CN113862495A - Preparation method of high-purity manganese - Google Patents
Preparation method of high-purity manganese Download PDFInfo
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- CN113862495A CN113862495A CN202111161331.XA CN202111161331A CN113862495A CN 113862495 A CN113862495 A CN 113862495A CN 202111161331 A CN202111161331 A CN 202111161331A CN 113862495 A CN113862495 A CN 113862495A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
- B24C1/08—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for polishing surfaces, e.g. smoothing a surface by making use of liquid-borne abrasives
- B24C1/086—Descaling; Removing coating films
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/04—Refining by applying a vacuum
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
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Abstract
The invention relates to a preparation method of high-purity manganese, which comprises the following steps: (1) obtaining primary manganese by vacuum distillation; (2) carrying out sand blasting treatment on the primary manganese to obtain sand blasting manganese; (3) and carrying out acid washing treatment on the sand-blasting manganese to obtain the high-purity manganese. The preparation method provided by the invention has the advantages of simple flow, low production cost, high yield and easiness in production monitoring, can effectively reduce the LPC value of high-purity manganese, and is favorable for industrial popularization.
Description
Technical Field
The invention relates to the field of semiconductors, in particular to a preparation method of high-purity manganese.
Background
With the development of metallurgical industry and new material industry, the application of manganese metal, particularly high-purity manganese (w (Mn)) is more than or equal to 99.9 percent in the fields of electronics, functional materials and fine manganese products, is gradually wide, and a wide space is provided for the development of the manganese industry. The market puts more and more demands on the refinement and diversification of manganese products.
In the field of electronic products, as the size of devices is continuously reduced, the speed requirement is continuously increased, and high-density current becomes a future development trend. Since the resistance of copper materials is much smaller than that of conventional aluminum or aluminum alloys, conventional aluminum or aluminum alloy connection lines are gradually replaced by copper connection lines. However, below the 28nm process node, electromigration of copper material is serious, which is likely to cause open circuit and thus affect the lifetime of the device. A self-diffusion barrier layer can be formed by adding high-purity manganese into a copper material, so that the electromigration problem is effectively relieved. Thus, the demand for high purity manganese is currently increasing in the electronics industry.
The vacuum distillation is a main method for preparing high-purity manganese, the purity of the obtained high-purity manganese can reach 4N5, and compared with an electrolytic refining method for preparing the high-purity manganese, the method has the advantages of simple production process, large treatment capacity, low production cost and good purification effect. However, the number of insoluble particles of manganese (LPC) obtained by vacuum distillation is high, and the number of insoluble particles of manganese 1.3 μm or more per 1g of manganese exceeds 10000, which seriously affects the yield of sputtered films. Therefore, it is necessary to reprocess the manganese obtained by vacuum distillation to reduce the LPC value.
CN104040030A discloses a high purity manganese and a method for producing the same, wherein a secondary raw material is obtained by acid-washing a manganese raw material, and the secondary raw material is subjected to electrolytic refining to obtain manganese with a purity of 3N or more. The manufacturing method has complex process flow and low product purity.
CN105200453A discloses a preparation process for electrolytic refining of high-purity manganese, which is to perform electrolytic refining twice on a purified manganese sulfate solution to obtain the high-purity manganese. The process flow is complex, the production cost is high, and the expanded production has certain limitation.
CN103114303A discloses a method for preparing high-purity manganese by taking ammonium sulfite as an additive and adopting a production process of deep purification, three-time filter pressing and layered filtration of supernatant and lower turbid liquid of a purified liquid.
Therefore, how to simplify the production process of high-purity manganese and reduce the LPC value of the high-purity manganese is a problem to be solved at present.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of high-purity manganese, and compared with the prior art, the LPC value of the high-purity manganese obtained by the invention is reduced by more than 50% compared with the traditional process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of high-purity manganese, which comprises the following steps:
(1) obtaining primary manganese by vacuum distillation;
(2) carrying out sand blasting treatment on the primary manganese to obtain sand blasting manganese;
(3) and carrying out acid washing treatment on the sand-blasting manganese to obtain the high-purity manganese.
In the invention, the high purity of the high-purity manganese means that the purity of Mn is more than or equal to 99.9%.
In the invention, the process for preparing the primary manganese by adopting the vacuum distillation method is simple, the production cost is low, and the purification effect is good. Because high-purity manganese for semiconductors has strict requirements on gas content, compared with the traditional electrolytic refining process, the vacuum distillation method can greatly reduce the content of C, H, O, N and other gas elements in electrolytic manganese, and the high-purity manganese obtained by electrolytic refining generally contains hundreds of ppm of metal impurities and thousands of ppm of non-metal impurities, and cannot meet the requirements of semiconductor target raw materials.
In the invention, the sand blasting process is to impact and cut the primary manganese surface by sand grains sprayed at high speed, so that the oxide layer on the primary manganese surface can be effectively removed at high speed. The acid washing treatment process can effectively remove metal and non-metal impurities on the surface of the sand-blasting manganese, greatly reduce particle pollution on the surface of the sand-blasting manganese and ensure that the surface of the manganese sheet has metal luster.
In the invention, firstly, the primary manganese with the purity of more than 4N5 is prepared by vacuum distillation, then the oxide layer on the surface of the primary manganese is removed by sand blasting, further, the metal and non-metal impurities on the surface are removed by acid washing, and the manganese sheet has metal luster, if the impurities are embedded into the surface of the manganese sheet in the sand blasting treatment, the impurities can also be removed by acid washing. Through the combined operation of vacuum distillation, sand blasting and acid washing, the number of insoluble residue particles with the particle size of more than 1.3 mu m in 1g of high-purity manganese is not more than 5000, and the number of insoluble residue particles with the particle size of more than 0.5 mu m is not more than 10000.
Preferably, the temperature in step (1) is 1200-1400 ℃, and may be, for example, 1200 ℃, 1220 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1280 ℃, 1300 ℃, 1320 ℃, 1340 ℃, 1350 ℃, 1360 ℃, 1380 ℃ or 1400 ℃, but is not limited to the values listed, and other values not listed in the value range are equally applicable, preferably 1300-1350 ℃.
Preferably, the sand blasting treatment of the step (2) comprises surface sand blasting and primary cleaning which are sequentially carried out.
Preferably, the grit used in the surface blasting comprises white corundum.
In the present invention, white corundum (Al) is used2O3) No other impurities, Al2O3And will dissolve in the acid solution during the subsequent pickling process. If the hardness or strength of the sand grains is too high, a great cutting effect is generated on the surface of the manganese sheet, and the high-hardness sand grains are easily embedded in the surface of the material, so that the difficulty of subsequent acid washing treatment is increased.
Preferably, the sand particles have a particle size of 200-.
Preferably, the pressure of the surface blasting is 0.3-0.5MPa, and may be, for example, 0.3MPa, 0.32MPa, 0.34MPa, 0.35MPa, 0.36MPa, 0.38MPa, 0.4MPa, 0.42MPa, 0.44MPa, 0.45MPa, 0.46MPa, 0.48MPa or 0.5MPa, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable, preferably 0.35-0.45 MPa.
Preferably, the surface is blasted at a distance of 200-.
In the invention, when the granularity of sand used for surface sand blasting is too large or the distance of the surface sand blasting is too close, the sand sprayed at high speed generates strong impact and cutting action on the surface of the manganese sheet, so that the shape of the manganese sheet is damaged, and the loss of manganese materials is caused. When the grit size of the sand used for surface blasting is too small or the distance of surface blasting is too far, it is difficult to completely remove the oxide layer on the manganese piece surface.
According to the method, through setting the sand blasting parameters, the oxide layer on the surface of the manganese sheet is effectively removed, and the loss of the raw material during treatment is reduced.
Preferably, the one-time washing includes: and (3) placing the primary manganese with the sand-blasted surface into a first solvent for primary cleaning.
In the invention, the manganese sheet after sand blasting is cleaned, so that solid dust particles on the surface of the manganese sheet are removed.
Preferably, the one-time cleaning includes one-time ultrasonic cleaning.
Preferably, the frequency of the one ultrasonic cleaning is 25 to 120kHz, and may be, for example, 25kHz, 30kHz, 35kHz, 40kHz, 45kHz, 50kHz, 55kHz, 60kHz, 65kHz, 70kHz, 75kHz, 80kHz, 85kHz, 90kHz, 95kHz, 100kHz, 105kHz, 110kHz, 105kHz or 120kHz, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable, preferably 60 to 100 kHz.
Preferably, the power of the one-time ultrasonic cleaning is 600-2400W, for example, 600W, 700W, 800W, 900W, 1000W, 1100W, 1200W, 1300W, 1400W, 1500W, 1600W, 1700W, 1800W, 1900W, 2000W, 2100W, 2200W, 2300W or 2400W, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable, preferably 800-1500W.
Preferably, the time of the one-time washing is 5 to 20 minutes, for example, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes or 20 minutes, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable, preferably 10 to 15 minutes.
Preferably, the first solvent comprises an isopropanol solution.
In the present invention, the purity of the isopropyl alcohol solution used was 99.99%.
Preferably, the acid washing treatment of the step (3) comprises primary acid washing, secondary acid washing and secondary cleaning which are sequentially carried out.
Preferably, the primary pickling comprises: and (4) putting the sand-blasting manganese into the first acid solution for primary acid washing.
Preferably, the first acid solution comprises a dilute nitric acid solution.
Preferably, the first acid solution has a mass concentration of 5 to 20%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 10 to 15%.
When the mass concentration of the acid washing is too high, not only the metal and nonmetal particles on the surface of the manganese are dissolved in the acid liquor, but also part of the manganese enters the acid liquor and is difficult to recover, so that the loss of raw materials is caused. When the mass concentration of the pickling is too low, it is difficult to completely remove particles on the surface of the manganese piece.
In the invention, the pickling basket needs to be shaken in the pickling process to ensure that the manganese sheets and the acid liquor fully react so as to avoid incomplete pickling of the product caused by product accumulation.
Preferably, the time of the primary acid washing is 3 to 15 minutes, for example, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes, but is not limited to the recited values, and other values not recited in the range of values are also applicable, preferably 5 to 10 minutes.
In the invention, the pickling time is too long, so that raw material loss is easily caused, and when the pickling time is too short, particle impurities on the surface are difficult to effectively remove.
In the invention, through setting the pickling treatment parameters, the particle pollutants on the surface of the manganese sheet are greatly reduced, and the loss of the raw materials during treatment is reduced.
Preferably, the temperature of the primary acid washing is 25-60 ℃, for example, 25 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 35 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 45 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 55 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the cited values, and other values not listed in the range of values are equally applicable, preferably 35-50 ℃.
Preferably, the secondary acid washing comprises: and (4) placing the sand-blasting manganese subjected to the primary acid washing into a second acid solution for secondary acid washing.
Preferably, the second acid solution comprises a dilute nitric acid solution.
Preferably, the second acid solution has a mass concentration of 1-5%, for example 1%, 2%, 3%, 4% or 5%, but not limited to the recited values, and other values within the range of values are equally applicable, preferably 3-4%.
Preferably, the time of the second acid washing is 5 to 15 minutes, for example, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes or 15 minutes, but not limited to the recited values, and other values not recited in the range of values are also applicable, preferably 8 to 10 minutes;
preferably, the temperature of the secondary acid washing is 25-60 ℃, for example, 25 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 35 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 45 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 55 ℃, 56 ℃, 58 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 35-50 ℃.
Preferably, the secondary cleaning comprises: and (4) putting the sand-blasting manganese subjected to the secondary acid washing into a second solvent for secondary washing.
In the invention, the secondary cleaning is carried out to remove the residual acid solution on the surface of the manganese sheet, and the acid-washed manganese sheet needs to be quickly put into a second solvent to prevent the manganese sheet from being oxidized again.
Preferably, the second solvent comprises an isopropanol solution.
In the present invention, the purity of the isopropyl alcohol solution used was 99.99%.
Preferably, the secondary cleaning comprises secondary ultrasonic cleaning.
Preferably, the frequency of the second ultrasonic cleaning is 25 to 120kHz, and may be, for example, 25kHz, 30kHz, 35kHz, 40kHz, 45kHz, 50kHz, 55kHz, 60kHz, 65kHz, 70kHz, 75kHz, 80kHz, 85kHz, 90kHz, 95kHz, 100kHz, 105kHz, 110kHz, 105kHz or 120kHz, but is not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 60 to 100 kHz.
Preferably, the power of the secondary ultrasonic cleaning is 600-2400W, for example, 600W, 700W, 800W, 900W, 1000W, 1100W, 1200W, 1300W, 1400W, 1500W, 1600W, 1700W, 1800W, 1900W, 2000W, 2100W, 2200W, 2300W or 2400W, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable, preferably 800-1500W.
Preferably, the time of the second washing is 3 to 20 minutes, for example, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes or 20 minutes, but not limited to the recited values, and other values not recited in the numerical range are also applicable, preferably 5 to 10 minutes.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) vacuum distillation is carried out at 1200 ℃ and 1400 ℃ to obtain primary manganese;
(2) sequentially carrying out surface sand blasting and primary ultrasonic cleaning on the primary manganese obtained in the step (1), wherein sand grains are white corundum, the granularity is 200-2500 meshes, the pressure of the surface sand blasting is 0.3-0.5MPa, the distance of the surface sand blasting is 200-300mm, and the primary ultrasonic cleaning is carried out in an isopropanol solution after the surface sand blasting, the frequency is 25-120kHz, the power is 600-2400W, and the time is 5-20 minutes, so as to obtain the sand blasting manganese;
(3) sequentially carrying out primary acid washing, secondary acid washing and secondary ultrasonic cleaning on the sand-blasting manganese obtained in the step (2); the primary acid washing comprises the steps of putting the sand blasting manganese into 5-20% dilute nitric acid, and carrying out acid washing for 3-15 minutes at 25-60 ℃; the secondary acid washing comprises the steps of putting the sand-blasting manganese after the primary acid washing into 1-5% dilute nitric acid solution, and carrying out acid washing for 5-15 minutes at 25-60 ℃; after secondary acid washing, secondary ultrasonic wave washing is carried out in isopropanol solution, the frequency is 25-120kHz, the power is 600-2400W, and the time is 3-20 minutes, so that the high-purity manganese is obtained.
In the invention, the obtained high-purity manganese is dried and packaged in sequence.
Preferably, the drying comprises vacuum drying.
Preferably, the vacuum degree of the vacuum drying is 0.01 to 0.04MPa, for example, 0.01MPa, 0.015MPa, 0.02MPa, 0.025MPa, 0.03MPa, 0.035MPa or 0.04MPa, but not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 0.02 to 0.03 MPa.
Preferably, the drying temperature is 50-80 ℃, for example 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 60-70 ℃.
Preferably, the drying time is 0.5 to 3 hours, and may be, for example, 0.5 hour, 0.6 hour, 0.8 hour, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, or 3 hours, but is not limited to the values recited, and other values not recited within the range of values are equally applicable, preferably 1 to 2 hours.
In the invention, the dried high-purity manganese is vacuum-packed by an aluminum-plastic bag.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation process of the high-purity manganese, the high-purity manganese with the purity of more than 4N5 can be obtained through the combined operation of vacuum distillation, sand blasting and acid pickling, the number of insoluble residue particles with the particle size of more than 1.3 mu m in each 1g of the high-purity manganese is not more than 5000, the number of insoluble residue particles with the particle size of more than 0.5 mu m is not more than 10000, and compared with the LPC value of the high-purity manganese prepared by the traditional vacuum distillation process, the high-purity manganese is bright and clean in surface and has metallic luster.
(2) The preparation process provided by the invention has the advantages of simple flow, low production cost, high yield, easiness in production monitoring and industrial popularization.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of high-purity manganese, which comprises the following steps:
(1) vacuum distilling at 1300 deg.C to obtain primary manganese;
(2) carrying out surface sand blasting and one-time ultrasonic cleaning on the primary manganese obtained in the step (1) in sequence, wherein sand grains are white corundum, the granularity is 1250 meshes, the pressure of the surface sand blasting is 0.4MPa, the distance of the surface sand blasting is 300mm, and after the surface sand blasting, one-time ultrasonic cleaning is carried out in an isopropanol solution, the frequency is 80kHz, the power is 1150W, and the time is 12 minutes, so that the sand blasting manganese is obtained;
(3) sequentially carrying out primary acid washing, secondary acid washing and secondary ultrasonic cleaning on the sand-blasting manganese obtained in the step (2); the primary acid washing comprises the steps of putting the sand-blasting manganese into 10% dilute nitric acid, and carrying out acid washing for 3 minutes at 40 ℃; the secondary acid washing comprises the steps of putting the sand-blasting manganese subjected to the primary acid washing into a dilute nitric acid solution with the concentration of 3 percent, and carrying out acid washing for 10 minutes at the temperature of 40 ℃; and after secondary acid washing, carrying out secondary ultrasonic cleaning in an isopropanol solution at the frequency of 80kHz and the power of 1150W for 7 minutes to obtain the high-purity manganese.
And (3) putting the high-purity manganese into a vacuum drying oven, drying for 1 hour at the vacuum degree of 0.02Pa and the temperature of 70 ℃, and then carrying out LPC detection.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 2
The embodiment provides a preparation method of high-purity manganese, which comprises the following steps:
(1) vacuum distilling at 1330 ℃ to obtain primary manganese;
(2) carrying out surface sand blasting and one-time ultrasonic cleaning on the primary manganese obtained in the step (1) in sequence, wherein sand grains are white corundum with the granularity of 625 meshes, the pressure of the surface sand blasting is 0.3MPa, the distance of the surface sand blasting is 300mm, and after the surface sand blasting, carrying out one-time ultrasonic cleaning in an isopropanol solution, wherein the frequency is 100kHz, the power is 800W, and the time is 5 minutes to obtain sand blasting manganese;
(3) sequentially carrying out primary acid washing, secondary acid washing and secondary ultrasonic cleaning on the sand-blasting manganese obtained in the step (2); the primary acid washing comprises the steps of putting the sand-blasting manganese into 20% dilute nitric acid, and carrying out acid washing for 3 minutes at 35 ℃; the secondary acid washing comprises the steps of putting the sand-blasting manganese subjected to the primary acid washing into a dilute nitric acid solution with the concentration of 5 percent, and carrying out acid washing for 5 minutes at the temperature of 50 ℃; and after secondary acid washing, carrying out secondary ultrasonic cleaning in an isopropanol solution at the frequency of 100kHz and the power of 800W for 20 minutes to obtain the high-purity manganese.
And (3) putting the high-purity manganese into a vacuum drying oven, drying for 1 hour at the vacuum degree of 0.02Pa and the temperature of 70 ℃, and then carrying out LPC detection.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 3
The embodiment provides a preparation method of high-purity manganese, which comprises the following steps:
(1) vacuum distilling at 1200 deg.C to obtain primary manganese;
(2) carrying out surface sand blasting and one-time ultrasonic cleaning on the primary manganese obtained in the step (1) in sequence, wherein sand grains are white corundum with the granularity of 2000 meshes, the pressure of the surface sand blasting is 0.5MPa, the distance of the surface sand blasting is 200mm, and after the surface sand blasting, carrying out one-time ultrasonic cleaning in an isopropanol solution, wherein the frequency is 60kHz, the power is 1500W, and the time is 20 minutes to obtain sand blasting manganese;
(3) sequentially carrying out primary acid washing, secondary acid washing and secondary ultrasonic cleaning on the sand-blasting manganese obtained in the step (2); the primary acid washing comprises the steps of putting the sand-blasting manganese into 5% dilute nitric acid, and carrying out acid washing for 15 minutes at 50 ℃; the secondary acid washing comprises the steps of putting the sand-blasting manganese subjected to the primary acid washing into a 1% dilute nitric acid solution, and carrying out acid washing for 15 minutes at 35 ℃; and after secondary acid washing, carrying out secondary ultrasonic cleaning in an isopropanol solution at the frequency of 60kHz and the power of 1500W for 3 minutes to obtain the high-purity manganese.
And (3) putting the high-purity manganese into a vacuum drying oven, drying for 1 hour at the vacuum degree of 0.02Pa and the temperature of 70 ℃, and then carrying out LPC detection.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 4
The embodiment provides a preparation method of high-purity manganese, which comprises the following steps:
(1) vacuum distilling at 1400 deg.C to obtain primary manganese;
(2) carrying out surface sand blasting and one-time ultrasonic cleaning on the primary manganese obtained in the step (1) in sequence, wherein sand grains are white corundum with the granularity of 200 meshes, the pressure of the surface sand blasting is 0.35MPa, the distance of the surface sand blasting is 280mm, and after the surface sand blasting, carrying out one-time ultrasonic cleaning in an isopropanol solution, wherein the frequency is 25kHz, the power is 2400W, and the time is 10 minutes to obtain sand blasting manganese;
(3) sequentially carrying out primary acid washing, secondary acid washing and secondary ultrasonic cleaning on the sand-blasting manganese obtained in the step (2); the primary acid washing comprises the steps of putting the sand-blasting manganese into 15% dilute nitric acid, and carrying out acid washing for 5 minutes at 60 ℃; the secondary acid washing comprises the steps of putting the sand-blasting manganese subjected to the primary acid washing into a dilute nitric acid solution with the concentration of 4 percent, and carrying out acid washing for 8 minutes at the temperature of 25 ℃; and after secondary acid washing, carrying out secondary ultrasonic cleaning in an isopropanol solution at the frequency of 120kHz and the power of 600W for 10 minutes to obtain the high-purity manganese.
And (3) putting the high-purity manganese into a vacuum drying oven, drying for 1 hour at the vacuum degree of 0.02Pa and the temperature of 70 ℃, and then carrying out LPC detection.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 5
The embodiment provides a preparation method of high-purity manganese, which comprises the following steps:
(1) vacuum distilling at 1350 deg.C to obtain primary manganese;
(2) carrying out surface sand blasting and one-time ultrasonic cleaning on the primary manganese obtained in the step (1) in sequence, wherein sand grains are white corundum with the granularity of 2500 meshes, the pressure of the surface sand blasting is 0.45MPa, the distance of the surface sand blasting is 220mm, and after the surface sand blasting, carrying out one-time ultrasonic cleaning in an isopropanol solution, wherein the frequency is 120kHz, the power is 600W, and the time is 15 minutes to obtain sand blasting manganese;
(3) sequentially carrying out primary acid washing, secondary acid washing and secondary ultrasonic cleaning on the sand-blasting manganese obtained in the step (2); the primary acid washing comprises the steps of putting the sand-blasting manganese into 10% dilute nitric acid, and carrying out acid washing for 10 minutes at 25 ℃; the secondary acid washing comprises the steps of putting the sand-blasting manganese subjected to the primary acid washing into a dilute nitric acid solution with the concentration of 3 percent, and carrying out acid washing for 10 minutes at the temperature of 60 ℃; and after secondary acid washing, carrying out secondary ultrasonic cleaning in an isopropanol solution at the frequency of 25kHz and the power of 2400W for 5 minutes to obtain the high-purity manganese.
And (3) putting the high-purity manganese into a vacuum drying oven, drying for 1 hour at the vacuum degree of 0.02Pa and the temperature of 70 ℃, and then carrying out LPC detection.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 6
This example provides a method for preparing high purity manganese, which is different from example 1 only in that the pressure of surface blasting is 0.2 MPa.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 7
This example provides a method for preparing high purity manganese, which is different from example 1 only in that the pressure of surface blasting is 0.6 MPa.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 8
This example provides a method for preparing high purity manganese, which is different from example 1 only in that the distance of surface blasting is 100 mm.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 9
This example provides a method for preparing high purity manganese, which is different from example 1 only in that the surface blasting distance is 400mm, and the rest is the same as example 1.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 10
This example provides a method for preparing high purity manganese, which differs from example 1 only in that the mass concentration of dilute nitric acid used in one pickling is 3%.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 11
This example provides a method for preparing high purity manganese, which is different from example 1 only in that the mass concentration of dilute nitric acid used in one pickling is 30%, and the rest is the same as example 1.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 12
This example provides a method for preparing high purity manganese, which is different from example 1 only in that the mass concentration of dilute nitric acid used in the second acid washing is 0.5%, and the rest is the same as example 1.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Example 13
This example provides a method for preparing high purity manganese, which is different from example 1 only in that the mass concentration of dilute nitric acid used in the second acid washing is 7%, and the rest is the same as example 1.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Comparative example 1
This comparative example provides a method for preparing high purity manganese, which is different from example 1 only in that step (1) is performed.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Comparative example 2
This comparative example provides a method for preparing high purity manganese, which is different from example 1 only in that step (1) and step (2) are performed.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Comparative example 3
This comparative example provides a method for preparing high purity manganese, which is different from example 1 only in that step (1) and step (3) are performed.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Comparative example 4
This comparative example provides a method for preparing high purity manganese, differing from example 1 only in that step (1) is replaced with electrolytic refining to prepare manganese.
The method for preparing manganese by electrolytic refining comprises the following steps: performing diaphragm electrolysis on manganese sulfate solution at pH 7 and 25 deg.C in electrolytic bath at current density of 200A/m2And obtaining the manganese.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Comparative example 5
This comparative example provides a method for preparing high purity manganese, which is different from example 1 only in that the steps (1), (3), and (2) are sequentially performed.
The LPC value of the high purity manganese obtained is detailed in Table 1.
Comparative example 6
This comparative example provides a method for preparing high purity manganese, which is different from example 1 only in that the steps (2), (3), and (1) are sequentially performed.
The LPC value of the high purity manganese obtained is detailed in Table 1.
The LPC values of the high purity manganese prepared in examples 1 to 13 and comparative examples 1 to 6 were measured by the following methods: and (3) taking 5g of high-purity manganese, slowly dissolving the high-purity manganese in 200mL of acid liquor, diluting the acid liquor to 500mL of acid liquor by using ultrapure water after the acid liquor and the high-purity manganese fully react, and taking 10mL of diluent to measure the LPC value by using a liquid particle counter.
TABLE 1
As is clear from Table 1, in the high purity manganese obtained in examples 1 to 13, the number of insoluble residue particles having a particle size of 1.3 μm or more was not more than 5000, and the number of insoluble residue particles having a particle size of 0.5 μm or more was not more than 10000, and thus the LPC value of the high purity manganese could be effectively reduced.
In example 6, the pressure of surface blasting was lower than that of example 1, the blasting effect was reduced, and the LPC values of the resulting high purity manganese were all increased relative to that of example 1.
In example 7, the pressure of surface blasting is higher than that of example 1, the blasting effect is improved, and the LPC value of the obtained high-purity manganese is reduced relative to that of example 1.
In example 8, the distance of surface blasting is less than that of example 1, the blasting effect is improved, and the LPC value of the obtained high-purity manganese is reduced relative to that of example 1.
In example 9, the distance of surface blasting is greater than that of example 1, the blasting effect is reduced, and the LPC value of the obtained high-purity manganese is increased relative to that of example 1.
In example 10, since the dilute nitric acid used for the primary pickling was lower in mass concentration than in example 1, the pickling effect was reduced, and the LPC value of high-purity manganese was increased relative to example 1.
In example 11, the mass concentration of dilute nitric acid used in the primary pickling was higher than that in example 1, so that the pickling effect was improved, and the LPC value of high-purity manganese was decreased relative to that in example 1.
In example 12, since the dilute nitric acid used for the second acid washing was lower in mass concentration than in example 1, the effect of the acid washing was reduced, and the LPC value of high purity manganese was increased relative to example 1.
In example 13, since the mass concentration of dilute nitric acid used in the secondary pickling was higher than that in example 1, the pickling effect was improved, and the LPC value of high-purity manganese was reduced relative to that in example 1.
In comparative example 1, in comparison with example 1 in which only step (1) was performed, the LPC values of the high purity manganese obtained were all increased, indicating that the LPC values of the high purity manganese obtained by vacuum distillation were still high without performing the blast treatment and the acid washing treatment, and insoluble residue particles contained in the high purity manganese were difficult to remove.
In comparative example 2, in comparison with example 1 in which only step (1) and step (2) were carried out, the LPC values of the obtained high purity manganese were both increased, indicating that the insoluble residue particles contained in the obtained high purity manganese were difficult to remove without carrying out the acid washing treatment.
In comparative example 3, in comparison with example 1 in which only step (1) and step (3) were performed, the LPC values of the obtained high purity manganese were both increased, indicating that insoluble residue particles contained in the obtained high purity manganese were difficult to remove without performing the blast treatment.
In comparative example 4, manganese was produced by replacing step (1) with electrolytic refining as compared with example 1. The method for preparing manganese by electrolytic refining comprises the following steps: diaphragm electrolysis is carried out on a manganese sulfate solution in an electrolytic cell under the conditions that the pH value is 7 and the temperature is 25 ℃, and the current density is 200A/m2, so that manganese is obtained. The LPC value of the obtained manganese was increased as compared with that of example 1, and it was confirmed that the high purity manganese prepared by the electrolytic refining method contained a large amount of insoluble residue particles.
In comparative example 5, it is compared with example 1 in that the procedure of steps (1), (3), (2) is followed. The LPC values of the manganese obtained were higher than those of the manganese obtained in all of the examples 1, and it was confirmed that the pickling treatment and then the blasting treatment were performed, and thus it was difficult to remove the insoluble residue particles, and the sand particles during blasting were likely to adhere to the manganese surface, which resulted in the increase in the LPC values.
In comparative example 6, it is compared with example 1 in that the procedure of steps (2), (3), (1) is followed. The LPC values of the obtained manganese were all higher than those of example 1, indicating that the insoluble residue particles contained in the high purity manganese obtained by sand blasting, then acid washing and finally vacuum distillation of the manganese-containing raw material were difficult to remove effectively.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of high-purity manganese is characterized by comprising the following steps of:
(1) obtaining primary manganese by vacuum distillation;
(2) carrying out sand blasting treatment on the primary manganese to obtain sand blasting manganese;
(3) and carrying out acid washing treatment on the sand-blasting manganese to obtain the high-purity manganese.
2. The method according to claim 1, wherein the temperature of the vacuum distillation in step (1) is 1200-1400 ℃, preferably 1300-1350 ℃.
3. The production method according to claim 1 or 2, wherein the blasting treatment of step (2) includes surface blasting and primary cleaning which are performed sequentially.
4. A producing method according to claim 3, wherein the sand for surface blasting includes white corundum;
preferably, the granularity of the sand grains is 200-;
preferably, the pressure of the surface blasting is 0.3-0.5MPa, preferably 0.35-0.45 MPa;
preferably, the distance of the surface blasting is 200-300mm, preferably 220-280 mm.
5. The production method according to claim 3 or 4, wherein the primary washing includes: placing the primary manganese with the sand-blasted surface into a first solvent for primary cleaning;
preferably, the one-time cleaning comprises one-time ultrasonic cleaning;
preferably, the frequency of the primary ultrasonic cleaning is 25-120kHz, preferably 60-100 kHz;
preferably, the power of the primary ultrasonic cleaning is 600-2400W, preferably 800-1500W;
preferably, the time of the primary cleaning is 5 to 20 minutes, preferably 10 to 15 minutes;
preferably, the first solvent comprises an isopropanol solution.
6. The production method according to any one of claims 1 to 5, wherein the acid washing treatment in step (3) comprises a primary acid washing, a secondary acid washing and a secondary washing which are performed in this order.
7. The method according to claim 6, wherein the primary acid washing comprises: placing the sand-blasting manganese into a first acid solution for primary acid washing;
preferably, the first acid solution comprises a dilute nitric acid solution;
preferably, the mass concentration of the first acid liquid is 5-20%, preferably 10-15%;
preferably, the time of the primary acid washing is 3 to 15 minutes, preferably 5 to 10 minutes;
preferably, the temperature of the primary acid washing is 25-60 ℃, preferably 35-50 ℃.
8. The production method according to claim 6 or 7, wherein the secondary acid washing comprises: placing the sand-blasting manganese subjected to primary acid washing into a second acid solution for secondary acid washing;
preferably, the second acid solution comprises a dilute nitric acid solution;
preferably, the mass concentration of the second acid liquid is 1-5%, preferably 3-4%;
preferably, the time of the secondary acid washing is 5 to 15 minutes, preferably 8 to 10 minutes;
preferably, the temperature of the secondary acid washing is 25-60 ℃, preferably 35-50 ℃.
9. The production method according to any one of claims 6 to 8, wherein the secondary washing includes: placing the sand-blasting manganese subjected to the secondary acid washing into a second solvent for secondary washing;
preferably, the second solvent comprises an isopropanol solution;
preferably, the secondary cleaning comprises secondary ultrasonic cleaning;
preferably, the frequency of the secondary ultrasonic cleaning is 25-120kHz, preferably 60-100 kHz;
preferably, the power of the secondary ultrasonic cleaning is 600-2400W, preferably 800-1500W;
preferably, the time of the second washing is 3 to 20 minutes, preferably 5 to 10 minutes.
10. The method of any one of claims 1 to 9, comprising the steps of:
(1) vacuum distillation is carried out at 1200 ℃ and 1400 ℃ to obtain primary manganese;
(2) sequentially carrying out surface sand blasting and primary ultrasonic cleaning on the primary manganese obtained in the step (1), wherein sand grains are white corundum, the granularity is 200-2500 meshes, the pressure of the surface sand blasting is 0.3-0.5MPa, the distance of the surface sand blasting is 200-300mm, and the primary ultrasonic cleaning is carried out in an isopropanol solution after the surface sand blasting, the frequency is 25-120kHz, the power is 600-2400W, and the time is 5-20 minutes, so as to obtain the sand blasting manganese;
(3) sequentially carrying out primary acid washing, secondary acid washing and secondary ultrasonic cleaning on the sand-blasting manganese obtained in the step (2); the primary acid washing comprises the steps of putting the sand blasting manganese into 5-20% dilute nitric acid, and carrying out acid washing for 3-15 minutes at 25-60 ℃; the secondary acid washing comprises the steps of putting the sand-blasting manganese after the primary acid washing into 1-5% dilute nitric acid solution, and carrying out acid washing for 5-15 minutes at 25-60 ℃; after secondary acid washing, secondary ultrasonic wave washing is carried out in isopropanol solution, the frequency is 25-120kHz, the power is 600-2400W, and the time is 3-20 minutes, so that the high-purity manganese is obtained.
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| CN104040030A (en) * | 2012-01-10 | 2014-09-10 | 吉坤日矿日石金属株式会社 | High-purity manganese and method for producing same |
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| CN112959224A (en) * | 2021-02-03 | 2021-06-15 | 合肥江丰电子材料有限公司 | Method for preventing oxidation of target material after sand blasting |
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| CN104040030A (en) * | 2012-01-10 | 2014-09-10 | 吉坤日矿日石金属株式会社 | High-purity manganese and method for producing same |
| CN107000164A (en) * | 2015-03-12 | 2017-08-01 | 新东工业株式会社 | The impeller blasting method of casting |
| CN112959224A (en) * | 2021-02-03 | 2021-06-15 | 合肥江丰电子材料有限公司 | Method for preventing oxidation of target material after sand blasting |
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