CN115896482A - Preparation method of high-purity metal zirconium - Google Patents
Preparation method of high-purity metal zirconium Download PDFInfo
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- CN115896482A CN115896482A CN202211672075.5A CN202211672075A CN115896482A CN 115896482 A CN115896482 A CN 115896482A CN 202211672075 A CN202211672075 A CN 202211672075A CN 115896482 A CN115896482 A CN 115896482A
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 115
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000002184 metal Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 37
- 239000011575 calcium Substances 0.000 claims abstract description 37
- 238000010894 electron beam technology Methods 0.000 claims abstract description 30
- 238000006192 iodination reaction Methods 0.000 claims abstract description 26
- 230000026045 iodination Effects 0.000 claims abstract description 25
- 239000010419 fine particle Substances 0.000 claims abstract description 23
- 238000000746 purification Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 14
- 238000003723 Smelting Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 230000002083 iodinating effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005660 chlorination reaction Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- OWDMWYGPNPPHFN-UHFFFAOYSA-N calcium;oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Zr+4] OWDMWYGPNPPHFN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000125 calcaemic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a preparation method of high-purity metal zirconium, and belongs to the field of metal preparation. According to the preparation method of the high-purity metal zirconium, zirconium oxide is directly prepared into fine-particle metal zirconium through a calcium thermal reduction method, then the fine-particle metal zirconium is pressed into an electrode and then is smelted through an electron beam cold bed, and finally, the high-purity metal zirconium is obtained through iodination and purification, so that the problems that the process for preparing the high-purity metal zirconium is complex, the equipment operation and maintenance cost is high, the labor cost is high and the like are solved. Compared with the traditional process for preparing high-purity metal zirconium by obtaining sponge zirconium through chlorination reduction, the technical scheme adopted by the invention does not use chlorine and various separation reagents, generates less waste and is easy to recycle. The calcium zirconium oxide is thermally reduced into fine-particle metal zirconium with high gas impurity content, other low-melting-point high-volatility metal impurities and gas impurities can be removed through electron beam cold bed smelting, and finally, the high-purity metal zirconium is obtained through further purification through iodination, wherein the content of impurities such as oxygen, calcium and the like in the product is low, and the purity is more than or equal to 99.95%.
Description
Technical Field
The invention belongs to the field of metal preparation, and particularly relates to a preparation method of high-purity metal zirconium.
Background
The following processes are mainly used for preparing high-purity metal zirconium in industry:
firstly, zirconium oxide is chloridized into zirconium tetrachloride, then sponge zirconium with lower purity is obtained through magnesiothermic reduction, and then the sponge zirconium is further purified through methods such as fused salt electrolysis, iodination refining or zone melting.
Secondly, after the zirconium oxide is chloridized into zirconium tetrachloride, the zirconium tetrachloride is purified, hydrolyzed and extracted to obtain high-purity zirconium oxide, then nuclear-grade sponge zirconium is obtained through chlorination and magnesiothermic reduction, and high-purity metal zirconium ingots are prepared through arc or electron beam melting.
In the prior art, the chlorination step can not avoid serious corrosion to equipment, high equipment cleaning and maintenance cost, high harm of three wastes to workers, high treatment or recovery cost and the like, and the development of the high-purity metal zirconium industry is restricted.
Disclosure of Invention
In order to solve the problems of preparing high-purity metal zirconium in the prior art, the invention provides a preparation method of high-purity metal zirconium, which is characterized in that zirconium oxide is directly prepared into fine-particle metal zirconium by a calcium thermal reduction method, then the fine-particle metal zirconium is pressed into an electrode and then is smelted by an electron beam cold hearth, and finally, the high-purity metal zirconium is obtained by iodination and purification, so that the problems of complex process, high equipment operation and maintenance cost, high labor cost and the like in the preparation of the high-purity metal zirconium are solved.
The main technical scheme of the invention is as follows:
a preparation method of high-purity metal zirconium comprises the following steps:
(1) Calcium thermal reduction:
putting zirconium oxide, anhydrous calcium chloride and metallic calcium into a reaction furnace, carrying out reduction reaction under a protective atmosphere, and respectively carrying out acid washing and water washing on a reduction product to remove impurities so as to prepare fine-particle metallic zirconium.
The reduction product is a mixture of fine-particle metal zirconium, calcium chloride, calcium oxide and fine-particle metal calcium, the calcium chloride, the calcium oxide and the fine-particle metal calcium are removed through low-concentration acid washing, and the acid washing reaction product is water-soluble calcium chloride, hydrogen which is easy to recycle and treat and solid fine-particle metal zirconium; then washing, filtering and drying to obtain the fine-particle metal zirconium. The oxygen content in the fine particle metal zirconium is 1-3 percent, and the calcium content is less than 0.3 percent.
(2) Electron beam cold bed smelting:
pressing fine particle metal zirconium into an electrode block, placing the electrode block in an electron beam cold bed furnace, and melting, refining, solidifying and cooling the raw materials to obtain a zirconium ingot.
The fine particle zirconium metal is smelted by an electron beam cold bed for 1 time, the oxygen content in a zirconium ingot is less than 0.2 percent, and the recovery rate is more than or equal to 97 percent. The electron beam cold bed smelting mainly aims at reducing the content of oxygen, chlorine and calcium in raw materials, ensuring the smooth proceeding of subsequent iodination and purification and effectively improving the yield and purity of high-purity zirconium.
(3) Iodination and purification:
turning a zirconium ingot smelted by an electron beam into zirconium scraps, pressing the zirconium scraps into cakes, filling the cakes into a reactor of an iodinating furnace, placing the reactor in a salt bath furnace, controlling the temperature of a mother wire in the reactor to 1350-1450 ℃, adding iodine to perform iodination purification, crystallizing zirconium on the mother wire, taking out the reactor after the reaction is finished, cooling, and taking out the crystallized zirconium to obtain the high-purity zirconium metal.
The main purpose of the iodination purification is to further purify the coarse material obtained by melting in an electron beam cold hearth furnace, and the purity of the crystallized zirconium obtained by the iodination reaction can reach more than 99.95 percent
In the step (1), the mass ratio of the zirconium oxide to the metallic calcium is 1.66-1.25, and the mass ratio of the metallic calcium to the anhydrous calcium chloride is 1.
The reduction reaction temperature in the step (1) is 1120-1374K.
The reduction reaction time in the step (1) is 8-60h.
The protective atmosphere in the step (1) is argon ， Protection ofThe flow rate of the atmosphere is more than or equal to 5L/min. Before introducing the protective atmosphere, the reaction furnace is vacuumized to less than or equal to 10Pa, and argon is introduced to wash the furnace for a plurality of times.
Before the smelting in the step (2), the electron beam cold bed furnace is vacuumized, and the vacuum degree is not more than 3.0 x 10 -3 Pa。
And (3) controlling the current of the melting zone in the step (2) to be 8-10A and the power to be 220-300kw.
And (3) controlling the current of the refining area in the step (2) to be 2-3A and controlling the power to be 40-80kw.
And (3) controlling the current of the solidification region in the step (2) to be 3-5A and the power to be 80-150kw.
The cooling time in the step (2) is 1-6h.
Before the iodination in the step (3), the reactor needs to be vacuumized, and the vacuum degree is less than or equal to 6.0 to 10 -3 Pa。
The temperature of the salt bath furnace in the step (3) is controlled to be 240-300 ℃.
The fine particle metal zirconium obtained by calcium thermal reduction can be smelted for multiple times only by adopting an electron beam cold bed smelting method to obtain a product with higher purity, and the fine particle metal zirconium can be greatly lost in multiple electron beam bombardment processes, so that the product yield is reduced; because the fine particle zirconium metal has high impurity content, the production efficiency is low by direct iodination purification, and the product yield is extremely low. Therefore, the electrode pressing step is added to reduce the loss in the electron beam bombardment process, the iodination purification is carried out after the primary electron beam cold bed smelting, and the two smelting modes are combined, so that the production efficiency and the product yield are improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts the method of combining calcium thermal reduction, smelting and iodination to prepare the zirconium oxide raw material into the high-purity metal zirconium, and has the advantages of short process flow, simple equipment structure, low maintenance cost and low labor cost.
2. Compared with the traditional process for preparing high-purity metal zirconium by sponge zirconium obtained by chlorination reduction, the technical scheme adopted by the invention does not use chlorine and various separation reagents, generates less waste and is easy to recycle.
3. The calcium zirconium oxide is thermally reduced into fine-particle metal zirconium with high gas impurity content, other low-melting-point high-volatility metal impurities and gas impurities can be removed through electron beam cold bed smelting, and finally, the high-purity metal zirconium is obtained through further purification through iodination, wherein the content of impurities such as oxygen, calcium and the like in the product is low, and the purity is more than or equal to 99.95%.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be described in further detail with reference to specific embodiments. It should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without inventive step, are within the scope of protection of the invention.
Example 1
S1, weighing zirconia, metallic calcium and anhydrous calcium chloride according to a weight ratio of 1. Firstly, putting a part of anhydrous calcium chloride into a crucible, then uniformly mixing zirconium oxide and metal calcium, putting the mixture into the crucible, and finally adding the rest anhydrous calcium chloride. Vacuumizing to less than or equal to 10Pa, and introducing argon to wash the furnace for 3 times. The reduction is carried out under the protection of argon with the flow rate of 5L/min, the reduction temperature is 1174K, and the reduction time is 8h. The reduced product was washed in 2% dilute hydrochloric acid, left to stand, and the precipitate was washed with water 3 times, filtered, and vacuum-dried at 130 ℃ to obtain 362.3kg of particulate metallic zirconium. The oxygen content of the fine-grained metal zirconium was measured by an ONH analyzer to be about 2.5%, and the calcium content was measured by ICP-OES to be 0.22%.
S2, placing the fine-particle metal zirconium in a 50-20-10 mm size die, pressing under the pressure of 60MPa for 2min, and pressing into an electrode block. The pressed electrode blocks are arranged in a zirconium material feeding box and are loaded into an electron beam cold bed furnace, and the electron beam cold bed furnace is vacuumized to be less than or equal to 3.0 x 10 -3 And Pa, melting the electrode block into a zirconium ingot through raw material melting, refining, solidifying and cooling to obtain 340.7kg of zirconium ingot. The current of a melting zone is controlled to be 8-10A in the melting process, and the power is 220-300kw. The current of the refining zone is controlled at 2-3A, and the power is 40-80kw; controlling the current of the solidification region to be 3-5A, and controlling the power to be 80-150kw; the cooling time was 2h.
S3, melting the zirconiumIngot scraps are pressed into zirconium cakes with the diameter less than or equal to 50mm, the zirconium cakes are filled into a reactor of an iodization furnace, the reactor is placed in a salt bath furnace, the reactor is vacuumized, and the vacuum degree is less than or equal to 6.0 x 10 -3 Pa, controlling the temperature of a salt bath furnace at 240-300 ℃, controlling the temperature of a mother wire in a reactor at 1370 ℃, adding iodine for iodination and purification, crystallizing zirconium on the mother wire, taking out the reactor after the reaction is finished, cooling, and taking out the crystallized zirconium to obtain 326.9kg of high-purity metal zirconium, wherein the purity of the product reaches 99.95%.
The yield of the high-purity zirconium is 88.3 percent by calcium thermal reduction, electron beam cold bed smelting and iodination purification.
Example 2
S1, weighing zirconia, metallic calcium and anhydrous calcium chloride according to a weight ratio of 1.79. Firstly, putting a part of anhydrous calcium chloride into a crucible, then uniformly mixing zirconium oxide and metal calcium, putting the mixture into the crucible, and finally adding the rest anhydrous calcium chloride. Vacuumizing to less than or equal to 10Pa, and introducing argon to wash the furnace for 3 times. And (3) carrying out reduction under the protection of argon at the flow rate of 6L/min, wherein the reduction temperature is 1254K, and the reduction time is 30h. The reduced product is washed in 3% dilute hydrochloric acid, and then is kept stand, and the precipitate is washed with water and filtered for 3 times, and is dried in vacuum at 130 ℃ to obtain 364.3kg of granular metal zirconium. The oxygen content of the fine-grained metal zirconium was determined to be about 1.8% by ONH analyzer and the calcium content was determined to be 0.25% by ICP-OES.
S2, carrying out static pressing on the fine particle metal zirconium to form an electrode block with the size of 1000 × 120 × 150mm, the pressure of 100MPa and the time of 2min. Arranging the pressed electrode blocks in a zirconium material feeding box, arranging the pressed electrode blocks in the zirconium material feeding box, and filling the zirconium material feeding box into an electron beam cold bed furnace, wherein the electron beam cold bed furnace is vacuumized to be less than or equal to 3.0 x 10 -3 And Pa, melting the electrode block into a zirconium ingot through raw material melting, refining, solidifying and cooling to obtain 335.7kg of zirconium ingot. The current of the melting zone is controlled to be 8-10A in the melting process, and the power is 220-300kw. Controlling the current of the refining zone at 2-3A and the power at 40-80kw; controlling the current of the solidification region to be 3-5A, and controlling the power to be 80-150kw; the cooling time was 4h.
S3, turning and pressing the melted zirconium ingot into zirconium cakes with the diameter less than or equal to 50mm, and filling the zirconium cakes into an iodizing furnaceIn the reactor, the reactor is placed in a salt bath furnace, the reactor is vacuumized, and the vacuum degree is less than or equal to 6.0 x 10 -3 Pa, controlling the temperature of a salt bath furnace at 240-300 ℃, controlling the temperature of a female wire in a reactor at 1430 ℃, adding iodine for iodination and purification, crystallizing zirconium on the female wire, taking out the reactor after the reaction is finished, cooling, and taking out the crystallized zirconium to obtain 327.7kg of high-purity zirconium, wherein the purity of the product reaches 99.98%.
The yield of the high-purity zirconium obtained by calcium thermal reduction, electron beam cold bed smelting and iodination purification is 88.5%.
Example 3
S1, weighing zirconia, anhydrous calcium chloride and metallic calcium according to a weight ratio of 1. Firstly, putting a part of anhydrous calcium chloride into a crucible, then uniformly mixing zirconium oxide and metal calcium, putting the mixture into the crucible, and finally adding the rest anhydrous calcium chloride. Vacuumizing to less than or equal to 10Pa, and introducing argon to wash the furnace for 3 times. And (3) carrying out reduction under the protection of argon at the flow rate of 7L/min, wherein the reduction temperature is 1374K, and the reduction time is 60h. The reduced product was washed in 3% dilute hydrochloric acid, left to stand, and the precipitate was washed with water 3 times, filtered, and vacuum-dried at 130 ℃ to obtain 365.3kg of particulate metallic zirconium. The oxygen content of the fine-grained metal zirconium was determined to be about 1.5% by ONH analyzer and the calcium content was determined to be 0.38% by ICP-OES.
And S2, isostatic pressing fine-particle metallic zirconium into an electrode with the size of 1000 × 120 × 150mm, the pressure of 100MPa and the time of 2min. Arranging the pressed electrode blocks in a zirconium material feeding box, arranging the pressed electrode blocks in the zirconium material feeding box, and filling the zirconium material feeding box into an electron beam cold bed furnace, wherein the electron beam cold bed furnace is vacuumized to be less than or equal to 3.0 x 10 -3 And Pa, melting the electrode block into a zirconium ingot through raw material melting, refining, solidifying and cooling to obtain 340.3kg of zirconium ingot. The current of the melting zone is controlled to be 8-10A in the melting process, and the power is 220-300kw. The current of the refining zone is controlled at 2-3A, and the power is 40-80kw; controlling the current of the solidification region to be 3-5A and the power to be 80-150kw; the cooling time was 6h.
S3, turning and pressing the melted zirconium ingot into zirconium cakes with the diameter less than or equal to 50mm, putting the zirconium cakes into a reactor of an iodinating furnace, putting the reactor into a salt bath furnace, vacuumizing the reactor, and keeping the vacuum degree≤6.0*10 -3 Pa, controlling the temperature of a salt bath furnace at 240-300 ℃, controlling the temperature of a female wire in a reactor at 1430 ℃, adding iodine for iodination and purification, crystallizing zirconium on the female wire, taking out the reactor after the reaction is finished, cooling, and taking out the crystallized zirconium to obtain 333.7kg of high-purity zirconium, wherein the purity of the product reaches 99.99%.
The yield of the high-purity zirconium is 90.2 percent by calcium thermal reduction, electron beam cold bed smelting and iodination purification.
Comparative example 1
Comparative example 1 was set up based on example 1, except that comparative example 1 was subjected to iodination purification directly under calthermic reduction without electron beam cold hearth melting.
S1, weighing zirconia, metallic calcium and anhydrous calcium chloride according to a weight ratio of 1. Firstly, putting a part of anhydrous calcium chloride into a crucible, then uniformly mixing zirconium oxide and metal calcium, then putting the mixture into the crucible, and finally adding the rest anhydrous calcium chloride. Vacuumizing to less than or equal to 10Pa, and introducing argon to wash the furnace for 3 times. The reduction is carried out under the protection of argon with the flow rate of 5L/min, the reduction temperature is 1174K, and the reduction time is 8h. The reduction product is washed in 2% dilute hydrochloric acid, and is kept stand, and the precipitate is washed with water and filtered for 3 times and is dried in vacuum at 130 ℃ to obtain 362.3kg of granular metallic zirconium. The oxygen content of the fine-grained metal zirconium was determined to be about 2.5% by ONH analyzer and the calcium content was determined to be 0.34% by ICP-OES.
S2, pressing the molten granular metal zirconium into zirconium cakes with the diameter of less than or equal to 50mm, filling the zirconium cakes into a reactor of an iodization furnace, placing the reactor into a salt bath furnace, vacuumizing the reactor, and enabling the vacuum degree to be less than or equal to 6.0 x 10 -3 Pa, controlling the temperature of a salt bath furnace at 240-300 ℃, controlling the temperature of a mother wire in a reactor at 1370 ℃, adding iodine for iodination and purification, crystallizing zirconium on the mother wire, taking out the crystallized zirconium after the reaction is finished and cooling the reactor, and obtaining 93.4kg of high-purity zirconium with the purity of only 99.90 percent and the yield of 25.2 percent.
Performance testing
The oxygen and calcium percentages of the intermediate products and the final products of examples 1 to 3 and comparative example 1 were measured, respectively, the calcium content and the zirconium purity were measured by ICP-OES and GDMS, and the oxygen content was measured by ONH analyzer (ELEMENTRAC ONH), with the results shown in table 1.
TABLE 1 percent oxygen, calcium and zirconium purity of intermediate and final products
According to the detection results in table 1, the purity of the high purity zirconium obtained by calcium thermal reduction, electron beam cold bed melting and iodination purification in examples 1-3 can reach more than 99.95%, and the yield can reach more than 88%. Comparative example 1 after direct purification by iodination after calcemic reduction, the product had more oxygen and calcium contents than in examples 1-3, and resulted in very low yield of metallic zirconium, only 25.2%.
Claims (7)
1. The preparation method of the high-purity metal zirconium is characterized by comprising the following steps of:
(1) Calcium thermal reduction:
putting zirconium oxide, anhydrous calcium chloride and metallic calcium into a reaction furnace, carrying out reduction reaction under a protective atmosphere, and respectively carrying out acid washing and water washing on a reduction product to remove impurities so as to prepare fine-particle metallic zirconium;
(2) Electron beam cold bed smelting:
pressing fine particle metal zirconium into an electrode block, placing the electrode block in an electron beam cold bed furnace, and melting, refining, solidifying and cooling the raw materials to obtain a zirconium ingot;
(3) Iodination and purification:
turning a zirconium ingot smelted by an electron beam into zirconium scraps, pressing the zirconium scraps into cakes, filling the cakes into a reactor of an iodinating furnace, placing the reactor in a salt bath furnace, controlling the temperature of a mother wire in the reactor to 1350-1450 ℃, adding iodine to perform iodination purification, crystallizing zirconium on the mother wire, taking out the reactor after the reaction is finished, cooling, and taking out the crystallized zirconium to obtain the high-purity zirconium metal.
2. The method for preparing high-purity metallic zirconium according to claim 1, wherein the mass ratio of zirconium oxide to metallic calcium in step (1) is 1.
3. The method for preparing high-purity metallic zirconium according to claim 1, wherein the reduction reaction temperature in the step (1) is 1120 to 1374K.
4. The method for preparing high-purity metallic zirconium according to claim 1, wherein the reduction reaction time in the step (1) is 8 to 60 hours.
5. The method for preparing high-purity zirconium metal according to claim 1, wherein the protective atmosphere in the step (1) is argon ， The flow rate of the protective atmosphere is more than or equal to 5L/min.
6. The method for preparing high-purity metallic zirconium according to claim 1, wherein the melting zone current of the step (2) is controlled to be 8 to 10A, and the power is 220 to 300kw; the current of the refining zone is controlled at 2-3A, and the power is 40-80kw; the current in the coagulation zone is controlled to be 3-5A, and the power is 80-150kw.
7. The method for preparing high-purity zirconium metal according to claim 1, wherein the temperature of the salt bath furnace in the step (3) is controlled to 240 ℃ to 300 ℃.
Priority Applications (1)
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