CN1317405C - High vacuum in-situ two-step refining process for high purity material - Google Patents
High vacuum in-situ two-step refining process for high purity material Download PDFInfo
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Abstract
The present invention discloses a high vacuum in-situ two-step refining process for materials with high purity and super high purity, which is characterized in that a double-heater diffusion furnace is utilized to independently heat the upper part and the lower part of a crucible under the condition of high vacuum, so that the temperature of the crucible can be distributed in the mode of high temperature in the upper part and low temperature in the lower part, or low temperature in the upper part and high temperature in the lower part in different stages; then, the crucible is heated in two steps so as to respectively and effectively remove high saturation vapor pressure impurities and low saturation vapor pressure impurities, and finally, a process for a high purity material is obtained; the whole production process is separated from atmosphere so as to greatly reduce the pollution of atmosphere to raw materials. The process has the characteristics of high quality of products, large production capacity, stable performance, reliability, no environmental pollution, etc., and is suitable for the production of materials with high purity and super high purity, particularly for the preparation of high purity materials with high activity.
Description
Technical field
The present invention relates to a kind of high-vacuum in-situ refining method of producing high-purity and ultra-pure material, particularly distribute and remove the method for high saturated vapor pressure impurity and low saturated vapor pressure impurity in two steps, belong to high-purity and ultra-pure material field of smelting in metallurgical and the chemical industry by the control crucible temperature.
Background technology
High-purity material such as high pure metal, high-purity nonmetal and high-purity inorganic compound-material etc. have a wide range of applications at preparation compound semiconductor materials and fields such as device and Aeronautics and Astronautics, as metals such as the zinc that uses in II-VI, the III-V compound semiconductor, magnesium, calcium, aluminium, arsenic, phosphorus and its purity requirement of non-metallic material more than 99.999% (5N), otherwise too much impurity can have a strong impact on the crystallinity and the photoelectric characteristic of semiconductor material, thereby device performance is descended greatly.At present, vacuum distilling method or zone melting method etc. are adopted in the production of high pure metal more, as Chinese patent 98113973.6,200320115091.0,200320115092.5 and foreign patent KR2004022842-A, RU2236476-C1, the process for extracting of JP10121163-A etc. report, when metal is in high temperature, its vacuum tightness generally at 10 handkerchiefs between 0.01 handkerchief, residual gas in the vacuum chamber is also quite a lot of, and this refinement for the active metal is quite harmful; In addition, very big to the separation and the removal effect difference of different impurities in the refining hihg purity metal process, lack the efficient simultaneously method of removing high saturated vapor pressure and low saturated vapor pressure impurity, thereby influence total refining effect.In addition, adopt reaction method to make more, still lack the means of purifying efficiently some mineral compound materials.
Summary of the invention
The objective of the invention is provides a kind of brand-new high-purity material high-vacuum in-situ refining method at the deficiencies in the prior art, and not only refining effect is good, steady quality is reliable for this method, environmentally friendly, and refinement technique has important industrial application value.
The objective of the invention is to realize by the following technical solutions:
1) in high-vacuum in-situ refining apparatus, selects the shielding gas that is fit to the purification material for use;
2) crucible in the high-vacuum in-situ refining apparatus is divided into upper and lower two portions, its position corresponding respectively upper and lower two heater strips of diffusion furnace, just allow the top heater strip of diffusion furnace heat the top of crucible, the bottom of lower heating silk heating crucible, and, make it just in time to fill up the bottom of crucible with an amount of thick pure material crucible of packing into;
3) crucible that the material of waiting to purify will be housed imports in the diffusion furnace, and the chamber is refined in sealing, and pumping high vacuum then makes and refines chamber air pressure and be lower than 1.0 * 10
-4Pa;
4) two heater strips of independent control diffusion furnace heat the upper and lower part of crucibles and make upper temp be higher than temperature of lower, staged heating crucible is to the vertex of design temperature and keep the some time, allow having in the aperture of high saturation vapour pressure impurity by crucible cover of from raw material, being evaporated discharge, prevent that high saturated vapor pressure impurity steam from condensing on diffusion furnace top, remains the crucible upper temp in this course and be higher than the bottom;
5) reduce the temperature on crucible top, the temperature of the crucible bottom that raises simultaneously is to the vertex of design temperature and keep the some time, makes the raw materials evaporate of crucible bottom, and makes low saturated vapor pressure impurity remain in the bottom of crucible; In this step, the purification material evaporates from the bottom, condense in colder crucible top then, form high purity granular, and low saturated vapor pressure impurity remains in the crucible bottom, realize that the purification material separates with the original position of impurity, the cryogenic purpose in top is to allow near the rapid coagulation and block the crucible cover aperture crucible mouth of raw material steam;
6) diffusion furnace stops heating, and crucible cools is to room temperature, and crucible taken out from the refinement chamber moves in the transparent sealing case that is full of shielding gas; Open crucible cover, the high purity granular of crystallization on crucible top taken out;
7) collect crucible bottom impurity, and crucible is carried out matting, standby behind thorough removal of contamination;
8) to high purity granular take a sample, go-on-go, qualified product are encapsulated, then can be according to step 1) to 7 to substandard product) refine again.
Further, described high-purity material comprises that boiling point is lower than 2100 ℃ metal, nonmetal and compound.
Further, described metal comprises: lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, cadmium, europium, ytterbium or thallium, described nonmetal comprising: arsenic or selenium, described compound comprises: lithiumbromide, lithium iodide, lithium hydroxide, Sodium Bromide, sodium hydroxide, magnesium nitride or magnesium chloride.
The present invention utilizes two heater strip diffusion furnaces independently to control the temperature of crucible top and bottom, on different steps forms relative superiority or inferiority low and on low high temperature distribution, two-step approach is removed high saturated vapor pressure and low saturated vapor pressure impurity respectively under high vacuum condition: the first step crucible is removed high saturated vapor pressure impurity according to the low temperature distribution temperature-gradient method of last relative superiority or inferiority, the second step crucible forms low high temperature distribution, temperature of lower is risen to vertex keep the some time, allow the raw materials evaporate that is in the bottom, and near the crucible mouth the lower local recrystallize of temperature, the purification material is separated with low saturated vapor pressure impurity, thereby obtain high-purity material.Therefore, the present invention has following characteristics:
1, the present invention adopts high-vacuum in-situ refining apparatus to be connected fully and isolated from atmosphere with the tight of refinement chamber by watertight chest, whole process of production is all carried out under shielding gas, simultaneously according to material characteristics, can select shielding gas flexibly for use, thereby greatly reduce in the air multiple composition the pollution of high-purity material;
2, when refining material, whole refinement chamber keeps high vacuum state, and the background vacuum is 1 * 10
-4Below the handkerchief, thereby reduced the reaction that is in pyritous high-purity material and residual gas when refining and compound effectively, reduced the influence of gas widely, be particularly suitable for the purification of active material material;
3, the upper and lower part of heating crucible separately by two heater strip diffusion furnaces upper and lower part heater strip, can be on different steps forms relative superiority or inferiority low and on low high temperature distribution, two-step approach is removed high saturated vapor pressure and low saturated vapor pressure impurity respectively under high vacuum condition.Therefore, present method is removed the efficient height to plurality of impurities, is particularly suitable for the refinement requirement of high-purity and ultra-pure material;
When 4, producing, the staff isolates fully with the refinement material, and labor condition is good; The poisonous steam that produces during refinement is condensable, collect, therefore can appropriate right processing, and free from environmental pollution;
5, this high-vacuum in-situ refining method is simple to operate, convenient, constant product quality.
Description of drawings
Fig. 1 is the process flow sheet of the high vacuum in-situ two-step refining process of high-purity material of the present invention.
Fig. 2 is the used crucible structural representation of the present invention.
34 crucible tops, 35 crucible bottoms, 36 crucible cover sides are with positive, and 37 crucibles are linked up with.
Fig. 3 is the equipment schematic of the high-vacuum in-situ refining method of high-purity material of the present invention.
1 refines chamber, 2 vacuum systems, 3 special diffusion furnaces; 4 special crucibles, the material system is got in 5 chargings, 6 shielding gas devices; 7 temperature controllers, 8 refine top, chamber, and 9 refine the bottom, chamber; 10 slide valves, 11 transparent sealing chambeies, 12 molecular pumps; 13 forepumps, 14 ionic pumps, 15 ion gauges or compound gauge; 16 Pirani gauges, 17 protection gas cylinders, 18 condensation baffle plates.
Fig. 4 is the used diffusion furnace structural representation of the present invention.
19 body of heater shells, 20 radioprotective metallic cylinder, 21 PBN insulating supports, 22 top heater strips, 23 lower heating silks, 24 top thermocouples, 25 bottom thermocouples, 26 multilayer radioprotective tinsels, 27 vacuum flanges, 28 thermocouple joints, 29 power connections.
Fig. 5 a, b are respectively the photo in kind before and after the embodiment of the invention one refining hihg purity metal magnesium.
30 refine before purity be 99.95% magnesium grain, 31 purity that obtain after refining are greater than 99.999% recrystallize magnesium grain cluster.
Fig. 6 a, b are respectively the photo in kind before and after the embodiment of the invention two refining hihg purity metal calcium.
32 refine before purity be 99.5% calcium grain, 33 purity that obtain after refining are greater than 99.999% recrystallize calcium grain.
Embodiment
The present invention is described in detail below in conjunction with accompanying drawing, but can not be interpreted as limiting the scope of the invention.
The high vacuum in-situ two-step refining process of embodiment one producing high purity metal magnesium
Process flow sheet of the present invention as shown in Figure 1, utilize the concrete steps of high vacuum in-situ two-step refining process refining hihg purity metal magnesium as follows:
1) in high-vacuum in-situ refining apparatus, selects the shielding gas of high-purity argon gas for use as the magnesium of purifying metals;
2) crucible as shown in Figure 4 is divided into upper and lower two portions 34,35, its position corresponding respectively upper and lower two heater strips 22,23 of diffusion furnace as shown in Figure 4, just allow the top 34 of top heater strip 22 heating crucibles of diffusion furnace, the bottom 35 of lower heating silk 23 heating crucibles, and, make it just in time to fill up the bottom 35 of crucible with an amount of thick pure metal magnesium (99.95%) crucible of packing into;
3) will be equipped with in the crucible importing diffusion furnace of thick pure metal magnesium, the chamber is refined in sealing, and pumping high vacuum makes and refines chamber air pressure less than 1.0 * 10 then
-4Pa;
4) independently add two heater strips 22,23 of thermal diffusion furnace, upper and lower part 34,35 temperature by thermocouple control crucible make it to present the low temperature distribution of relative superiority or inferiority, and crucible top 34 temperature are higher than bottom 35 temperature 50～100 and spend; Heating crucible staged heats up, insulation is until the vertex of design temperature and keep the some time; Concrete heating step is (1) crucible bottom room temperature, and 80 ℃ on crucible top kept 5 minutes; (2) 200 ℃ of room temperatures in bottom, 280 ℃ on top kept 10 minutes, the 400 ℃ of room temperatures in (3) bottom, 480 ℃ on top kept 10 minutes; (4) 500 ℃ of room temperatures in bottom, 580 ℃ on top kept 10 minutes; (5) 600 ℃ of room temperatures in bottom, 680 ℃ on top kept 10 minutes; (6) 660 ℃ of room temperatures in bottom, 710 ℃ on top kept 20 minutes; In above-mentioned temperature-rise period, (1)～(5) step temperature rise rate be 5～20 the degree/minute, (6) step be 2～5 the degree/minute.In the temperature-rise period in this stage, remain crucible top 34 temperature and be higher than the bottom.Top 34 pyritous purposes are to allow discharge in the aperture of high saturated vapor pressure impurity by crucible cover 36 that is evaporated from thick pure metal magnesium.In order to allow the high saturated vapor pressure impurity in the thick pure magnesium grain fully evaporate, to discharge, the crucible temperature of lower in (6) step is set in the fusing point of magnesium more than 650 ℃, its objective is and allow the magnesium grain melt, the impurity that is positioned at magnesium grain the inside can be evaporated rapidly, discharge by the aperture in the crucible cover 36, thereby improve the efficient of removing high saturated vapor pressure impurity;
5) power that reduced diffusion furnace top heater strip 22 at 10 minutes in the clock time gradually is zero, thereby reduces the temperature on crucible top, the temperature to 680 of the crucible bottom 35 that raises simultaneously ℃, and kept 3 hours.In this stage, MAGNESIUM METAL is evaporated from the bottom, condenses in colder crucible top 34 then, forms high-purity magnesium grain.And low saturated vapor pressure impurity remains in the bottom of crucible, and the realization MAGNESIUM METAL is separated with the original position of impurity.Crucible top 34 cryogenic purposes are to allow near the rapid coagulation and the block crucible cover 36 apertures crucible mouth of MAGNESIUM METAL steam;
6) power that reduced diffusion furnace lower heating silk 23 at 30 minutes in the clock time gradually is zero, allows crucible cools to room temperature then, crucible is taken out move in the transparent sealing case that is full of high-purity argon gas from refine the chamber; Open crucible cover 36, the high-purity magnesium grain of crystallization on crucible top 34 taken out;
7) collect crucible bottom impurity, and crucible is carried out matting, standby behind thorough removal of contamination;
8) to high-purity magnesium grain take a sample, go-on-go, qualified product are encapsulated, then can be according to step 1) to 7 to substandard product) refine again.
Be illustrated in figure 4 as the structural representation of crucible, crucible is divided into top 34 and bottom 35 two portions, on its mouthful a crucible cover 36 is arranged, can with the crucible tight joint, it is that aperture about 1mm is used for discharging high saturated vapor pressure impurity that equally distributed aperture is arranged on the crucible cover.In crucible, load onto an amount of raw material, make it just in time to fill up crucible bottom 35.Hook 37 is arranged at crucible top 34, is used for sending and gets crucible.The crucible main body adopts materials such as high-purity PBN, high purity quartz or high-purity ceramic to make, crucible cover 36, the hook 37 high-purity refractory materials of employing such as High-purity Tantalum, niobium, molybdenum, PBN, quartz, high-purity corundum pottery etc. are made, thereby it is at high temperature pollution-free to guarantee to be refined starting material.
Be illustrated in figure 3 as the structural representation of the high-vacuum in-situ refining equipment of high pure metal calcium of the present invention, this equipment comprises refinement chamber 1, vacuum system 2; special diffusion furnace 3, special crucible 4, material system 5 is got in charging; shielding gas device 6, temperature controller 7, transparent sealing chamber 11; molecular pump 12, forepump 13, ionic pump 14; ion gauge or compound gauge 15; Pirani gauge 16, protection gas cylinder 17, condensation baffle plate 18.Wherein, refine chamber 1 by refining top, chamber 8 and refining bottom, chamber 9 two portions and form, they connect by slide valve 10.
Be illustrated in figure 4 as the diffusion furnace structural representation of extracting high-purity material, on PBN insulating support 21, be wound with upper and lower two-layer independent heater strip, be top heater strip 22 and lower heating silk 23, its position just in time corresponding the top 34 and bottom 35 of crucible, can realize independent control to crucible upper and lower part 34,35 temperature, on different steps forms relative superiority or inferiority low and on low high temperature distribution.As shown in Figure 4, other parts of stove are body of heater shell 19, radioprotective metallic cylinder 20, PBN insulating support 21, top heater strip 22, lower heating silk 23, top thermocouple 24, bottom thermocouple 25, multilayer radioprotective tinsel 26, vacuum flange 27, thermocouple joint 28, power connection 29; Wherein body of heater shell 19, radioprotective tinsel 26, heater strip 22,23 are high-purity refractory material as being not less than 99.99% High-purity Tantalum, niobium, molybdenum etc., and it is at high temperature pollution-free to guarantee to be refined starting material.
The advantage of two-step approach refinement material is to remove high saturated vapor pressure and low saturated vapor pressure impurity respectively under high vacuum condition.The first step crucible is removed high saturated vapor pressure impurity according to the low temperature distribution temperature-gradient method of last relative superiority or inferiority; High saturated vapor pressure impurity evaporates then from raw material discharges from the aperture of crucible cover; The purpose that the crucible upper temp is high is to stop impurity steam to condense on top.The second step crucible forms low high temperature distribution, temperature of lower is risen to vertex keeps the some time, allow the raw materials evaporate that is in the bottom, and near the crucible mouth the lower local recrystallize of temperature, the purification material is separated with low saturated vapor pressure impurity, reach the purpose of extracting high-purity material.
Be depicted as the photo in kind of using the high-purity magnesium of the embodiment of the invention one refinement front and back as Fig. 5 a, b.Magnesium grain 30 before refining is commercially available 99.95% MAGNESIUM METAL, utilize the present invention to refine after, near the crucible mouth, obtained the magnesium grain cluster 31 of recrystallize.Magnesium grain for primary purification can carry out secondary, three times or repeatedly purification, to obtain ultra-high purity metal magnesium.We utilize the inductively coupled plasma emission spectrometer preceding to refining, once refine and the impurity that MAGNESIUM METAL comprised of secondary after refining is tested, its result is as shown in table 1; The result shows that the purity of utilizing high vacuum in-situ two-step refining process of the present invention once to refine the back MAGNESIUM METAL reaches more than 99.995%, and the purity after the secondary refinement reaches more than 99.9992%, satisfy of the harsh requirement of industries such as semi-conductor, Aeronautics and Astronautics fully, have very big economic benefit and social benefit MAGNESIUM METAL purity.
Analysis before purity that table 1 once refines for the present invention, secondary refines the high-purity magnesium of gained and contained major impurity and the refinement relatively
| Refine number of times | The content of major impurity (ppm) in the MAGNESIUM METAL | The purity of magnesium (%) magnesium (Mg) | ||
| Zinc (Zn) | Silicon (Si) | Iron (Fe) | ||
| Refine and once refine the secondary refinement | 53 0.9 0.2 | 47 8.2 1.9 | 35 1.4 0.2 | 99.95％ ≥99.995％ ≥99.9992％ |
The high vacuum in-situ two-step refining process of embodiment two high pure metal calcium
Process flow sheet of the present invention as shown in Figure 1, utilize the concrete steps of high vacuum in-situ two-step refining process refining hihg purity metal calcium as follows:
1) in high-vacuum in-situ refining apparatus, selects the shielding gas of high-purity argon gas for use as the calcium of purifying metals;
2) crucible as shown in Figure 4 is divided into upper and lower two portions 34,35, its position corresponding respectively upper and lower two heater strips 22,23 of diffusion furnace as shown in Figure 4, just allow the top 34 of top heater strip 22 heating crucibles of diffusion furnace, the bottom 35 of lower heating silk 23 heating crucibles, and, make it just in time to fill up the bottom 35 of crucible with an amount of thick pure metal calcium (99.5%) crucible of packing into;
3) will be equipped with in the crucible importing diffusion furnace of thick pure metal calcium, the chamber is refined in sealing, and pumping high vacuum makes and refines chamber air pressure less than 1.0 * 10 then
-4Pa;
4) independently add two heater strips 22,23 of thermal diffusion furnace, upper and lower part 34,35 temperature by thermocouple control crucible make it to present the low temperature distribution of relative superiority or inferiority, and crucible top 34 temperature are higher than bottom 35 temperature 20～100 and spend; Heating crucible staged heating and heat preservation is until the vertex of design temperature and keep the some time; Concrete heating step is (1) crucible bottom room temperature, and 80 ℃ on crucible top kept 5 minutes; (2) 200 ℃ of room temperatures in bottom, 280 ℃ on top kept 10 minutes, the 500 ℃ of room temperatures in (3) bottom, 580 ℃ on top kept 10 minutes; (4) 650 ℃ of room temperatures in bottom, 720 ℃ on top kept 10 minutes; (5) 800 ℃ of room temperatures in bottom, 850 ℃ on top kept 10 minutes; (6) 850 ℃ of room temperatures in bottom, 880 ℃ on top kept 10 minutes; In above-mentioned temperature-rise period, (1)～(5) step temperature rise rate be 5 the degree/minute, (6) step be 2 the degree/minute.In the temperature-rise period in this stage, remain the crucible upper temp and be higher than the bottom.Top pyritous purpose is to allow discharge in the aperture of high saturated impurity by crucible cover that is evaporated from thick pure metal calcium.In order to allow the high saturated vapor pressure impurity in the thick pure calcium grain fully evaporate, to discharge, the crucible temperature of lower in (6) step is set in the fusing point of calcium more than 842 ℃, its objective is and allow the calcium grain melt, the impurity that is positioned at calcium grain the inside can be evaporated rapidly, discharge by the aperture in the crucible cover, thereby improve the efficient of removing high saturated vapor pressure impurity.
5) power that reduced diffusion furnace top heater strip 22 at 15 minutes in the clock time gradually is zero, thereby reduces the temperature on crucible top, the temperature to 860 of the crucible bottom 35 that raises simultaneously ℃, and kept 3 hours.In this stage, calcium metal evaporates from the bottom, condenses in colder crucible top 34 then, forms high-purity calcium grain.And low saturated vapor pressure impurity remains in the bottom of crucible, realizes that calcium metal separates with the original position of impurity.Crucible top 34 cryogenic purposes are to allow near the rapid coagulation and the block crucible cover 36 apertures crucible mouth of calcium metal steam;
6) power that reduced diffusion furnace lower heating silk 23 at 30 minutes in the clock time gradually is zero, allows crucible cools to room temperature then, crucible is taken out move in the transparent sealing case that is full of high-purity argon gas from refine the chamber; Open crucible cover 36, the high-purity calcium grain of crystallization on crucible top 34 taken out;
7) collect crucible bottom impurity, and crucible is carried out matting, standby behind thorough removal of contamination;
8) to high-purity calcium grain take a sample, go-on-go, qualified product are encapsulated, then can be according to step 1) to 7 to substandard product) refine again.
II family element calcium and magnesium all belong to the active metal, have many similar character, therefore it is similar to utilize the present invention to refine the processing step of high-purity magnesium, calcium, difference is that the fusing point of calcium is than magnesium height, its saturation steam is pressed under the uniform temp lower than magnesium simultaneously, therefore in above-mentioned steps 4) with 5) in each section refine also height when refining magnesium of temperature, but refining effect is very approaching, and the purification of the very suitable active metal of the present invention is described.
Shown in Fig. 6 a, the b is the photo in kind of the embodiment of the invention two extracting metals calcium front and back.Calcium bits 32 before refining be commercially available 99.5% calcium metal, utilize the inventive method refinement after, near the crucible mouth, obtained the granules of metal Ca 33 of recrystallize.We utilize the inductively coupled plasma emission spectrometer preceding to refining, once refine and the major impurity that calcium metal comprised of secondary after refining tested, its result is as shown in table 2; The result shows that the purity of utilizing high vacuum in-situ two-step refining process of the present invention once to refine the back calcium metal reaches more than 99.99%, and the purity after the secondary refinement reaches more than 99.999%, satisfy the demand of most advanced and sophisticated industries such as semiconductor material and device, aerospace fully, have very big economic benefit and social benefit.
Analysis before purity that table 2 once refines for the present invention, secondary refines the high-purity calcium of gained and contained major impurity and the refinement relatively
| Refine number of times | The content of major impurity (ppm) in the calcium metal | The purity of calcium (%) calcium (Ca) | ||
| Magnesium (Mg) | Silicon (Si) | Copper (Cu) | ||
| Refine and once refine the secondary refinement | 530 2.9 0.6 | 247 17 2.7 | 335 4.4 0.2 | 99.5％ ≥99.99％ ≥99.999％ |
The high vacuum in-situ two-step refining process of embodiment three high purity sodium hydroxide
Process flow sheet of the present invention as shown in Figure 1, utilize the concrete steps of high vacuum in-situ two-step refining process refinement high purity sodium hydroxide as follows:
1) in high-vacuum in-situ refining apparatus, selects the shielding gas of high-purity argon gas for use as the purified hydrogen sodium oxide;
2) crucible as shown in Figure 4 is divided into upper and lower two portions 34,35, its position corresponding respectively upper and lower two heater strips 22,23 of diffusion furnace as shown in Figure 4, just allow the top 34 of top heater strip 22 heating crucibles of diffusion furnace, the bottom 35 of lower heating silk 23 heating crucibles, and, make it just in time to fill up the bottom 35 of crucible with an amount of thick pure cerium hydroxide sodium (97%) crucible of packing into;
3) will be equipped with in the crucible importing diffusion furnace of thick pure cerium hydroxide sodium, the chamber is refined in sealing, and pumping high vacuum makes and refines chamber air pressure less than 1.0 * 10 then
-4Pa;
4) independently add two heater strips 22,23 of thermal diffusion furnace, upper and lower part 34,35 temperature by thermocouple control crucible make it to present the low temperature distribution of relative superiority or inferiority, and crucible top 34 temperature are higher than bottom 35 temperature 20～100 and spend; Heating crucible staged heating and heat preservation is until the vertex of design temperature and keep the some time; Concrete heating step is (1) crucible bottom room temperature, and 80 ℃ on crucible top kept 5 minutes; (2) 300 ℃ of room temperatures in bottom, 350 ℃ on top kept 10 minutes, the 330 ℃ of room temperatures in (3) bottom, 360 ℃ on top kept 10 minutes; (4) 780 ℃ of room temperatures in bottom, 800 ℃ on top kept 20 minutes; In above-mentioned temperature-rise period, (1)～(2) step temperature rise rate be 3 the degree/minute, (3) step be 1 the degree/minute, (4) step be 3 the degree/minute, in the temperature-rise period in this stage, remain the crucible upper temp and be higher than the bottom.Top pyritous purpose is to allow discharge in the aperture of high saturated impurity by crucible cover that is evaporated from thick pure cerium hydroxide sodium.Because the fusing point of sodium hydroxide is 318 ℃, in this temperature, combine with residual water and the water sodium hydroxide that forms will decompose and be evaporated rapidly, need slowly to heat up in this temperature, therefore, above-mentioned the 3rd step employing 1 spends/minute temperature rise rate.Thick pure cerium hydroxide sodium particle is after the fusing of the 3rd step, and the steam of the inside and other high saturated vapor pressure impurity fully evaporate, discharge.Major impurity yellow soda ash in the thick pure cerium hydroxide sodium begins to have carbonic acid gas to decompose out in the time of 400 ℃, and therefore in above-mentioned (4) step, the crucible temperature of lower is set in this more than temperature, its objective is to allow yellow soda ash resolve into carbonic acid gas and rapid evaporation.
5) power that reduced diffusion furnace top heater strip 22 at 15 minutes in the clock time gradually is zero, thereby reduces the temperature on crucible top, the temperature to 790 of the crucible bottom 35 that raises simultaneously ℃, and kept 4 hours.In this stage, sodium hydroxide evaporates from the bottom, condenses in colder crucible top 34 then, forms the high purity sodium hydroxide grain.And low saturated vapor pressure impurity remains in the bottom of crucible, realizes that sodium hydroxide separates with the original position of impurity.Crucible top 34 cryogenic purposes are to allow near the rapid coagulation and the block crucible cover 36 apertures crucible mouth of sodium hydroxide steam;
6) power that reduced diffusion furnace lower heating silk 23 at 30 minutes in the clock time gradually is zero, allows crucible cools to room temperature then, crucible is taken out move in the transparent sealing case that is full of high-purity argon gas from refine the chamber; Open crucible cover 36, the high purity sodium hydroxide grain of crystallization on crucible top 34 taken out;
7) collect crucible bottom impurity, and crucible is carried out matting, standby behind thorough removal of contamination;
8) to the high purity sodium hydroxide grain take a sample, go-on-go, qualified product are encapsulated, then can be according to step 1) to 7 to substandard product) refine again.
We utilize the inductively coupled plasma emission spectrometer preceding to refining, once refine and the major impurity that sodium hydroxide comprised of secondary after refining tested, its result is as shown in table 3; The result shows that the purity of utilizing high vacuum in-situ two-step refining process of the present invention once to refine back sodium hydroxide reaches more than 99.5%, and the purity after the secondary refinement reaches more than 99.95%, therefore utilizes purified hydrogen sodium oxide of the present invention to have good effect.
Analysis before purity that table 3 once refines for the present invention, secondary refines gained sodium hydroxide and contained major impurity and the refinement relatively
| Refine number of times | The content of major impurity in the sodium hydroxide | The purity NaOH of sodium hydroxide (%) | ||
| Carbon (C) | Potassium (K) | Silver (Ag) | ||
| Refine and once refine the secondary refinement | 0.21％ 0.02％ 30ppm | 0.02％ 0.003％ 4ppm | 0.002％ 0.0005％ 1ppm | 97％ ≥99.5％ ≥99.95％ |
The boiling point that the present invention can be applied to beyond demagging, calcium and the sodium hydroxide equally is lower than 2100 ℃ metal, nonmetal and compound, as lithium, sodium, potassium, strontium, barium, zinc, cadmium, europium, ytterbium, thallium, arsenic, selenium, lithiumbromide, lithium iodide, lithium hydroxide, Sodium Bromide, magnesium nitride, magnesium chloride etc.
Claims (3)
1, a kind of high vacuum in-situ two-step refining process of extracting high-purity material is characterized in that comprising the following steps:
1) in high-vacuum in-situ refining apparatus, selects the shielding gas that is fit to the purification material for use;
2) crucible in the high-vacuum in-situ refining apparatus is divided into upper and lower two portions, its position corresponding respectively upper and lower two heater strips of diffusion furnace, just allow the top heater strip of diffusion furnace heat the top of crucible, the bottom of lower heating silk heating crucible, and, make it just in time to fill up the bottom of crucible with an amount of thick pure material crucible of packing into;
3) crucible that the material of waiting to purify will be housed imports in the diffusion furnace, and the chamber is refined in sealing, and pumping high vacuum then makes and refines chamber air pressure and be lower than 1.0 * 10
-4Pa;
4) two heater strips of independent control diffusion furnace heat the upper and lower part of crucibles and make upper temp be higher than temperature of lower, staged heating crucible is to the vertex of design temperature and keep the some time, allow having in the aperture of high saturation vapour pressure impurity by crucible cover of from raw material, being evaporated discharge, prevent that high saturated vapor pressure impurity steam from condensing on diffusion furnace top, remains the crucible upper temp in this course and be higher than the bottom;
5) reduce the temperature on crucible top, the temperature of the crucible bottom that raises simultaneously is to the vertex of design temperature and keep the some time, makes the raw materials evaporate of crucible bottom, and makes low saturated vapor pressure impurity remain in the bottom of crucible; In this step, the purification material evaporates from the bottom, condense in colder crucible top then, form high purity granular, and low saturated vapor pressure impurity remains in the bottom of crucible, realize that the purification material separates with the original position of impurity, the cryogenic purpose in top is to allow near the rapid coagulation and block the crucible cover aperture crucible mouth of raw material steam;
6) diffusion furnace stops heating, and crucible cools is to room temperature, and crucible taken out from the refinement chamber moves in the transparent sealing case that is full of shielding gas; Open crucible cover, the high purity granular of crystallization on crucible top taken out;
7) collect crucible bottom impurity, and crucible is carried out matting, standby behind thorough removal of contamination;
8) to high purity granular take a sample, go-on-go, qualified product are encapsulated, then can be according to step 1) to 7 to substandard product) refine again.
2, the high vacuum in-situ two-step refining process of a kind of extracting high-purity material according to claim 1 is characterized in that, described high-purity material comprises that boiling point is lower than 2100 ℃ metal, nonmetal and compound.
3, the high vacuum in-situ two-step refining process of a kind of extracting high-purity material according to claim 2, it is characterized in that, described metal comprises: lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, cadmium, europium, ytterbium or thallium, described nonmetal comprising: arsenic or selenium, described compound comprises: lithiumbromide, lithium iodide, lithium hydroxide, Sodium Bromide, sodium hydroxide, magnesium nitride or magnesium chloride.
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| CNB2005101054546A CN1317405C (en) | 2005-09-28 | 2005-09-28 | High vacuum in-situ two-step refining process for high purity material |
| US12/067,835 US7753987B2 (en) | 2005-09-28 | 2006-04-11 | High vacuum in-situ refining method for high-purity materials and an apparatus thereof |
| PCT/CN2006/000645 WO2007036094A1 (en) | 2005-09-28 | 2006-04-11 | A high vacuum in-situ refining method for high-purity materials and a apparatus thereof |
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| CNB2005101054546A CN1317405C (en) | 2005-09-28 | 2005-09-28 | High vacuum in-situ two-step refining process for high purity material |
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| CN1317405C true CN1317405C (en) | 2007-05-23 |
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| CN101386919B (en) * | 2008-10-24 | 2011-12-28 | 贵阳铝镁设计研究院有限公司 | High-pure magnesium preparation method and apparatus |
| JP5290387B2 (en) * | 2011-12-07 | 2013-09-18 | Ｊｘ日鉱日石金属株式会社 | Method for producing high purity calcium |
| CN102766769B (en) * | 2012-07-12 | 2014-08-06 | 东莞宜安科技股份有限公司 | Method for high-vacuum low-temperature purification of high-purity magnesium and purification device |
| CN103557704B (en) * | 2013-10-12 | 2015-12-09 | 深圳市华星光电技术有限公司 | Crucible heating Apparatus and method for |
| CN104674016B (en) * | 2015-02-09 | 2017-04-19 | 牛强 | Method and device for condensing magnesium vapor generated by evaporation and heat absorption of magnesium liquid and coproducing refined magnesium |
| CN105063375B (en) * | 2015-09-02 | 2017-06-23 | 班辉 | A kind of method of vacuum-thermal reduction mode high-purity metal caesium |
| CN105543510A (en) * | 2016-01-04 | 2016-05-04 | 李梅 | Method for preparing rare earth chloride from mixed rare earth concentrate or monazite concentrate |
| CN107586970A (en) * | 2017-09-06 | 2018-01-16 | 长沙科力威蒸馏技术有限公司 | A kind of method for purifying magnesium |
| CN107937738A (en) * | 2017-12-21 | 2018-04-20 | 李本根 | A kind of new purifying plant for rare earth feed liquid |
| CN109082542B (en) * | 2018-02-24 | 2019-05-07 | 虔东稀土集团股份有限公司 | A method of it preparing the vacuum drying oven of high pure metal ytterbium and its prepares high pure metal ytterbium |
| CN111424184B (en) * | 2020-04-17 | 2022-04-22 | 包头稀土研究院 | Method for preparing high-purity metal ytterbium by one-time continuous reduction distillation |
| CN111440947B (en) * | 2020-04-17 | 2022-02-15 | 包头稀土研究院 | Method for preparing metal ytterbium by reducing and distilling ytterbium oxide raw material |
| CN112374474B (en) * | 2020-11-13 | 2022-10-21 | 广东先导微电子科技有限公司 | Preparation method of compact ultrahigh-purity material |
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