thirdly, filtering and separating the precipitated manganese sulfate crystals from the solution, reserving the filtrate for later use, and drying the manganese sulfate crystals by using an oven to obtain high-purity manganese sulfate crystals; the filtrate was subjected to distillation to separate the organic solvent therefrom.
Further, the stirring conditions of the stirrer are as follows: the speed is 3010 rpm, the time is 4 hours, and the standing time at room temperature is 20 hours.
Further, the drying condition is 271 ℃ for 50 hours.
Further, the preparation method of the crude manganese sulfate comprises the following steps:
(1) Taking modified manganese dioxide ore powder as a raw material, wherein 91 percent of the modified manganese dioxide ore powder can pass through a 100-mesh sieve, preparing the modified manganese dioxide ore powder into slurry with the solid content of 31 percent by weight by using an ammonium sulfate solution, and carrying out multi-stage countercurrent gas-liquid reaction on the slurry and sulfur-containing flue gas until the MnO2 content in the slurry is less than 2 percent by weight; after the reaction is finished, neutralizing the slurry until the pH value is 7, performing filter pressing separation, and performing the next operation on the obtained filtrate;
(2) Introducing hydrogen sulfide gas into the filtrate obtained by desulfurization to carry out a vulcanization reaction, controlling the pH value at the end point of the reaction to be 5, carrying out filter pressing separation, carrying out the next operation on the obtained filtrate, acidifying the filter cake, returning the hydrogen sulfide generated by acidification to the vulcanization reaction, and using the manganese sulfate solution generated by acidification to produce a manganese sulfate product; and obtaining crude manganese sulfate.
Further, the maintenance ammonium sulfate concentration is more than 151g/L;
preparing modified manganese dioxide ore into slurry with the solid content of 26 percent by weight;
in the modified manganese dioxide ore, the manganese content is 16-46% by weight percentage;
reacting until the MnO2 in the slurry is less than 1.6 percent by weight;
the multistage countercurrent gas-liquid reaction is a three-stage countercurrent gas-liquid reaction, and specifically comprises the following steps:
firstly, introducing sulfur-containing flue gas into the first stage of a countercurrent gas-liquid reaction device, controlling the gas velocity to be less than or equal to 1.6m/sec and the gas-liquid ratio to be 9-13L/m 3 ；
Adding modified manganese dioxide slurry into the third stage of the countercurrent gas-liquid reaction device, and controlling the modified manganese dioxide slurry to flow in a reverse direction relative to the sulfur-containing flue gas;
the three stages of the three-stage countercurrent gas-liquid reaction device respectively carry out self circulation at the same time;
the first stage reaction slurry is continuously supplemented from the second stage, and the third stage reaction slurry is continuously supplemented to the second stage reaction slurry;
the newly prepared modified manganese dioxide slurry is continuously supplemented to the third stage;
after the reaction is finished, the slurry enters a separation process from the first stage, and the desulfurized flue gas is discharged from the third stage of the reaction device;
stirring and washing a filter cake obtained by filter pressing separation for 3 hours by using tap water with the temperature of 67 ℃, wherein the weight ratio of the material to the water is 1-2, and then pressing and filter pressing;
washing residues obtained after filter pressing separation, wherein the washing water can be used for preparing modified manganese dioxide ore slurry.
Further, the stirrer control method comprises the following steps:
1) Configuring working parameters of a stirrer, and sending a fan starting control signal to the fan when a stirring starting instruction is obtained, so that the fan runs at a preset fan rotating speed value; sending a motor starting control signal to the motor to enable the motor to operate at a preset motor rotating speed value within a set stirring time; wherein the start stirring instruction comprises the stirring time;
2) After the stirring time is over, sending a motor stop control signal to the motor to stop the motor; and after a preset first delay time, sending a fan stop control signal to the fan to stop the fan.
Further, the step of sending a motor start control signal to the motor to enable the motor to operate at a preset motor rotating speed value within a set stirring time specifically includes:
and when a stirring starting instruction is obtained and a preset second delay time duration elapses, sending a motor starting control signal to the motor, so that the motor operates at a preset motor rotating speed value within a preset stirring time.
Further, the specific step of enabling the motor to operate at a preset motor rotating speed value within a preset stirring time is as follows:
enabling the motor to run at a first motor rotating speed value at a constant speed within set stirring time; the stirring starting command comprises the first motor rotating speed value.
Further, the control method of the agitator further includes:
when a rotating speed switching instruction is obtained within the stirring time, a rotating speed switching control signal is sent to the motor, so that the motor runs at a second motor rotating speed value at a constant speed; the rotating speed switching instruction comprises the rotating speed value of the second motor.
Further, the stirring time comprises N consecutive time periods; a motor rotating speed value is preset in each time period; the motor rotating speed value preset in at least one time period is different from the motor rotating speed values set in other time periods;
the stirring starting instruction comprises a stirring working mode selected from M preset stirring working modes; each stirring working mode is respectively configured with the motor rotating speed value of each time period in the N continuous time periods;
the control method of the agitator further includes:
when a stirring prolonging instruction is obtained within the stirring time, the stirring time needing to be prolonged is increased to the originally set stirring time so as to update the stirring time; the extended stirring instruction comprises the time length of stirring needing to be extended;
and when the originally set stirring time is over, acquiring the current motor rotating speed value, and sending a rotating speed maintaining signal to the motor, so that the motor runs at the current motor rotating speed value at a constant speed within the time period needing to be stirred.
In combination with the technical solutions and the technical problems to be solved, please analyze the advantages and positive effects of the technical solutions to be protected in the present invention from the following aspects:
first, aiming at the technical problems existing in the prior art and the difficulty in solving the problems, the technical problems to be solved by the technical scheme of the present invention are closely combined with results, data and the like in the research and development process, and some creative technical effects are brought after the problems are solved. The specific description is as follows:
according to the invention, the crude manganese sulfate preparation method adopts a desulfurization-vulcanization-circulation process, so that manganese forms a solid and is separated from the system, the problem of influence of manganese dithionate in a manganese sulfate solution is solved, and the process cost is reduced; meanwhile, the blower is delayed from stopping the motor by a stirrer control method, so that the waste heat of the motor is dissipated, the damage to an inner coil of the motor caused by the waste heat is avoided, and the service life of the motor is prolonged; the problem of because motor and fan synchronous revolution lead to producing vibrations and noise easily to and make fan wearing and tearing accelerate, seriously influence the life of fan is avoided.
Secondly, considering the technical scheme as a whole or from the perspective of products, the technical effect and advantages of the technical scheme to be protected by the invention are specifically described as follows:
according to the invention, the crude manganese sulfate preparation method adopts a desulfurization-vulcanization-circulation process, so that manganese forms a solid and is separated from the system, the problem of influence of manganese dithionate in a manganese sulfate solution is solved, and the process cost is reduced; meanwhile, the blower is delayed from stopping the motor by a stirrer control method, so that the waste heat of the motor is dissipated, the damage to an inner coil of the motor caused by the waste heat is avoided, and the service life of the motor is prolonged; the problem that the motor and the fan rotate synchronously, vibration and noise are easy to generate, abrasion of the fan is accelerated, and the service life of the fan is seriously influenced is solved.
Drawings
FIG. 1 is a flow chart of a method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to an embodiment of the invention.
FIG. 2 is a flow chart of a method for preparing crude manganese sulfate according to an embodiment of the present invention.
Fig. 3 is a flowchart of a method for controlling a blender according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
1. Illustrative embodiments are explained. This section is an explanatory embodiment expanding on the claims so as to fully understand how the present invention is embodied by those skilled in the art.
As shown in FIG. 1, the invention provides a method for removing calcium and magnesium ions in the production of high-purity manganese sulfate, which comprises the following steps:
s101, preparing crude manganese sulfate; dispersing the crude manganese sulfate in water to obtain a manganese sulfate solution; the crude manganese sulfate comprises calcium and magnesium elements;
s102, adding an organic solvent into a manganese sulfate solution, continuously mechanically stirring the mixed solution at the temperature of 31 ℃ by using a stirrer to quickly separate manganese sulfate crystals out, and standing at room temperature after the manganese sulfate crystals are separated out; the organic solvent is any one of propanol, butanol, acetone and propiophenone; the volume ratio of the manganese sulfate solution to the organic solvent is 1.3-6;
s103, filtering and separating the precipitated manganese sulfate crystals from the solution, reserving the filtrate, and drying the manganese sulfate crystals by using an oven to obtain high-purity manganese sulfate crystals; the filtrate was subjected to distillation to separate the organic solvent therefrom.
The stirring conditions of the stirrer provided by the invention are as follows: the speed is 3010 rpm, the time is 4 hours, and the standing time at room temperature is 20 hours.
The drying condition provided by the invention is 271 ℃ and the time is 50 hours.
As shown in fig. 2, the preparation method of the crude manganese sulfate provided by the invention is as follows:
s201, taking modified manganese dioxide ore powder as a raw material, enabling 91% of the modified manganese dioxide ore powder to pass through a 100-mesh sieve, preparing the modified manganese dioxide ore powder into slurry with the solid content of 31% by weight by using an ammonium sulfate solution, and carrying out multi-stage countercurrent gas-liquid reaction on the slurry and sulfur-containing flue gas until the MnO2 content in the slurry is less than 2% by weight; after the reaction is finished, neutralizing the slurry until the pH value is 7, performing filter pressing separation, and performing the next operation on the obtained filtrate;
s202, introducing hydrogen sulfide gas into the filtrate obtained by desulfurization to carry out a vulcanization reaction, controlling the pH value at the end of the reaction to be 5, carrying out filter pressing separation, carrying out the next operation on the obtained filtrate, acidifying the filter cake, returning the hydrogen sulfide generated by acidification to the vulcanization reaction, and using the manganese sulfate solution generated by acidification to produce a manganese sulfate product; obtaining crude manganese sulfate.
The concentration of the ammonium sulfate is maintained to be more than 151g/L;
preparing modified manganese dioxide ore into slurry with the solid content of 26 percent by weight;
in the modified manganese dioxide ore, the manganese content is 16-46% by weight percentage;
reacting until the MnO2 in the slurry is less than 1.6 percent by weight;
the multistage countercurrent gas-liquid reaction is a three-stage countercurrent gas-liquid reaction, and specifically comprises the following steps:
firstly, introducing sulfur-containing flue gas into the first stage of a countercurrent gas-liquid reaction device, controlling the gas velocity to be less than or equal to 1.6m/sec and the gas-liquid ratio to be 9-13L/m 3 ；
Adding modified manganese dioxide slurry into the third stage of the countercurrent gas-liquid reaction device, and controlling the modified manganese dioxide slurry to flow reversely relative to the sulfur-containing flue gas;
the three stages of the three-stage countercurrent gas-liquid reaction device respectively carry out self circulation at the same time;
the first stage reaction slurry is continuously supplemented from the second stage, and the third stage reaction slurry is continuously supplemented to the second stage reaction slurry;
newly prepared modified manganese dioxide slurry is continuously supplemented to the third stage;
after the reaction is finished, the slurry enters a separation process from the first stage, and the desulfurized flue gas is discharged from the third stage of the reaction device;
stirring and washing a filter cake obtained by the filter-pressing separation for 3 hours by using tap water at the temperature of 67 ℃, wherein the weight ratio of the material to the water is 1-2, and then pressing and filter-pressing;
washing residues obtained after filter pressing separation, wherein the washing water can be used for preparing modified manganese dioxide ore slurry.
As shown in fig. 3, the control method of the agitator provided by the present invention is as follows:
s301, configuring working parameters of a stirrer, and sending a fan starting control signal to the fan when a stirring starting instruction is obtained, so that the fan runs at a preset fan rotating speed value; sending a motor starting control signal to the motor to enable the motor to operate at a preset motor rotating speed value within a set stirring time; wherein the start stirring instruction comprises the stirring time;
s302, after the stirring time is over, a motor stop control signal is sent to the motor, so that the motor stops running; and after a preset first delay time, sending a fan stop control signal to the fan to stop the fan.
The invention provides a method for sending a motor starting control signal to a motor to enable the motor to run at a preset motor rotating speed value within a set stirring time, which comprises the following steps:
and when a stirring starting instruction is acquired and a preset second delay time duration elapses, sending a motor starting control signal to the motor, so that the motor operates at a preset motor rotating speed value within a preset stirring time.
The invention provides a method for enabling a motor to run at a preset motor rotating speed value within a preset stirring time, which comprises the following steps:
enabling the motor to run at a constant speed according to a first motor rotating speed value within set stirring time; the start stirring instruction includes the first motor rotation speed value.
The control method of the stirrer provided by the invention further comprises the following steps:
when a rotating speed switching instruction is obtained within the stirring time, a rotating speed switching control signal is sent to the motor, so that the motor runs at a second motor rotating speed value at a constant speed; the rotating speed switching instruction comprises the rotating speed value of the second motor.
The stirring time provided by the invention comprises N continuous time periods; a motor rotating speed value is preset in each time period; the motor rotating speed value preset in at least one time period is different from the motor rotating speed values set in other time periods;
the stirring starting instruction comprises a stirring working mode selected from M preset stirring working modes; each stirring working mode is respectively configured with a motor rotating speed value of each time period in the N continuous time periods;
the control method of the agitator further includes:
when a stirring prolonging instruction is obtained within the stirring time, the stirring time needing to be prolonged is increased to the original set stirring time so as to update the stirring time; the extended stirring instruction comprises the time length of stirring needing to be extended;
and when the originally set stirring time is over, acquiring the current motor rotating speed value, and sending a rotating speed maintaining signal to the motor, so that the motor runs at the current motor rotating speed value at a constant speed within the time period needing to be stirred.
2. Application examples. In order to prove the creativity and the technical value of the technical scheme of the invention, the part is the application example of the technical scheme of the claims on specific products or related technologies.
Example 1:
the invention provides a method for removing calcium and magnesium ions in the production of high-purity manganese sulfate, which comprises the following steps:
s101, preparing crude manganese sulfate; dispersing the crude manganese sulfate in water to obtain a manganese sulfate solution; the crude manganese sulfate comprises calcium and magnesium elements;
s102, adding an organic solvent into a manganese sulfate solution, continuously mechanically stirring the mixed solution at the temperature of 31 ℃ by using a stirrer to quickly separate manganese sulfate crystals out, and standing at room temperature after the manganese sulfate crystals are separated out; the organic solvent is any one of propanol, butanol, acetone and propiophenone; the volume ratio of the manganese sulfate solution to the organic solvent is 1;
s103, filtering and separating the precipitated manganese sulfate crystals from the solution, reserving the filtrate, and drying the manganese sulfate crystals by using an oven to obtain high-purity manganese sulfate crystals; the filtrate was subjected to distillation to separate the organic solvent therefrom.
The stirring conditions of the stirrer provided by the invention are as follows: the speed is 3010 rpm, the time is 4 hours, and the standing time at room temperature is 20 hours.
The drying condition provided by the invention is 271 ℃ and the time is 50 hours.
Example 2:
the invention provides a method for removing calcium and magnesium ions in the production of high-purity manganese sulfate, which comprises the following steps:
s101, preparing crude manganese sulfate; dispersing the crude manganese sulfate in water to obtain a manganese sulfate solution; the crude manganese sulfate comprises calcium and magnesium elements;
s102, adding an organic solvent into a manganese sulfate solution, continuously and mechanically stirring the mixed solution at the temperature of 31 ℃ through a stirrer to quickly separate manganese sulfate crystals out, and standing at room temperature after the manganese sulfate crystals are separated out; the organic solvent is any one of propanol, butanol, acetone and propiophenone; the volume ratio of the manganese sulfate solution to the organic solvent is 1;
s103, filtering and separating the precipitated manganese sulfate crystals from the solution, reserving the filtrate, and drying the manganese sulfate crystals by using an oven to obtain high-purity manganese sulfate crystals; the filtrate was subjected to distillation to separate the organic solvent therefrom.
The stirring conditions of the stirrer provided by the invention are as follows: the speed is 3010 rpm, the time is 4 hours, and the standing time at room temperature is 20 hours.
The drying condition provided by the invention is 271 ℃ and the time is 50 hours.
3. Evidence of the relevant effects of the examples. The embodiment of the invention achieves some positive effects in the process of research and development or use, and has great advantages compared with the prior art, and the following contents are described by combining data, diagrams and the like in the test process.
The following is a high-purity manganese sulfate product produced by the method, and the detection data of the product is as follows through the detection of a quality detection center:
the product name is as follows: high-purity manganese sulfate;
the detection basis is as follows: reference HG2936-1999; the results of the measurements are given in Table 1 below.
TABLE 1
| Inspection item | Unit of | Test results |
| Ca | ％ | 0.0003 |
| Mg | ％ | 0.0020 |
| Fe | ％ | 0.0002 |
| Zn | ％ | 0.0020 |
| Cr | ％ | 0.0003 |
| Cd | ％ | 0.0001 |
The above table illustrates: the data detected in the table above show the depth of each impurity metal ion in the high-purity manganese sulfate, and the data in the table above show that the high-purity manganese sulfate product produced by the method meets the quality requirements of battery-grade manganese sulfate and can be used as a manganese source of a lithium ion battery anode material.
According to the invention, the crude manganese sulfate preparation method adopts a desulfurization-vulcanization-circulation process, so that manganese forms a solid and is separated from a system, the problem of influence of manganese dithionate in a manganese sulfate solution is solved, and the process cost is reduced; meanwhile, the blower is delayed from stopping the motor by a stirrer control method, so that the waste heat of the motor is dissipated, the damage to an inner coil of the motor caused by the waste heat is avoided, and the service life of the motor is prolonged; the problem that the motor and the fan rotate synchronously, vibration and noise are easy to generate, abrasion of the fan is accelerated, and the service life of the fan is seriously influenced is solved.
The above description is only for the purpose of illustrating the embodiments of the present invention, and the scope of the present invention should not be limited thereto, and any modifications, equivalents and improvements made by those skilled in the art within the technical scope of the present invention as disclosed in the present invention should be covered by the scope of the present invention.
Claims (10)
1. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate is characterized by comprising the following steps of:
step one, preparing crude manganese sulfate; dispersing the crude manganese sulfate in water to obtain a manganese sulfate solution; the crude manganese sulfate comprises calcium and magnesium elements;
adding an organic solvent into the manganese sulfate solution, continuously mechanically stirring the mixed solution at the temperature of 31 ℃ by using a stirrer to quickly separate manganese sulfate crystals, and standing at room temperature after the manganese sulfate crystals are separated; the organic solvent is any one of propanol, butanol, acetone and propiophenone; the volume ratio of the manganese sulfate solution to the organic solvent is 1.3-6;
thirdly, filtering and separating the precipitated manganese sulfate crystals from the solution, reserving the filtrate for later use, and drying the manganese sulfate crystals by using an oven to obtain high-purity manganese sulfate crystals; the filtrate was subjected to distillation to separate the organic solvent therefrom.
2. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 1, wherein the stirring conditions of the stirrer are as follows: the speed is 3010 rpm, the time is 4 hours, and the standing time at room temperature is 20 hours.
3. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 1, wherein the drying condition is 271 ℃ and the time is 50 hours.
4. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 1, wherein the crude manganese sulfate is prepared by the following steps:
(1) Taking modified manganese dioxide ore powder as a raw material, wherein 91 percent of the modified manganese dioxide ore powder can pass through a 100-mesh sieve, preparing the modified manganese dioxide ore powder into slurry with the solid content of 31 percent by weight by using an ammonium sulfate solution, and carrying out multi-stage countercurrent gas-liquid reaction on the slurry and sulfur-containing flue gas until the MnO2 content in the slurry is less than 2 percent by weight; after the reaction is finished, neutralizing the slurry until the pH value is 7, performing filter pressing separation, and performing the next operation on the obtained filtrate;
(2) Introducing hydrogen sulfide gas into the filtrate obtained by desulfurization to carry out a vulcanization reaction, controlling the pH value at the end point of the reaction to be 5, carrying out filter pressing separation, carrying out the next operation on the obtained filtrate, acidifying the filter cake, returning the hydrogen sulfide generated by acidification to the vulcanization reaction, and using the manganese sulfate solution generated by acidification to produce a manganese sulfate product; obtaining crude manganese sulfate.
5. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 4, wherein the concentration of ammonium sulfate is maintained to be higher than 151g/L;
preparing modified manganese dioxide ore into slurry with the solid content of 26 percent by weight;
in the modified manganese dioxide ore, the manganese content is 16-46% by weight percentage;
reacting until the MnO2 in the slurry is less than 1.6 percent by weight;
the multistage countercurrent gas-liquid reaction is a three-stage countercurrent gas-liquid reaction, and specifically comprises the following steps:
firstly, introducing sulfur-containing flue gas into the first stage of a countercurrent gas-liquid reaction device, controlling the gas velocity to be less than or equal to 1.6m/sec and the gas-liquid ratio to be 9-13L/m 3 ；
Adding modified manganese dioxide slurry into the third stage of the countercurrent gas-liquid reaction device, and controlling the modified manganese dioxide slurry to flow in a reverse direction relative to the sulfur-containing flue gas;
the three stages of the three-stage countercurrent gas-liquid reaction device respectively carry out self circulation at the same time;
the first stage reaction slurry is continuously supplemented from the second stage, and the third stage reaction slurry is continuously supplemented to the second stage reaction slurry;
newly prepared modified manganese dioxide slurry is continuously supplemented to the third stage;
after the reaction is finished, the slurry enters a separation process from the first stage, and the desulfurized flue gas is discharged from the third stage of the reaction device;
stirring and washing a filter cake obtained by filter pressing separation for 3 hours by using tap water with the temperature of 67 ℃, wherein the weight ratio of the material to the water is 1-2, and then pressing and filter pressing;
washing residues obtained after filter pressing separation, wherein the washing water can be used for preparing modified manganese dioxide ore slurry.
6. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 1, wherein the stirrer control method comprises the following steps:
1) Configuring working parameters of a stirrer, and sending a fan starting control signal to the fan when a stirring starting instruction is obtained, so that the fan runs at a preset fan rotating speed value; sending a motor starting control signal to the motor to enable the motor to operate at a preset motor rotating speed value within a set stirring time; wherein the start stirring instruction comprises the stirring time;
2) After the stirring time is over, sending a motor stop control signal to the motor to stop the motor; and after a preset first delay time, sending a fan stop control signal to the fan to stop the fan.
7. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 6, wherein the step of sending a motor start control signal to the motor to enable the motor to operate at a preset motor speed value within a set stirring time specifically comprises the following steps:
and when a stirring starting instruction is obtained and a preset second delay time duration elapses, sending a motor starting control signal to the motor, so that the motor operates at a preset motor rotating speed value within a preset stirring time.
8. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 6, wherein the step of operating the motor at a preset motor rotating speed value within a preset stirring time is as follows:
enabling the motor to run at a first motor rotating speed value at a constant speed within set stirring time; the start stirring instruction includes the first motor rotation speed value.
9. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 6, wherein the method for controlling the stirrer further comprises the following steps:
when a rotating speed switching instruction is obtained within the stirring time, a rotating speed switching control signal is sent to the motor, so that the motor runs at a second motor rotating speed value at a constant speed; the rotating speed switching instruction comprises the rotating speed value of the second motor.
10. The method for removing calcium and magnesium ions in the production of high-purity manganese sulfate according to claim 6, wherein the stirring time comprises N consecutive time periods; a motor rotating speed value is preset in each time period; the motor rotating speed value preset in at least one time period is different from the motor rotating speed values set in other time periods;
the stirring starting instruction comprises a stirring working mode selected from M preset stirring working modes; each stirring working mode is respectively configured with the motor rotating speed value of each time period in the N continuous time periods;
the control method of the agitator further includes:
when a stirring prolonging instruction is obtained within the stirring time, the stirring time needing to be prolonged is increased to the originally set stirring time so as to update the stirring time; the extended stirring instruction comprises the time length of stirring needing to be extended;
and when the originally set stirring time is over, acquiring the current motor rotating speed value, and sending a rotating speed maintaining signal to the motor, so that the motor runs at the current motor rotating speed value at a constant speed within the time period needing to be stirred.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104645815A (en) * | 2015-01-26 | 2015-05-27 | 贵州红星发展大龙锰业有限责任公司 | Cycling separation method for manganous dithionate in desulfurized liquid |
| CN105326411A (en) * | 2015-12-11 | 2016-02-17 | 佛山市顺德区巨天电器有限公司 | Stirrer and control method and controller thereof |
| CN110642297A (en) * | 2019-09-04 | 2020-01-03 | 广西大学 | Method for removing calcium and magnesium ions in manganese sulfate solution through low-temperature crystallization |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104645815A (en) * | 2015-01-26 | 2015-05-27 | 贵州红星发展大龙锰业有限责任公司 | Cycling separation method for manganous dithionate in desulfurized liquid |
| CN105326411A (en) * | 2015-12-11 | 2016-02-17 | 佛山市顺德区巨天电器有限公司 | Stirrer and control method and controller thereof |
| CN110642297A (en) * | 2019-09-04 | 2020-01-03 | 广西大学 | Method for removing calcium and magnesium ions in manganese sulfate solution through low-temperature crystallization |
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