CN110835694B - Gas-phase magnesium purification method and device based on simple substance silicon filter material - Google Patents
Gas-phase magnesium purification method and device based on simple substance silicon filter material Download PDFInfo
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- CN110835694B CN110835694B CN201911178331.3A CN201911178331A CN110835694B CN 110835694 B CN110835694 B CN 110835694B CN 201911178331 A CN201911178331 A CN 201911178331A CN 110835694 B CN110835694 B CN 110835694B
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Abstract
The invention provides a gas-phase magnesium purification method based on an elemental silicon filter material, which adopts the elemental silicon filter material to filter magnesium vapor. In a certain temperature and vacuum degree range, the simple substance silicon does not react with magnesium vapor and does not bring new impurities to the system; on the other hand, the simple substance silicon has special affinity with Ca, Al and Mn in magnesium vapor, and can form a more stable solid solution with silicon; meanwhile, the simple substance silicon can be used as a nucleation site of impurities in magnesium vapor, so that the nucleation energy barrier is reduced, certain impurities are deposited in advance, and the impurities are removed. The method provided by the invention can be applied to large-scale industrialized gas-phase magnesium purification, improves the production efficiency of magnesium purification by increasing the temperature in a magnitude order, reduces the content of impurities Mn in the magnesium raw material to be less than 4ppm, the content of Al in the magnesium raw material to be less than 10ppm and the content of Ca in the magnesium raw material to be less than 10ppm, and obtains the magnesium with the purity of more than 99.99 percent.
Description
Technical Field
The invention belongs to the technical field of magnesium metal purification, and particularly relates to a method and a device for purifying gas-phase magnesium based on an elemental silicon filter material.
Background
The magnesium alloy has the advantages of low density, strong damping and shock absorption, excellent electromagnetic shielding performance, relatively low recovery cost and the like, so the magnesium alloy is regarded as a green and environment-friendly engineering structure material in the 21 st century and important strategic materials. Currently, the magnesium purification field has aeipathia diseases such as low overall purity (only 99.90%), many types of impurity elements (mainly containing Mn, Al, Ca, Si, Fe, Ni and the like), large content fluctuation and the like. These maladies severely degrade the performance of the magnesium alloy, which in turn makes its practical application far less than desired.
There are two main methods for purifying magnesium: flux refining and vacuum distillation. The former has the advantage of realizing the mass purification of the raw magnesium, but because the refining agent does not react with impurity elements such as Mn, Al, Fe, Ni and the like of the reduced magnesium ingot, the magnesium with the purity of more than 99.95 percent is difficult to produce; the latter has the advantages of being capable of preparing ultra-high-purity magnesium with the purity of 99.9999 percent (not counting Zn content), and having the disadvantages of low preparation efficiency and high cost, and being incapable of meeting the requirements of industrialized large-scale production.
Investigations have shown that different users of the magnesium industry have special requirements for different impurity contents of magnesium metal. For example: the magnesium used as the high-potential sacrificial anode is required to have the magnesium content of more than 99.95 percent, and simultaneously required to have Fe of less than 30ppm, Si of less than 100ppm and Al of less than 100 ppm; the titanium sponge used as a reducing agent is required to have the magnesium content of more than 99.95 percent, and simultaneously required to have Fe less than 30ppm, Mn less than 150ppm and Si less than 100 ppm. Therefore, it is not only necessary but also urgent to develop a technology capable of producing high purity magnesium (> 99.95%) at low cost and high efficiency, and particularly, capable of reducing specific impurities in a targeted manner.
Patents CN203429230U, CN208562489U and CN201024206Y mention that "catcher", "interceptor" or "filter" is arranged at the mouth of the pijiang process reduction tank, and some special geometric structures are arranged at the mouth of the pijiang process reduction tank to intercept dust or some precondensate, but the overall purification effect is limited, and some impurity or some impurities cannot be removed in a targeted manner.
In addition, the method for purifying magnesium in the prior art also adopts a vapor deposition method of removing impurities with the aid of a filter material, but the common filter material adopts stainless steel fibers or a method of combining the stainless steel fibers and copper fibers, and the stainless steel is not suitable for the working condition of overhigh vapor pressure of magnesium and is suitable for the working condition of low-temperature sublimation with lower heating temperature, so that the magnesium purification efficiency is low, and the yield of high-purity magnesium is extremely low.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method and a device for purifying gas-phase magnesium based on an elemental silicon filter material. The method comprises the steps of heating a magnesium raw material to magnesium vapor, and then enabling the magnesium vapor to pass through a simple substance silicon filter material to remove impurities in the magnesium vapor, thereby obtaining high-purity magnesium.
The invention aims to provide a method for purifying gas-phase magnesium based on an elemental silicon filter material.
The invention also aims to provide a device for realizing the gas-phase magnesium purification method.
The invention provides a method for purifying gas-phase magnesium based on an elemental silicon filter material, which comprises the following steps:
(1) placing a magnesium raw material in a reaction zone in a sealed crucible, and vacuumizing the interior of the crucible;
(2) heating the magnesium raw material by a heating mechanism until magnesium steam is generated, and condensing the magnesium steam on a crystallizer of which the crucible is far away from the reaction zone through the simple substance silicon filter material to obtain high-purity magnesium.
According to thermodynamic calculation, the invention discovers that as shown in fig. 1, compared with magnesium, the vapor pressure of elemental silicon is extremely low, and almost no elemental silicon enters a magnesium vapor system, while impurities contained in magnesium vapor, such as Mn, Al and Ca, can form a stable solid solution with the elemental silicon at a higher temperature, so that the impurities can be removed from the magnesium vapor system; in addition, other impurities in the magnesium vapor can be condensed, enriched and separated from a gas phase system by virtue of attachment sites provided by the simple substance silicon filter material; there are also some impurities that can be effectively removed by physical adsorption of elemental silicon. Because the evaporation temperature in the gas-phase magnesium purification method based on the simple substance silicon filter material is high, the magnesium raw material can be quickly changed into magnesium vapor, and the magnesium with the purity higher than 99.99 percent can be obtained through one-time gasification-filtration-condensation process, so the magnesium purification efficiency is high, and the method is suitable for large-scale industrial production. The simple substance silicon filter material adopted in the method provided by the invention is a semiconductor material, the current semiconductor industry is mature, high-purity silicon above 5N grade is easy to obtain at low cost, and the high-purity silicon can be directly used as the filter material without complex pretreatment, so that the cost of the filter material is greatly reduced.
Preferably, in the step (1), the degree of vacuum inside the crucible is 100Pa or less. The vacuum degree in the crucible provided by the invention is below 100Pa, and the efficiency of purifying magnesium can be ensured to be improved.
Preferably, in the step (2), the heating temperature is 650-.
The melting range of the magnesium raw material containing trace impurities is 650-700 ℃, and the invention is 10 DEG C5The temperature in the crucible is set to 650-1350 ℃ under the vacuum degree below Pa, the magnesium raw material containing impurities can be changed into magnesium vapor, and the evaporation rate of magnesium can be exponentially increased by increasing the temperature, so that the production efficiency can be increased by orders of magnitude. And at the temperature, elemental silicon as a filter material cannot enter a magnesium vapor system, after magnesium passes through the elemental silicon filter material, impurities in magnesium vapor can be well combined with the elemental silicon filter material, the impurities can obtain corresponding attachment points on the elemental silicon filter material, the impurities are left in the elemental silicon filter material, the magnesium vapor further rises to a crystallization area, and the magnesium vapor is condensed on a crystallizer to obtain high-purity magnesium.
Preferably, in the step (2), the heating is performed in three sections, wherein the first section heats the reaction zone of the crucible provided with the magnesium raw material, and the temperature is 700-1300 ℃; the second section and the third section sequentially heat an impurity condensation zone provided with a pure iron filter material in the crucible, the setting temperature of the second section is 700-1300 ℃, and the setting temperature of the third section is 650-1000 ℃. In the method provided by the invention, the heating is carried out in three sections, wherein the first section is mainly used for heating magnesium raw materials to generate magnesium steam, and the second section and the third section are used for keeping the steam state of magnesium on one hand and heating the simple substance silicon filter material on the other hand, so that the simple substance silicon filter material ensures the optimal working temperature and is beneficial to removing impurities in the magnesium steam.
Preferably, in the step (2), the heating is performed in three sections, wherein the first section heats the reaction zone of the crucible provided with the magnesium raw material, and the temperature is 1200-1300 ℃; the second section and the third section sequentially heat an impurity condensation zone provided with the simple substance silicon filter material in the crucible, wherein the temperature of the second section is 1200-1300 ℃, and the temperature of the third section is 700-1000 ℃. According to the method adopted by the invention, on one hand, the raw material balls can be used as the magnesium source material, and on the other hand, the metal magnesium with the purity of less than 99.99 percent can be used as the magnesium source material. When the raw material ball is used as the magnesium source material, the magnesium source material needs to be subjected to chemical reaction, so that the temperature for heating the magnesium source material needs to be over 1200 ℃, the vacuum degree is below 20Pa, and the reduced material ball can react at the temperature and the vacuum degree and obtain magnesium vapor.
Preferably, in the step (2), the heating temperature is 700-. Further preferably, the first section heats the reaction area of the crucible provided with the magnesium raw material, and the temperature is 700-; the second section and the third section sequentially heat an impurity condensation zone provided with the simple substance silicon filter material in the crucible, the temperature of the second section is 700-1050 ℃, and the temperature of the third section is 650-800 ℃.
The magnesium source material provided by the invention can be metal magnesium containing impurities besides the reducing material balls, when the metal magnesium is used as the magnesium source material, because the melting point of the magnesium is 649.85 ℃ and the boiling point is 1094.54 ℃, the evaporation is generally carried out at the vacuum degree of below 10Pa and below 750 ℃ by adopting a conventional vacuum distillation method, and the magnesium source material can be heated to the temperature of above 750 ℃ and below 1050 ℃, so that the evaporation rate of the magnesium can be exponentially improved by the temperature increase, and the production efficiency is improved by orders of magnitude.
Preferably, in the step (2), the three-stage heating process is as follows: firstly, the second section and the third section are heated to rated temperature, the temperature is kept for 20-35min, and then the first section is heated to rated temperature.
Because simple substance silicon can form stable solid solution with calcium impurity in magnesium steam when being used as a filter material, thereby removing calcium impurity, but calcium and magnesium belong to the same group elements, and the calcium and the magnesium have similar properties.
Preferably, in the step (2), the elemental silicon filter material is arranged in an impurity condensation zone in the crucible.
Further preferably, in the step (2), the working temperature of the simple substance silicon filter material is 700-.
Due to the high impurity content in the magnesium raw material, Ca, F and Al impurities are distributed over the respective temperatures of the condensation zone and are usually accompanied, and Mn condensate occurs at 765-832 ℃ and lower. Most of impurities in the magnesium can be effectively removed on the simple substance silicon filter material at 586 and 950 ℃.
The principle of removing elemental silicon by its specific affinity for certain impurity elements can be illustrated by simplified thermodynamic calculations. By assuming an initial mixed steam entry: 98.6mol of Mg, 0.1mol of Al, 0.1mol of Mn, 0.1mol of Ca and 0.1mol of Zn. Sufficient solid Si (1mol) is arranged in the system as a filter material, and the equilibrium state composition is determined by utilizing the Gibbs free energy minimum principle at the temperature of 1000 ℃, 900 ℃, 800 ℃, 700 ℃ and the like. As shown in figure 1, at 1000 ℃, 900 ℃ and 800 ℃, the simple substance silicon can form a more stable solid solution with the impurities Mn, Al and Ca contained in the magnesium vapor, and the condensed substances are all solid solutions with a tP20 structure according to calculation; the structure is aC1#1 or B20#1 at 700 ℃, but a part of Mg is condensed at the time. Wherein tP20, aC1#1, B20#1 are crystal structure types under the Pearson and Strukturbericht naming rules. This shows that the impurities Mn, Al, Ca in the magnesium vapor can be condensed in the temperature range of 700-1000 ℃, but the magnesium will partially condense below 700 ℃, so the optimum working temperature of the simple substance silicon filter material is 700-1000 ℃ in order to increase the yield of magnesium. According to the invention, a more stable solid solution can be formed at a higher temperature between the simple substance silicon filter material and Mn, Al and Ca in magnesium vapor, so that impurities Mn, Al and Ca can be removed from a magnesium vapor system in advance, and in the temperature range, the residual impurities in the magnesium vapor can be effectively removed through the physical adsorption effect of the simple substance silicon filter material or the effect of providing condensation sites for the impurities, so that the purity of the obtained magnesium is ensured to be more than 99.99%.
The invention provides a device for purifying gas-phase magnesium containing an elemental silicon filter material for realizing the method, which comprises an electric furnace body, a crucible, a heating mechanism, a thermocouple and a vacuum mechanism;
the crucible comprises a reaction zone, an impurity condensation zone and a crystallization zone which are arranged in sequence,
the reaction zone is provided with a hopper,
the impurity condensing zone is provided with a filtering component,
the filtering component is provided with a filtering material which is simple substance silicon,
the crystallization zone is provided with a crystallizer;
the vacuum mechanism is arranged in the electric furnace body, and the crucible is arranged in the vacuum mechanism;
the thermocouple is arranged on the outer wall of the crucible;
the heating mechanism is arranged in the electric furnace body to heat the crucible.
In order to realize the purpose of purifying magnesium by using the method for purifying the gas-phase magnesium of the simple substance silicon filter material, the invention provides a device matched with the method for use, a crucible impurity condensation zone in the device is provided with a filtering component, the filtering component is internally provided with the simple substance silicon filter material, and the device is also provided with a heating mechanism for realizing magnesium gas phase, a thermocouple and a vacuum mechanism for keeping the vacuum degree of the system.
The device provided by the invention has a simple structure, is suitable for large-scale industrial production, improves the efficiency of purifying magnesium, and has great economic benefit.
The filter assembly in the device provided by the invention can be detached, impurities attached to the filter material can be removed in acid washing and other modes, the purpose of repeatedly using the filter material for multiple times is achieved, and the production cost is reduced.
According to the device for purifying gas-phase magnesium containing the simple substance silicon filter material provided by the invention, preferably, the filter material is simple substance silicon particles.
The device for purifying the gas-phase magnesium containing the simple substance silicon filter material provided by the invention is further preferable that the particle size of the simple substance silicon particles is 0.1-10 mm.
The simple substance silicon filter material in the device provided by the invention has special affinity with impurities in magnesium vapor, is used as a nucleation site of the impurities in the magnesium vapor to reduce the nucleation energy barrier and enable the impurities to be deposited in advance, and has the physical interception function of the filter material. No matter the magnesium vapor is used as a nucleation site or physical interception of impurities, the filter material can be realized only by needing a larger contact area with the magnesium vapor, and the filter material adopts a form of simple substance silicon particles, so that the contact area of the filter material and the magnesium vapor can be effectively improved, and the filtering efficiency is improved.
In the device for purifying magnesium in gas phase containing the simple substance silicon filter material, preferably, the crystallization zone is provided with a plurality of crystallizers arranged in a stage-by-stage manner.
The device provided by the invention is provided with the plurality of crystallizers, the plurality of crystallizers are arranged step by step, most impurities in magnesium are retained in the simple substance silicon filter material in the impurity condensation zone in the magnesium purification process, but zinc cannot be removed through the simple substance silicon filter material, and the zinc can be removed through the multistage crystallizers.
The device for purifying the gas-phase magnesium containing the simple substance silicon filter material, provided by the invention, preferably comprises a heating mechanism, a heating mechanism and a control mechanism, wherein the heating mechanism comprises a first heating component, a second heating component and a third heating component; the first heating assembly heats a reaction zone of the crucible; the second heating assembly and the third heating assembly heat an impurity condensing region of the crucible. The purpose of multistage temperature control is to accurately control the temperature and prolong the length of the proper filter material working temperature. Therefore, the multi-stage temperature control is more accurate in temperature gradient, the physical space for properly removing impurities is longer, and the high-purity magnesium can be obtained more favorably.
Preferably, the vacuum mechanism comprises a vacuum cabin, a water-cooling flange, an end cover and a vacuumizing assembly; the vacuum cabin body is arranged inside the electric furnace body; the water-cooling flanges are arranged at two ends of the vacuum cabin body; the end cover is arranged at the end part of the water-cooling flange far away from the vacuum cabin body; the vacuumizing assembly can vacuumize the interior of the vacuum cabin; the crucible is arranged inside the vacuum cabin.
According to the invention, different sections of the crucible are heated through the first heating assembly, the second heating assembly and the third heating assembly, the temperature in the crucible is monitored through the thermocouple arranged on the outer wall of the crucible, and the temperature of the crucible is used as feedback to adjust. The water-cooled flanges at the two ends mainly reduce the temperature of the flange interface, protect the flange rubber ring from being burnt by overheating, and keep vacuum. In addition, the temperature of the crystallizer can also be indirectly adjusted by adjusting the flow rate of the cooling water.
According to the device for purifying the gas-phase magnesium containing the simple substance silicon filter material, provided by the invention, preferably, the crucible is formed by assembling a plurality of sections of high-purity graphite pipe fittings, and the two sections of pipe fittings are connected in an insertion manner. The thermocouples in the invention are arranged on different sections of the high-purity graphite pipe fitting and are used for monitoring the temperature of each section of the crucible.
The high-purity graphite pipe fitting is prepared by taking high-purity graphite as a raw material, wherein the high-purity graphite means that the carbon content of the graphite is higher than 99.99%.
The invention has the beneficial effects that:
1. the method for purifying the gas-phase magnesium based on the simple substance silicon filter material provided by the invention adopts the simple substance silicon filter material to filter magnesium vapor under specific temperature and vacuum degree. The application of the simple substance silicon filter material in the gas-phase magnesium purification process breaks through the technical prejudice that the silicon is avoided contacting as much as possible in the traditional magnesium purification process. The invention provides a method for purifying magnesium by using simple substance silicon as a filter material in a gas phase, on one hand, the simple substance silicon does not react with magnesium vapor, does not form more stable substances with magnesium thermodynamically, and does not bring new impurities to a system; on the other hand, Mn, Al and Ca in the magnesium vapor have special affinity with silicon and can form a stable solid solution with the silicon at a higher temperature, so that the impurities of Mn, Al and Ca are removed; meanwhile, the simple substance silicon can be used as the nucleation sites of certain impurities in the magnesium vapor, the nucleation energy barrier is reduced, and certain impurities are deposited in advance, so that the impurities in the magnesium vapor are removed.
2. The method provided by the invention can be applied to industrial large-scale gas-phase magnesium purification, the evaporation rate is exponentially improved by improving the temperature of the system, so that the production efficiency of magnesium purification can be improved by orders of magnitude, and on the premise of industrial large-scale crude production, the method provided by the invention can reduce the content of impurities Mn in the magnesium raw material to be less than 4ppm, the content of Al to be less than 10ppm, the content of Ca to be less than 10ppm, the content of Si to be less than 10ppm, and the purity of the obtained magnesium to be more than 99.99%.
3. The method provided by the invention simplifies the production process flow, impurities such as Ca, Mn, Al, Fe, Ni and the like are mainly enriched on the filter material, a multi-stage tray is not required to be arranged, the yield of high-purity magnesium is obviously improved, and thus the production cost of the high-purity magnesium is obviously reduced.
4. The device provided by the invention has a simple structure, is suitable for large-scale industrial production, improves the efficiency of purifying magnesium, and has great economic benefit. The filter assembly in the device provided by the invention can be detached, impurities attached to the filter material can be removed in acid washing and other modes, the purpose of repeatedly using the filter material for multiple times is achieved, and the production cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a diagram showing thermodynamic calculations of the composition and content of condensed materials at different temperatures;
FIG. 2 is a schematic structural view of the apparatus provided in example 1;
FIG. 3 is a schematic view of the structure of the apparatus provided in example 2;
FIG. 4 is a schematic Scanning Electron Microscope (SEM) view of the pre-test filter of example 3;
FIG. 5 is a schematic representation of the energy dispersive X-ray Spectroscopy (EDS) of the pre-experimental filter of example 3;
FIG. 6 is a schematic view of a Scanning Electron Microscope (SEM) on the filter after the experiment of example 3;
FIG. 7 is a schematic representation of the energy dispersive X-ray Spectroscopy (EDS) of the filter after the experiment of example 3;
FIG. 8 is a graph showing a comparison of the content of calcium as an impurity in the raw material and the magnesium obtained in example 3 and comparative example 1;
FIG. 9 is a Scanning Electron Microscope (SEM) representation of the filter after the experiment of example 5;
FIG. 10 is a schematic representation of the energy dispersive X-ray Spectroscopy (EDS) of the filter after the experiment of example 5;
FIG. 11 is a Scanning Electron Microscope (SEM) representation of the filter of example 6 after the experiment;
FIG. 12 is a schematic representation of the energy dispersive X-ray Spectroscopy (EDS) of the filter after the experiment of example 6; .
In the figure 1, an electric furnace body; 2. a crucible; 3. a heating mechanism; 4. a thermocouple; 5. a vacuum mechanism; 21. a reaction zone; 22. an impurity condensation zone; 23. a crystallization zone; 211. a hopper; 221. a filter assembly; 231. a crystallizer; 31. a first heating assembly; 32. a second heating assembly; 33. a third heating assembly; 51. a vacuum chamber; 52. water-cooling the flange; 53. an end cap; 54. and a vacuum pumping assembly.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
As shown in fig. 2, an apparatus for purifying magnesium in gas phase containing an elemental silicon filter material comprises an electric furnace body 1, a crucible 2, a heating mechanism 3, a thermocouple 4 and a vacuum mechanism 5;
the crucible 2 comprises a reaction zone 21, an impurity condensation zone 22 and a crystallization zone 23 which are arranged in sequence,
the reaction zone 21 is provided with a hopper 211,
the impurity condensing region 22 is provided with a filtering member 221,
a filter material is arranged in the filter component 221, the filter material is simple substance silicon particles, and the particle size of the simple substance silicon particles is 0.1-10 mm;
the crystallization zone 23 is provided with a crystallizer 231;
the heating mechanism 3 is arranged in the electric furnace body 1 to heat the crucible 2;
the vacuum mechanism 5 comprises a vacuum cabin body 51, a water-cooling flange 52, an end cover 53 and a vacuum pumping assembly 54; the vacuum chamber 51 is arranged inside the electric furnace body 1; the water-cooling flanges 52 are arranged at two ends of the vacuum cabin body 51; the end cover 53 is arranged at the end part of the water-cooled flange 52 far away from the vacuum cabin 51; the vacuum-pumping assembly 54 can perform vacuum-pumping treatment on the interior of the vacuum chamber 51; the crucible 2 is arranged in the vacuum chamber 51 and is in contact with the water-cooling flange 52 arranged at one end of the vacuum chamber 51;
the thermocouple 4 is arranged on the outer wall of the crucible 2; the thermocouples 4 are arranged on different sections of the high-purity graphite pipe fitting and used for monitoring the temperature of each section of the crucible 2.
Example 2
As shown in fig. 3, a device for purifying gas-phase magnesium containing an elemental silicon filter material comprises an electric furnace body 1, a crucible 2, a heating mechanism 3, a thermocouple 4 and a vacuum mechanism 5;
the crucible 2 comprises a reaction zone 21, an impurity condensation zone 22 and a crystallization zone 23 which are arranged in sequence,
the reaction zone 21 is provided with a hopper 211,
the impurity condensing region 22 is provided with a filtering member 221,
a filter material is arranged in the filter component 221, the filter material is simple substance silicon particles, and the particle size of the simple substance silicon particles is 5-10 mm;
the crystallization zone 23 is provided with a crystallizer 231;
the heating mechanism 3 is arranged in the electric furnace body 1 to heat the crucible 2;
the heating mechanism 3 comprises a first heating assembly 31, a second heating assembly 32 and a third heating assembly 33; the first heating assembly 31 heats the reaction zone 21 of the crucible 2; the second heating assembly 32 and the third heating assembly 33 heat the impurity condensation zone 22 of the crucible 2;
the crucible 2 is formed by assembling a plurality of sections of high-purity graphite pipe fittings, and the two sections of pipe fittings are connected in an inserting manner; the impurity condensing zone 22 in the crucible 2 consists of No. 1-8 high-purity graphite pipe fittings which are connected in sequence, the No. 1 high-purity graphite pipe fitting is connected with the reaction zone 21, and the No. 8 high-purity graphite pipe fitting is connected with the crystallization zone 23; the filter assembly 221 is arranged between No. 4 and No. 5 high-purity graphite pipe fittings;
the vacuum mechanism 5 comprises a vacuum cabin body 51, a water-cooling flange 52, an end cover 53 and a vacuum pumping assembly 54; the vacuum chamber 51 is arranged inside the electric furnace body 1; the water-cooling flanges 52 are arranged at two ends of the vacuum cabin body 51; the end cover 53 is arranged at the end part of the water-cooled flange 52 far away from the vacuum cabin 51; the vacuum-pumping assembly 54 can perform vacuum-pumping treatment on the interior of the vacuum chamber 51; the crucible 2 is arranged in the vacuum chamber 51 and is in contact with the water-cooling flange 52 arranged at one end of the vacuum chamber 51;
the vacuum mechanism 5 is arranged inside the electric furnace body 1;
the thermocouple 4 is arranged on the outer wall of the crucible 2; the thermocouples 4 are arranged on different sections of the high-purity graphite pipe fitting and are used for monitoring the temperature of each section of the crucible 2;
the heating mechanism 3 is arranged inside the electric furnace body 1 to heat the crucible 2.
Example 3
The method for realizing gas-phase magnesium purification based on the simple substance silicon filter material by using the device in the embodiment 1 comprises the following steps:
placing industrial crude magnesium in a hopper 211, starting a heating mechanism 3, setting the temperature of the heating mechanism 3 to be 1000 ℃, reducing the raw material, preserving the heat for 40min after the magnesium raw material is changed into magnesium vapor, starting a vacuumizing assembly 54, keeping the vacuum degree in a crucible 2 to be 20Pa, at the moment, because the simple substance silicon filter material is placed in an impurity condensation zone 22 in the crucible 2, the corresponding temperature range is 700-1000 ℃, and after reaction, collecting the high-purity magnesium on a crystallizer 231.
Example 4
The method for purifying gas-phase magnesium based on the simple substance silicon filter material by using the device in the embodiment 1 comprises the following steps:
placing industrial reducing material magnesium balls in a hopper 211, starting a heating mechanism 3, setting the temperature of the heating mechanism 3 at 1200 ℃, reducing the raw material, keeping the temperature for 60min after the magnesium raw material is changed into magnesium vapor, starting a vacuumizing assembly 54, keeping the vacuum degree in a crucible 2 at 100Pa, and collecting high-purity magnesium on a crystallizer 231 after reaction because the simple substance silicon filter material is placed in an impurity condensation zone 22 in the crucible 2 and the corresponding temperature range is 700-1000 ℃.
Example 5
The method for purifying gas-phase magnesium based on the simple substance silicon filter material by using the device of the embodiment 2 comprises the following steps:
putting metal magnesium containing impurities into a hopper 211, starting a heating mechanism 3, respectively setting the temperatures of a first heating component 31, a second heating component 32 and a third heating component 33 of the heating mechanism 3 at 850 ℃, 1000 ℃ and 800 ℃, firstly heating a second section and a third section to rated temperatures, then preserving the heat for 20-35min, then heating the first section to 850 ℃, carrying out reduction, wherein the reduction period is 345min, starting a vacuumizing component 54, keeping the vacuum degree in a crucible 2 at 100Pa, and collecting high-purity magnesium on a crystallizer 231 after reaction because an elemental silicon filter material is placed in an impurity condensation zone 22 and the corresponding temperature range is 850-900 ℃.
Example 6
The method for purifying gas-phase magnesium based on the simple substance silicon filter material by using the device of the embodiment 2 comprises the following steps:
putting metal magnesium containing impurities into a hopper 211, starting a heating mechanism 3, respectively setting the temperatures of a first heating component 31, a second heating component 32 and a third heating component 33 of the heating mechanism 3 at 850 ℃, 1000 ℃ and 800 ℃, firstly heating a second section and a third section to rated temperatures, then preserving the heat for 20-35min, then heating the first section to 850 ℃, carrying out reduction, wherein the reduction period is 345min, starting a vacuumizing component 54, keeping the vacuum degree in a crucible 2 at 100Pa, and collecting high-purity magnesium on a crystallizer 231 after reaction, wherein the corresponding temperature range is 900-1000 ℃ because the simple substance silicon filter material is placed in an impurity condensation zone 22.
Comparative example 1
The crude magnesium raw material from example 3 was distilled by vacuum distillation.
Comparative example 2
A gas-phase magnesium purification device is different from the device in the embodiment 1 in that no filter material is arranged in a crucible 22.
The method for purifying the gas-phase magnesium by using the device comprises the following steps:
placing industrial reducing material magnesium balls in a hopper 211, starting a heating mechanism 3, setting the temperature of the heating mechanism 3 at 1200 ℃, reducing the raw material, keeping the temperature for 60min after the magnesium raw material is changed into magnesium vapor, starting a vacuumizing assembly 54, keeping the vacuum degree in a crucible 2 at 100Pa, and collecting high-purity magnesium on a crystallizer 231 after reaction because the simple substance silicon filter material is placed in an impurity condensation zone 22 in the crucible 2 and the corresponding temperature range is 700-1000 ℃.
Test examples
1. The impurity components on the filter before and after the experiment of example 3 were characterized, and the results are shown in fig. 4-7, in which fig. 4 is a Scanning Electron Microscope (SEM) image on the filter before the experiment; FIG. 5 shows the energy dispersive X-ray spectroscopy (EDS) of the filter before the experiment of example 3, and the results for the respective components are shown in Table 1.
TABLE 1 EDS component analysis table on filter material before experiment
| Element(s) | Mass percent/wt. -%) | Atom percent/at% | Net |
| Si K | |||
| 100 | 100 | 723.84 |
As can be seen from the results in FIG. 4, the simple substance silicon of the filter material has a relatively flat and clean appearance before the experiment; as can be seen from fig. 5 and the results in table 1, the component on the filter medium was high-purity silicon, and no other impurities were contained.
FIG. 6 is a Scanning Electron Microscope (SEM) image of the filter after the experiment of example 3; FIG. 7 shows the energy dispersive X-ray spectroscopy (EDS) of the filter after the experiment of example 3, and the results for the respective components are shown in Table 2.
Table 2 table for EDS ingredient analysis on filter media after experiment
| Element(s) | Mass percent/wt. -%) | Atom percent/at% | Net strength |
| O K | 4.05 | 7.8 | 58.05 |
| Mn K | 5.27 | 2.96 | 33.64 |
| Mg K | 3.42 | 4.34 | 85.43 |
| Al K | 1.05 | 1.2 | 24.02 |
| Si K | 52.83 | 58.01 | 1132.36 |
| Ca K | 33.38 | 25.69 | 154.09 |
As can be seen from the results of fig. 6, after the experiment, a layer of impurities is obviously attached to the surface of the simple substance silicon of the filter material; from the results corresponding to fig. 7 and table 2, it can be seen that impurities of Ca, Mn, Al, etc. are attached to the surface of the filter medium, which shows that impurities in magnesium can be effectively removed by the method provided by the present invention.
2. The raw magnesium and the obtained magnesium of example 3 and comparative example 1 were measured for their calcium content using a spark direct-reading spectrometer, at least three points were measured, and the results were averaged and shown in fig. 8.
As can be seen from the results of fig. 8, compared with comparative example 1, the method provided by the present invention can effectively remove Ca, an impurity in magnesium vapor, because elemental silicon has a particularly good affinity for calcium.
3. The raw materials of example 4 and comparative example 2 and the obtained magnesium were subjected to component detection using a spark direct-reading spectrometer, and at least three points were detected, and the results were averaged and shown in table 3.
Table 3 results of measuring the content of impurities in the magnesium raw material and the magnesium obtained in example 2 and comparative example 2
From the results in table 3, it can be seen that the impurity in the crude magnesium can be effectively reduced by performing the method provided by the present invention with the apparatus provided by the present invention, and the content of the impurity element Ca in the magnesium raw material is reduced from 4740ppm in the raw material to less than 10 ppm; the content of Al is reduced to below 2ppm from 1764ppm in the raw material; the content of Mn is reduced to 4ppm from 111ppm in the raw material, the content of Si is less than 10ppm, and the purity of magnesium is more than 99.990%.
4. The impurity content of the post-test filter of example 5 was characterized and the results are shown in FIGS. 9-10, where FIG. 9 is a Scanning Electron Microscope (SEM) image of the pre-test filter; FIG. 10 shows the energy dispersive X-ray spectroscopy (EDS) of the filter after the experiment of example 5, and the results for the respective components are shown in Table 4.
TABLE 4 EDS compositional analysis chart on the filter after the experiment
As can be seen from FIG. 9, after the experiment of example 5, there was impurity deposition on the filter material; as can be seen from fig. 10 and the results in table 4, the impurities on the simple substance silicon filter material are deposited as Al, Si, and Ca, and it can be seen that when the magnesium vapor passes through the simple substance silicon filter material, the impurities in the magnesium vapor can be trapped on the simple substance silicon filter material, thereby removing the impurities in the magnesium vapor.
The raw material magnesium before the experiment of example 5 and the components in the high-purity magnesium obtained after the experiment were characterized by using a spark direct-reading spectrometer, at least five points were detected, and the results are shown in table 5.
Table 5 measurement results of impurity contents in magnesium raw material and magnesium obtained in example 5
From the results in table 5, it can be seen that the impurity in the crude magnesium can be effectively reduced by performing the method provided by the present invention with the apparatus provided by the present invention, and the content of the impurity element Ca in the magnesium raw material is reduced from 30ppm in the raw material to less than 10 ppm; the content of Al is reduced to below 10ppm from 265ppm in the raw materials; the content of Mn is reduced to 2ppm from 235ppm in the raw material, the content of Si is less than 10ppm, and the purity of magnesium is above 99.992%.
5. The impurity content of the filter after the experiment of example 6 was characterized and the results are shown in FIGS. 11-12. FIG. 11 is a Scanning Electron Microscope (SEM) image of the filter material before experiment; FIG. 12 shows the energy dispersive X-ray spectroscopy (EDS) of the filter after the experiment of example 6, and the results for the respective components are shown in Table 6.
| Element(s) | Mass percent/wt. -%) | Atom percent/at% |
| O K | 2.36 | 4.42 |
| F K | 1.69 | 2.66 |
| Mg K | 0.62 | 0.76 |
| Al K | 23.31 | 25.9 |
| Si K | 40.68 | 43.42 |
| Ca K | 26.44 | 19.77 |
| Ti K | 4.9 | 3.07 |
As can be seen from FIG. 11, after the experiment of example 6, a large amount of impurities are deposited on the simple substance silicon filter material; as can be seen from the results in fig. 12 and table 5, the impurities on the simple substance silicon filter material are deposited as Al, Si, Ca, etc., and it can be seen that when the magnesium vapor passes through the simple substance silicon filter material, the impurities in the magnesium vapor can be trapped on the simple substance silicon filter material, thereby removing the impurities in the magnesium vapor.
The raw material magnesium before the experiment of example 6 and the components in the high-purity magnesium obtained after the experiment were characterized by using a spark direct-reading spectrometer, at least five points were detected, and the results are shown in table 7.
TABLE 7 results of measuring the contents of impurities in the magnesium raw material and the magnesium obtained in example 6
From the results in table 7, it can be seen that the impurity in the crude magnesium can be effectively reduced by performing the method provided by the present invention with the apparatus provided by the present invention, and the content of the impurity element Ca in the magnesium raw material is reduced to less than 10 ppm; the content of Al is reduced to below 5 ppm; the Mn content is reduced to 2ppm, the Si content is reduced to 14ppm, and the purity of the magnesium is over 99.99 percent.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. A method for purifying gas-phase magnesium based on an elemental silicon filter material is characterized by comprising the following steps:
(1) placing a magnesium raw material in a reaction zone in a sealed crucible, and vacuumizing the interior of the crucible, wherein the vacuum degree of the interior of the crucible is below 100 Pa;
(2) heating the magnesium raw material by a heating mechanism until magnesium steam is generated, wherein the heating temperature is 650-;
after purification, the content of impurities Mn in the magnesium raw material is reduced to be below 4ppm, the content of Al is reduced to be below 10ppm, the content of Ca is reduced to be below 10ppm, the content of Si is reduced to be below 10ppm, and the purity of the obtained magnesium is more than 99.99 percent;
the device on which the method is based comprises an electric furnace body, a crucible, a heating mechanism, a thermocouple and a vacuum mechanism;
the crucible comprises a reaction zone, an impurity condensation zone and a crystallization zone which are arranged in sequence,
the reaction zone is provided with a hopper,
the impurity condensing zone is provided with a filtering component,
the filtering component is internally provided with a filtering material which is simple substance silicon particles, the particle size of the simple substance silicon particles is 0.1-10mm,
the crystallization zone is provided with a crystallizer;
the vacuum mechanism is arranged in the electric furnace body, and the crucible is arranged in the vacuum mechanism;
the thermocouple is arranged on the outer wall of the crucible;
the heating mechanism is arranged in the electric furnace body to heat the crucible.
2. The method for purifying magnesium in a gas phase based on an elemental silicon filter material as claimed in claim 1, wherein the heating mechanism comprises a first heating element, a second heating element and a third heating element; the first heating assembly heats a reaction zone of the crucible; the second heating assembly and the third heating assembly heat an impurity condensing region of the crucible.
3. The method for purifying gas-phase magnesium based on the elemental silicon filter material as claimed in claim 1, wherein the vacuum mechanism comprises a vacuum chamber, a water-cooled flange, an end cap and a vacuum-pumping assembly; the vacuum cabin body is arranged inside the electric furnace body; the water-cooling flanges are arranged at two ends of the vacuum cabin body; the end cover is arranged at the end part of the water-cooling flange far away from the vacuum cabin body; the vacuumizing assembly can vacuumize the interior of the vacuum cabin; the crucible is arranged inside the vacuum cabin.
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