WO2018052232A1 - 지르코늄계 금속의 제조 시스템 - Google Patents

지르코늄계 금속의 제조 시스템 Download PDF

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WO2018052232A1
WO2018052232A1 PCT/KR2017/009999 KR2017009999W WO2018052232A1 WO 2018052232 A1 WO2018052232 A1 WO 2018052232A1 KR 2017009999 W KR2017009999 W KR 2017009999W WO 2018052232 A1 WO2018052232 A1 WO 2018052232A1
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zrf
zirconium
baf
based metal
metal
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PCT/KR2017/009999
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English (en)
French (fr)
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이종현
하이크 네르시시얀
이영준
한슬기
최정훈
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충남대학교 산학협력단
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Publication of WO2018052232A1 publication Critical patent/WO2018052232A1/ko

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/22—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

Definitions

  • the present invention relates to a manufacturing system of zirconium metal.
  • Zirconium is indispensable for nuclear energy, electronics, mechanics, metals and ceramics because of its high permeability and its inherent properties of corrosion resistance.
  • zirconium has high strength and circulation at high temperatures. It is not easily corroded to coolant, does not form radioisotopes well and has little mechanical damage by neutron irradiation, so 90% of the world's zirconium production is used for nuclear power industry. It is very important for coating pipes coated with heavy water pressure pipe materials, nuclear fuel rods to nuclear reactors, and alloys with uranium, and the demand is increasing rapidly.
  • the metal reduction method and the direct reduction method are used, and the crawl method is mainly used for the mass production process.
  • the crawl method is highly toxic from the metallization step of the ore, the chlorination step and the reduction step by the magnet metal.
  • Chlorine gas is used, and there are many reduction stages, making the process less efficient and environmentally friendly.
  • commercially available products are difficult to separate hafnium from their coexisting cousins, and thus contain 2 to 3% of hafnium.
  • Electrolysis is also not economical because halogen compounds such as ZrC are used as raw materials and chlorine gas is generated during the process.
  • the metallothermic which has been reported and studied in the past, is used as an oxide raw material.
  • the developed direct reduction method has advantages such as no need for reducing agent and direct emission of toxic substances through direct reduction of oxide in molten salt. However, there are still limitations due to low current efficiency and slow production speed.
  • the zirconium tetrafluoride (ZrF 4 ) contained in the pickling liquor may be dissolved in sodium fluoride (NaF) or the like. It is a technology that produces crystalline zirconium compound by precipitating with reducing agent.This technology has the advantage of high process efficiency because it is environmentally friendly because there is no chlorine gas discharge and no additional removal process of hafnium is required compared to Kroll method. .
  • the crystalline zirconium compound produced by the above technique is not high in purity, and the concentration of impurities such as Na remaining after reaction is very high, as well as a disadvantage in that the yield of the produced zirconium compound is not high.
  • Patent Document 1 Korea Patent Publication KR2016-0099504A (2016.08.22)
  • the object of the present invention is to efficiently and economically manufacture and recover zirconium-based metals, while significantly improving the purity and yield of zirconium-based metals prepared using the electrolytes and the electrolytes. To provide a production system of zirconium-based metals.
  • a specific object of the present invention is to provide a method for preparing Ba-Zr-F based electrolytes for the production of zirconium based metals having excellent purity and yield using BaF 2 as a reducing agent in a Zr-containing acid solution.
  • a specific object of the present invention is to provide a method for synthesizing Ba 2 ZrF 8 into BaZrF 6 having a lower melting point using ZrF 4 .
  • the specific purpose of the present invention is to provide an electrolyte for the production of zirconium-based metals.
  • the average particle diameter of BaF 2 may be 0.1-50 days.
  • the Ba 2 ZrF ⁇ purity obtained in step b) may be 99.98% or more.
  • the method for producing an zirconia-based metal of one embodiment of the present invention may include the step of reducing Ba 2 ZrF 8 or BaZrF 6 as an electrolyte to reduce and precipitate the zirconium-based metal as a cathode.
  • step b) to precipitate the Ba 2 ZrF 8 can be prepared by a step of obtaining a Ba 2 ZrF 8 precipitated in the a) step.
  • BaZrF 6 is mixed with Ba 2 Zri la ZrF 4 and heated to
  • step of synthesizing the 802 ⁇ 6 Ba 2 ZrF 8 is a) Zr should steps and b) to reduce the lactic acid to BaF 2 by precipitation with Ba 2 ZrF 8 wherein a) It can be manufactured, including the step 8: Acquisition of settled 8: in step.
  • the method for producing the zirconium-based metal is c) Ba 2 ZrF 8
  • the method for producing the zirconium-based metal is c) Ba 2 Zri ⁇
  • the method for producing the zirconium-based metal is c) B rF
  • the method may further include a step of separating BaF 2 and ZrF 4 , wherein BaF 2 in step a) may use BaF 2 separated in step c) and synthesize the BaZrF 6 .
  • ZrF 4 may be used ZrF 4 separated in step c).
  • the step c) is introduced into Ba 2 ZrF ⁇ reaction chamber and heated to l, 000 to l, 150 o C for 1 to 15 hours in a vacuum state to BaF 2 and ZrF 4 . It may include a step of separating.
  • the cathode may be a zirconium-based metal electrode, and the reduction and precipitation of the zirconium-based metal may be Zr metal.
  • the cathode may be a copper metal electrode
  • the reduced and precipitated ruconium metal may be a Cu—Zr alloy.
  • the zirconium-based metal manufacturing system of the present invention is efficient and economically
  • the electrolyte and the electrolyte for preparing the zirconium-based metal can be used to significantly improve the purity and yield of the zirconium-based metal.
  • the method for producing Ba-Zr-F-based electrolyte which is one embodiment of the present invention, uses BaF 2 as a reducing agent, so that even though the Zr-containing acid solution is highly recycled, It has the advantage of producing Ba-Zr-F based electrolyte and zirconium based metal in yield.
  • the separation method of BaF 2 and ZrF 4 from 8 which is an aspect of the present invention, has the advantage of separating each component with a very high purity, and subsequently has the advantage of manufacturing a zirconium-based metal with high purity and process efficiency.
  • Ba 2 ZrF 8 which is one embodiment of the present invention, is prepared using BaZrF ( ⁇ synthesis) to produce a zirconium-based metal using 803 ⁇ 4 having a lower melting point than Ba 2 ZrF 8 as an electrolyte.
  • the recycling system for the production of zirconium-based metals of the present invention has the advantage of being able to manufacture zirconium-based metals economically and efficiently in connection with the aforementioned methods.
  • the zirconium-based metal manufacturing system of the present invention is a chlorine gas
  • FIG. 1 is a schematic diagram showing each process of a zirconium-based metal manufacturing system and a circulation system of the processes according to an example of the present invention.
  • FIG. 2 is a scanning electron microscope image and ax-ray diffraction spectrum of the final compound (Ba 2 ZrF 8 ) according to Example 1.
  • FIG. 2 is a scanning electron microscope image and ax-ray diffraction spectrum of the final compound (Ba 2 ZrF 8 ) according to Example 1.
  • FIG. 3 shows data on scanning electron microscopy images and ax-ray diffraction spectra of impurities remaining in the filtrate according to Example 1.
  • Example 6 is an image showing an enlarged image of BaF 2 powder according to Example 3, and a table showing the weight ratio and atomic ratio of the BaF 2 powder component.
  • Example 7 shows BaF 2 powder according to Example 3 measured by X-ray diffraction analysis.
  • FIG. 8 is an image showing an enlarged image of ZrF 4 powder according to Example 3 and a weight ratio and atomic ratio of the ZrF 4 powder component.
  • Example 11 shows ZrF 4 powder according to Example 5 measured by X-ray diffraction analysis.
  • FIG. 13 is a schematic view showing the process principle of the circulating current method in Example 10.
  • FIG. 14 shows data analyzing redox behavior of zirconium prepared according to Example 10.
  • Example 15 is an image showing an example of the electrolytic smelting process of Example 10 and a graph showing the voltage over time during the electrolytic smelting process.
  • Example 16 shows a scanning electron microscope and an element of a product obtained according to Example 10.
  • Example 17 shows the product of Example 10 measured by X-ray diffraction analysis.
  • Example 18 shows the zirconium metal prepared according to Example 11 by X-ray diffraction analysis.
  • Example 20 is an image of a Cu—Zr based metal prepared according to Example 12.
  • FIG. 21 shows data obtained by measuring Cu-Zr-based metals prepared according to Example 12 using an scanning electron microscope and an element analyzer (Energy Dispersive x-ray Spectroscopy, EDS).
  • EDS Electronic x-ray Spectroscopy
  • FIG. 22 is a spectrum measured by X-ray diffraction analysis of a Cu—Zr based metal prepared according to Example 12.
  • the present invention relates to a manufacturing system of zirconium-based metals.
  • the present invention integrates and applies various processes involved in the production of zirconium-based metals as a series of processes as shown in FIG. 1 and systemizes each process to be recycled, thereby making it possible to manufacture economical, efficient and high-purity zirconium-based metals. To provide a system.
  • the present invention can be classified into three steps including a process for producing a Ba-Zr-F based electrolyte using a Zr-containing acid solution, a separation process for Ba 2 ZrF 8, and / or a smelting process for electrolysis.
  • the process for producing Ba-Zr-F based electrolyte using Zr-containing acid solution which is a process of the present invention, includes producing Ba 2 ZrF 8 by using BaF 2 as a reducing agent in a Zr-containing acid solution.
  • the method for producing Ba 2 ZrF 8 which is a Ba-Zr-F based electrolyte using Zr-containing acid solution, includes: a) reducing the Zr-containing acid solution to & 8 and reducing to Ba 2 ZrF 8 and b) It may comprise the step of obtaining Ba 2 ZrF 8 precipitated in step a).
  • the Zr-containing acid solution refers to an acid solution containing Zr or a Zr-based compound, and may be preferably a pickling solution in terms of economical and environmentally friendly aspects.
  • the solution may include a Zr-based compound of zirconium tetrafluoride (ZrF 4 ) and an acid of nitric acid, hydrochloric acid, or acid of hydrofluoric acid.
  • ZrF 4 zirconium tetrafluoride
  • zirconia depleted of Hf may be dissolved in an acid solution.
  • the Zr-containing acid solution may contain Zr or Zr compound in an amount of 0.01 to 15% by weight, specifically 0.1 to 10% by weight, but is not limited thereto.
  • nuclear fuel assemblies in particular light nuclear fuel assemblies, have a framework including longitudinal guide tubes consisting of zirconium tubes or zirconium alloy tubes and transverse spacer grids, consisting of mutually parallel rods of the form of a foot.
  • the production of a plurality of zirconium tubes or zirconium alloy tubes requires a continuous rolling process followed by a separate thermal annealing process, and degassing and chemical pickling processes are indispensable.
  • the pickling liquor collected after the process by the pickling process includes hydrofluoric acid, water, and nitrate, and in particular, may include a Zr compound of ZrF 4 which is generated during the process.
  • the a) step is a step of precipitating the Ba 2 ZrF 8 incorporating a BaF 2 to Zr also lactic acid and induce a reduction banung.
  • the Zr also lactic acid and BaF 2 uihon Hefei is Ba 2 ZrF ⁇ l Synthesis If possible, it is not limited, and may be, for example, 0.5 to 30 parts by weight based on 100 parts by weight of Zr-containing acid solution.
  • step b) Ba 2 ZrF 8 synthesized in step a) is obtained.
  • the product obtained in step a) is filtered into a filtrate and Ba 2 ZrF 8 through a filtration method and a drying method after filtration. can be separated by a step to obtain a Ba 2 ZrF 8.
  • the degree of drying and the drying time are not limited, for example 20 to 120 ° C and 1 to 20 hours.
  • the average particle diameter of BaF 2 may be 0.1 to 50 / ffli, preferably 0.1 to 10 and more preferably 0.1 to 1 / Hi.
  • the reaction rate can be significantly increased, the yield of the synthesized 8 1 ⁇ is greatly increased, and in particular, the concentration of unreacted water such as Ba and Zr, which is not reacted, is extremely reduced, thereby obtaining a very high purity of 8 & ⁇ .
  • the average particle diameter of BaF 2 is 0.1-50, preferably 0.1-10 ⁇ m,
  • the purity of the Ba 2 ZrF 8 obtained in step b) may be at least 99.98%, especially when used as BaF 2 commutative base agent that satisfies the above average particle diameter, NaF commutative circle zero It is possible to manufacture Ba 2 ⁇ of very high purity in a high yield in contrast to the case.
  • BaF 2 satisfying the average particle diameter it is not reacted in step a), but it reacts with acid as an impurity. There is a remarkable effect that the concentration of impurities in the remaining Ba (Na) column can be reduced by more than 10 times compared to the case where NaF is used.
  • the Ba 2 ZrI ⁇ thus prepared may have an average diameter in the range of 10 to 500 nm.
  • 8 3 ⁇ 4 may exist in various forms, for example, the average diameter may be present in a poly-microcrystalline form in which a plurality of particles are united.
  • the above production method of 8 3 4 ⁇ can produce 8 3 4 from the Zr-containing acid solution, and 8 3 4 4 ⁇ can be used for the production of zirconium-based metals.
  • the manufacturing method of the zirconium-based metal of the present invention may include an electrolytic smelting process including the step of reducing the Ba-Zr-F-based electrolyte and reducing and depositing the zirconium-based metal as the cathode.
  • -Zr-F-based electrolyte is a) Zr also to reduce the lactic acid to be produced as BaF 2, including the steps and b) to obtain a Ba 2 ZrF 8 settled in the steps of: a) precipitation with Ba 2 ZrF 8 Ba 2 ZrF 8 can be.
  • the method for producing zirconium-based metals uses Ba-Zr-F-based compounds as electrolytes.
  • the method of manufacturing the zirconium-based metal includes the step of heating and smelting the melting point of 8 3 ⁇ 4 ⁇ to a temperature higher than 8 3 ⁇ 4 to serve as an electrolyte, and thus requires a lot of energy for this.
  • Ba 2 ZrF ⁇ ] has a melting point of 1031 ° C
  • BaZrl ⁇ i has a low of 765 ° C.
  • the step of synthesizing BaZrF 6 when the zirconium-based metal is manufactured using BaZrF fi converted from 8 3 ⁇ 4 ⁇ as an electrolyte, the energy consumed during the electrolytic smelting process can be minimized, and the process efficiency is greatly increased. You can do it. It also minimizes the erosion and thermal fatigue of equipment used in the electrolysis process.
  • a method of manufacturing a zirconium-based metal includes a step of mixing Ba 2 ZrF 8 and ZrF 4 and heating to synthesize BaZrF 6 . May contain
  • 83213 ⁇ 4 synthesized in the step of synthesizing BaZrF 6 may be synthesized by injecting ZrF 4 and Ba 2 ZrF 8 into a reaction furnace and heating, if the heating temperature is such that BaZrF fi can be synthesized. It is not limited and can be, for example, 700 to 900 o C, specifically 750 to 850 o C.
  • the reaction atmosphere is preferably an inert atmosphere of argon and nitrogen in terms of minimizing the formation of by-products. Synthesis can be carried out with the reaction vessel sealed. Specifically, since ZrF 4 is at a low vapor pressure of 5.29X10 1 atm at a temperature of 1,000 ° C, the BaZrF 6 is added in a sealed reaction furnace. High yields can be guaranteed.
  • the ZrF 4 has a size of l ⁇ 10 urn through a shredding step for smooth reaction.
  • the mixing ratio of B ZrI ⁇ ZrF 4 is not limited as long as BaZrF 6 can be synthesized.
  • the molar ratio of Ba 2 ZrF 8 : ZrF 4 is 1: 0.5 to 2, preferably It can be 1: 1 to 1.5, and in one preferred embodiment, it can be 1: 1.
  • Ba 2 ZrF 8 is combined at a lower molar ratio than ZrF 4.
  • ZrF 4 may be prepared, but ZrF 4 obtained from the Ba 2 ZrF 8 separation process including the step of separating c) Ba 2 ZrF 8 into BaF 2 and ZrF 4 described below for maximum process efficiency is preferred. This is because BaF 2 obtained by separating with ZrF 4 in step c) can be used again in step a). Therefore, BaF ⁇ obtained in step c) not only can be used, since the c) ZrF 4 ballast group is separated and obtained in step BaZrF ⁇ it is for ZrF 4 Rosa of synthesizing, can be maximized than process efficiency.
  • the method for producing a zirconium-based metal of the present invention may further include c) separating Ba 2 ZrF 8 into BaF 2 and ZrF 4 in addition to steps a) and b). ) 8 ⁇ in step I can be used from Ba 2 ZrF 8 to be produced in the production method of ZrF Ba-based compound used in the preparation of zirconium-based metal by using the BaF 2, there sikilsu significantly increase the process efficiency.
  • step c) is added to Ba 2 ZrI ⁇ : Bungungro and heated to
  • Is BaF 2 and the space formed in the lower space in banung ungchuk outside can be a step which is isolated as ZrF 4 is formed. Step in which the separation is by putting the Ba 2 ZrF 8 in a banung heated and BaF 2 Phase separation with ZrF 4 .
  • the heating temperature of step c) may be 1,000 to 1,200 ° C in terms of melting Ba 2 ZrF ⁇ l and being able to exist as BaF 2 and ZrF 4 .
  • the heating of the step c) is more than 1,000 ⁇ 1,150 ° C,
  • BaF 2 and ZrF 4 can be selectively separated into extremely high purity.
  • Ba 2 Zrf ⁇ i BaF 2 and ZrF 4 are mixed at the melting point temperature, and BaF 2 is formed in the inner space of the reaction chamber in the liquid phase (melted state) and ZrF 4 is formed in the reaction chamber (vapor phase) inside or outside the space. Accordingly, in a later below the melting point saver FIG BaF 2 is formed in the inner bottom to banung, ZrF 4 is ungchuk outside the upper or the space in banung can be isolated.
  • the heating temperature when U50 or more, of the ZrF 4 rapid The increase in airflow due to evaporation may cause BaF 2 to enter the vapor phase, making it difficult to separate BaF ⁇ ZrF 4 .
  • the heating temperature is between 1,000 and 1,150 ° C and preferably between 1,000 and 1,100 ° C, BaF 2 and ZrF 4 can be automatically separated into separate spaces inside the reaction furnace.
  • the heating time of step c) is not limited so long as it can be Ba 2 ZrF melted and separated into Bai ⁇ f ⁇ , for example, 1 to 15 hours, preferably 5 to 13 hours, more preferably 5 It can be up to 11 hours. If this is satisfied, the yield of ZrF 4 obtained separately can be significantly increased.
  • step c) is performed by ZrF 4 phase phase and the liquid phase of 8 ⁇ 2 .
  • reaction furnace may be separate, preferably by vacuum distillation, in which the interior of the reaction furnace may be in close proximity to the vacuum, preferably in vacuum, for example at a pressure of lOHO "1 torr.
  • step c) since the melting point of 8 is higher than ZrF 4 at a temperature of 8, step c) may further include condensing ZrF 4 in the gas phase.
  • ZrF 4 can be obtained in a ZrF 4 powder of the solid phase from the vapor Hung accumulation eu temperature eseoui ungchuk flight of the gas phase is not greatly limited, e.g., in detail more than 25 ⁇ 300 ° C, particularly 50 ⁇ 200 ° C It can be 75 ⁇ 150 ° C.
  • the Ba 2 ZrF ⁇ 1 is formed in the space of the vessel portion 12; and the capture portion (11) formed outside the vessel portion 12 is separated and captured ZrF 4 ; may include. when the melt of the Ba 2 Z r F 8 take place, at the same time ZrF 4 is BaF 2 available melt from the container portion is elevated in the gas phase, so BaF 2 is and remains is solidified in a solid phase after the liquid phase in the unit container, ZrF 4 is The gas phase moves to a position outside the container and is then condensed and separated. As a result, BaF 2 and ZrF 4 can be effectively separated with very high purity due to the phase difference.
  • the banung roneun is provided within the lower space in banung separated from the ZrF 4 at a temperature of the melting point or more of BaF 2 gajan zone to the container portion 12 to be formed; and ZrF 4 is raised and ungchuk the vapor phase ZrF 4 may include a capture portion 11, which is a space excluding the vessel portion 12 in which the vessel portion 12 is formed.
  • the vessel portion 12 includes a space in which solid Ba 2 ZrF ⁇ l may be charged, The upper surface of the container section 12 and the top of the semi-reactor are separated from each other so that they can be separated from the temperature by rising to the top of the ZrF 4.
  • the separation distance of Ba 2 ZrF 8 into the container section 12 is formed by BaF 2 and ZrF 4 . Converting weather Any material that can be moved out of the ZrF 4 virtual airspace may be used.
  • the material of the reaction furnace is preferably not to be combined with BaF 2 and ZrF 4.
  • the main ingredient may be a material.
  • a nickel crucible manufactured as the main ingredient for nickelol may be exemplified as the container part included in the reaction furnace.
  • the method for producing a zirconium-based metal is electrolytic smelting of Ba 2 ZrF 8 or Ba-Zr-F-based compounds of BaZrF 6 as electrolyte to reduce and precipitate the zirconium-based metal by the cathode. It may include an electrolytic smelting process.
  • the zirconium-based metal thus deposited may be a high purity zirconium metal or a copper-zirconium alloy.
  • the electrolytic smelting may be carried out using an electrolytic reduction method as shown in FIG. 14, in which a zirconium ion is received at an anode and reduced to a zirconium metal or It can be carried out on the principle of precipitation in the form of a copper-zirconium alloy.
  • the anodes used in the electrolytic smelting process are silver (Ag), silver chloride (AgCl), tungsten, platinum, and carbon electrodes free of electrolytes and chemical reactions for the production of high purity zirconium-based metals.
  • the negative electrode may be a zirconium-based electrode or a copper-based electrode having a high reaction and electrolyte.
  • the cathode may be a zirconium-based metal electrode, and the reduction and precipitation of the zirconium-based metal may be Zr metal.
  • the zirconium metal is reduced and deposited into the zirconium-based cathode, , High purity zirconium metal can be obtained.
  • the cathode may be a copper metal electrode, and the reduced and precipitated zirconium metal may be a Cu-Zr alloy.
  • the zirconium ions react together to reduce and precipitate Cu-Zr based alloys on the cathode.
  • the deposited Cu-Zr based alloys are specifically CuZr, CuZr 2 , Cu 5 Zr, CugZr 3 , Cu 10 Zr 7 and One or more Cu-Zr compounds selected from Cu 5 and Zr 14 may be included.
  • alloys can be manufactured, it is possible to produce Cu-Zr alloys containing high concentrations of zirconium.
  • the zirconium-based metal is contained through the electrolytic smelting process.
  • the product can be obtained, but the product can comprise an electrolyte in the form of a molten salt with a zirconium-based metal.
  • the electrolytic smelting process is performed to remove the product deposited on the cathode after electrolytic smelting.
  • the method may further include a step of separating the zirconium-based metal and the molten salt.
  • a step of separating the zirconium-based metal and the molten salt using a distillation method there is a step of separating the zirconium-based metal and the molten salt using a distillation method.
  • a vacuum distillation column can be used, and the degree to which the molten salt in the product can be distilled may include, for example, heating to 700 ⁇ l, 200 ° C. Distillation can be carried out for 1 to 20 hours at pressures between 5 and 10 2 torr, but this is only an example and the present invention is not limited thereto.
  • the final compound has an average size of 20.
  • Ba 2 ZrF 8 had a poly-microcrystalline form and had only a characteristic peak corresponding to Ba 2 ZrF ⁇ . Also, as shown in FIG. 3, impurities remaining in the filtrate had a poly-microcrystalline form, and Sn, Zr It has been confirmed that it has a characteristic peak corresponding to, F, 0.
  • Example 1 NaF was used instead of BaF 2 , and the same procedure as in Example 1 was carried out.
  • Example 1 The average particle diameter in the 1 / m BaF 2 instead of the average particle diameter is 45; c is 2 and BaF
  • the filtrates of Examples 1 and 2 using 8 ⁇ 2 having an average particle diameter of 45 / mi or less were very low at concentrations of 250 ppm or less, whereas NaF was used.
  • the filtrate had a very high concentration of Na above 10,000 ppm that could be converted to sodium nitrate (NaNO 3 ).
  • BaF 2 has a much higher reaction rate as a reducing agent than NaF, minimizes the occurrence of impurities that can react with Ba or Na acid and significantly improves the reaction yield of Zr.
  • the residue has a poly-microcrystalline form from FIG. 6, and has a peak of barium difluoride (BaF 2 ) from the X-ray diffraction analysis spectrum of FIG.
  • the powder has a poly-micro form from FIG. 8, and from the X-ray diffraction analysis spectrum of FIG. 9.
  • Example 3 except that performed at 1,100 ° C instead of 1,000 ° C, it was carried out in the same manner as in Example 3.
  • Example 3 except for maintaining for 13 hours instead of 10 hours, The same was done.
  • Example 4 it carried out similarly to Example 3 except having kept for 13 hours instead of 10 hours.
  • Example 5 except for maintaining for 5 hours instead of 10 hours,
  • Example 5 except for maintaining for 7 hours instead of 10 hours,
  • Example 5 performed at 1,200 ° C did not selectively separate into BaF 2 and ZrF 4 , which can be seen from Figure 11, which is due to the high degree of It is judged to be due to the incorporation of BaF ⁇ in the vapor due to the rapid rise of the air due to rapid evaporation of ZrF 4.
  • Examples 3 and 4 and 6 performed at 1,000 ° C. and 1,100 ° C. example 7 for are selectively separated by, BaF 2 and ZrF 4 go, as shown in Figs. 7, 12 was able to confirm that the residues present in each and powders, that is, a BaF 2 and ZrF 4
  • Ba 2 ZrF 8 which is the final compound of Example 1, and ZrF 4 , which is a powder produced on the outer wall of Example 3, were mixed in a 1: 1 molar ratio, added to a semi-aerator, and sealed at 800 o C in an argon atmosphere. By heating, BaZrF 6 was synthesized.
  • 8 ⁇ 6 is used as an electrolyte, and the oxidation reduction behavior of zirconium metal production and zirconium metal production by circulating current method is carried out using an electrolytic smelting apparatus as shown in FIG. At this time,
  • Tungsten was used for positive electrode (reference electrode) and depleted rod for negative electrode (sacrificial electrode).
  • reference electrode positive electrode
  • negative electrode sacrificial electrode
  • reaction of + 2 ⁇ ⁇ ⁇ 2+ proceeded at 0.84 V as shown in FIG.
  • Reduction behavior of Zr 2+ + 2e ⁇ Zr was observed, and electrolytic smelting at a reduction potential of 1.17 V or higher was considered desirable.
  • the zirconium metal was produced using the electrolytic smelting apparatus using BaZrF fi as an electrolyte as shown in FIG. 13. At this time, a cathode (reference electrode) was used as a carbon rod, and a cathode (sacrificial electrode) was used as a zirconium metal electrode. Zirconium electrolytic smelting was performed for 180 minutes with a current applied at a constant current of 200 mA / cm 2 . [136] Electrolytic smelting to obtain the reduced precipitated product on the cathode, using an element dispersive x-ray spectroscopy (EDS), a scanning electron microscope and an X-ray diffractometer as shown in Figs. Analyzed.
  • EDS element dispersive x-ray spectroscopy
  • the product is a metal of an average of 2 ⁇ 5 mm, as shown in FIG.
  • Example 10 The product obtained in Example 10 was pulverized, charged into a nickel crucible in a vacuum distillation apparatus, and subjected to salt middle, to obtain a zirconium metal from which residual salts of Ba 2 ZrF 8 were removed. The reaction was carried out for 10 hours at an argon atmosphere and a pressure of lC torr at 850 ° C.
  • the residual salt-free zirconium metal was analyzed using an energy dispersive x-ray spectroscopy (EDS), a scanning electron microscope and an ax-ray diffractometer. The results are shown in FIG.
  • the zirconium metal from which the residual salt is removed is charged into an arc melting furnace.
  • a zirconium metal ingot was prepared and the residual impurities were analyzed by glow discharge mass spectrometry. The results are shown in FIG. 19.
  • the zirconium metal from which the residual salt was removed has only a characteristic peak corresponding to zirconium.
  • the purity of the zirconium metal was 99.98% by weight or more. This is a result that far exceeds the ASTM-B349 standard, which is a standard that can be used for reactor cladding.
  • Example 10 the cathode was carried out in the same manner as in Example 10, except that the copper electrode was used instead of the graphite rod, and the product was not pulverized.

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Abstract

본 발명은 지르코늄계 금속의 제조 시스템에 관한 것으로, 지르코늄계 금속의 제조를 위해 수반되는 다양한 공정들을 일련의 공정으로 통합 및 적용하고, 각 공정들이 재순활될 수 있도록 시스템화함으로써, 경제적이고 효율적이면서도 고순도의 지르코늄계 금속의 제조가 가능한 지르코늄계 금속의 제조 및 재숨환 시스템을 제공하는 것이다.

Description

명세서
발명의명칭:지르코늄계금속의제조시스템 기술분야
[1] 본발명은지르코늄계금속의제조시스템에관한것이다.
배경기술
[2] 지르코늄 (Zirconium)은증성자의투과성이높고，내식성둥자체의고유한여러 성질때문에핵에너지，전자,기계,금속및세라믹스분야등에서필수적으로 사용된다.특히지르코늄은고온에서강도가좋고，순환하는냉각제에쉽게 부식되지않으며，방사성동위원소를잘형성하지않고,중성자조사에의한 기계적손상이적기때문에전세계지르코늄생산량의 90%가원자력 산업용도로사용되고있다.특히원자로심구조물인지지격자，안내관,중수로 압력관소재,원자로의핵연료봉등에피복되는피복관,우라늄과의합금둥에 매우중요하게사용되고있으며,따라서수요가급증하고있는추세에 있다.
[3] 그러나국내에서는지르코니아및금속지르코늄을생산하는산업조차없어 전량수입하는실정이며，이에대한체계적인연구도이루어져있지못한 실정이다.현재까지국내에서수행되고있는연구는가성소다와의반웅에의한 지르콘사의분해반웅에관한연구들로서,효율적인공정연계및실제공정 운영이어려운기술적인한계가있었다.
[4] 현재까지지르코늄의제조공정은크롤법 (Kroll process),전기분해법 ,
금속환원법및직접환원법 (Fray Farthing Chen)둥이있으며，상기크롤법은주로 양산공정에이용되고있다.그러나크롤법은원광의금속화단계로부터，염소화 단계및마그네슴금속에의한환원단계등독성이강한염소가스가사용되며, 환원단계가많아공정의효율및환경친화성이떨어진다.또한시판제품은 본래공존해 있던동족의하프늄분리가어려워 2~3%의하프늄이함유되어 있으므로,별도의분리공정이필요하다.전기분해법도 ZrC 등의할로겐 화합물이원료로사용되고，공정시염소가스가발생하므로궁극적으로 경제적이지못하다.기존에보고되고연구된바있는금속열법 (metallothermic)은 산화물원료가사용되므로생성물에포함된산화물블순물제거를위한별도의 산침출공정이필요하며,공기와접촉시지르코늄의표면산화를막을수없어 고품질의지르코늄의제조가어렵다.최근에개발된직접환원법은용융염 내에서산화물의직접환원을통해환원제가필요없고독성물질올배출하지 않는등의장점이있으나，아직까지전류효율이낮고생산속도가느려 효율적이지못한한계가있다.
[5] 다른기슬로서한국공개특허 KR2016-0099504A에는지르코늄함유산세
폐액으로부터지르코늄의선택적인분리방법에대해서공지되어 있다.
구체적으로,산세폐액에함유된사불화지르코늄 (ZrF4)을불화나트륨 (NaF)등의 환원제로침전시켜결정성지르코늄화합물을제조하는기술이다.이러한 기술은크를 (Kroll)법에비해염소가스의배출이없어친환경적이고하프늄의 추가적인제거공정이불필요하기때문에비교적공정효율이높은장점이 있다. 그러나상기기술로제조되는결정성지르코늄화합물은순도가높지못하며， 반웅이후잔류하는 Na등의불순물의농도도현저히높은단점이 있다.뿐만 아니라제조되는지르코늄화합물의수율이높지못한단점이있다.
[6] 또한지르코늄금속의제조를위해서는다양한공정들이수반되는것은물론， 다양한원료들이사용되지만，상기공정및원료들을적재적소에효율적으로 지르코늄금속의제조에적용하기에는한계가있다.
[7] 따라서지르코늄금속을효율적이고경제적으로제조및회수할수
있으면서도,제조되는지르코늄금속의순도및수율도현저히향상시킬수있는 기술이필요하다.
[8] [선행기술문헌]
[9] [특허문헌]
[10] (특허문헌 1)한국공개특허 KR2016-0099504A (2016.08.22)
발명의상세한설명
기술적과제
[11] 본발명의목적은지르코늄계금속을효율적이고경제적으로제조및회수할 수있으면서도,지르코늄계금속의제조를위한전해질및상기전해질을 이용하여제조되는지르코늄계금속의순도및수율을현저히향상시킬수있는 지르코늄계금속의제조시스템을제공하는것이다.
[12] 본발명의구체적목적은 Zr함유산용액에 BaF2를환원제로사용하여순도및 수율이우수한지르코늄계금속의제조를위한 Ba-Zr-F계전해질의제조방법을 제공하는것이다.
[13] 또한본발명의구체적목적은 ZrF4를이용하여 Ba2ZrF8을상대적으로용융점이 더낮은 BaZrF6로합성하는방법을제공하는것이다.
[14] 또한본발명의구체적목적은지르코늄계금속의제조를위한전해질로
사용될수있는 Ba2ZrFs을 BaF2와 ZrF4로선택적으로분리하여분리된물질들올 상기 Ba-Zr-F계전해질의제조방법또는상기 BaZrF6의합성방법에사용할수 있는재순환방법을제공하는것이다.
[15] 따라서본발명의목적은상술한방법들을연계하여친환경적이고경제적이며 효율적인지르코늄계금속의제조를위한재순환시스템올제공하는것이다. 과제해결수단
[16] 본발명의일양태인 Ba2ZrFi^제조방법은 a) Zr함유산용액을 8& 로환원및 Ba2ZrF8으로침전하는단계및 b)상기 a)단계에서침전된 Ba2ZrF8을수득하는 단계를포함할수있다.
[17] 바람직한일예에 있어서，상기 BaF2의평균입경은 0.1-50 일수있다. [18] 본발명의일예에있어서,상기 b)단계에서수득된 Ba2ZrF^순도는 99.98% 이상일수있다.
[19] 본발명의일양태인지르코늄계금속의제조방법은 Ba2ZrF8또는 BaZrF6를 전해질로서전해하여음극으로지르코늄계금속을환원및석출하는단계를 포함할수있다.
[2이 본발명의일예에있어서，상기 8 ^은 a) Zr함유산용액을 BaF2로환원하여
Ba2ZrF8으로침전하는단계및 b)상기 a)단계에서침전된 Ba2ZrF8을수득하는 단계를포함하여제조될수있다.
[21] 본발명의일예에있어서，상기 BaZrF6는 Ba2Zri 라 ZrF4를흔합하고가열하여
832^6를합성하는단계를포함하여제조될수있다.
[22] 본발명의일예에있어서,상기 802^6를합성하는단계에서 Ba2ZrF8은 a) Zr 함유산용액을 BaF2로환원하여 Ba2ZrF8으로침전하는단계및 b)상기 a) 단계에서침전된 8 ： ^을수득하는단계를포함하여제조될수있다.
[23] 본발명의일예에있어서,상기지르코늄계금속의제조방법은 c) Ba2ZrF8을
BaF2및 ZrF4로분리하는단계를더포함할수있으며，상기 a)단계의 BaF2는 상기 c)단계에서분리된 BaF2가사용될수있다.
[24] 본발명의일예에있어서，상기지르코늄계금속의제조방법은 c) Ba2Zri ^
BaF2및 ZrF4로분리하는단계를더포함할수있으며,상기 BaZrF6를합성하는 단계의 ZrF4는상기 c)단계에서분리된 ZrF4가사용될수있다.
[25] 본발명의일예에있어서,상기지르코늄계금속의제조방법은 c) B rF
BaF2및 ZrF4로분리하는단계를더포함할수있으며，상기 a)단계의 BaF2는 상기 c)단계에서분리된 BaF2가사용될수있고,상기 BaZrF6를합성하는단계의
ZrF4는상기 c)단계에서분리된 ZrF4가사용될수있다.
[26] 본발명의일예에있어서,상기 c)단계는 Ba2ZrF^반웅로에투입하고진공 상태에서 1~15시간동안 l,000~l,150oC로가열하여 BaF2및 ZrF4로분리하는 단계를포함할수있다.
[27] 본발명의일예에있어서，상기음극은지르코늄계금속전극일수있으며， 상기환원및석출되는지르코늄계금속은 Zr금속일수있다.
[28] 본발명의일예에있어서，상기음극은구리계금속전극일수있으며，상기 환원및석출되는지르코늄계금속은 Cu-Zr계합금일수있다.
발명의효과
[29] 본발명의지르코늄계금속의제조시스템은효율적이고경제적으로
지르코늄계금속을제조및회수할수있으면서도,지르코늄계금속의제조를 위한전해질및상기전해질올이용하여제조되는지르코늄계금속의순도및 수율을현저히향상시킬수있는효과가있다.
[3이 구체적으로，본발명의일양태인 Ba-Zr— F계전해질의제조방법은 BaF2를 환원제로사용함으로서， Zr함유산용액을재활용함에도매우높은순도및 수율로 Ba-Zr-F계전해질및지르코늄계금속을제조할수있는장점이있다.
[31] 또한본발명의일양태인 8 으로부터 BaF2와 ZrF4의분리방법은매우 높은순도로각성분들을분리할수있는장점이 있어,이후높은순도및공정 효율로지르코늄계금속을제조할수있는장점이 있다.
[32] 또한본발명의일양태인 Ba2ZrF8을 BaZrF(^합성하는방법을통해 Ba2ZrF8 보다용융점이더낮은 80¾ 를전해질로사용하여지르코늄계금속을 제조함에따라공정효율및에너지효율을현저히증가시킬수있는장점이 있다.
[33] 따라서본발명의지르코늄계금속의제조를위한재순환시스템은상술한 방법들을연계하여경제적이고효율적으로지르코늄계금속올제조할수있는 장점이 있다.
[34] 따라서본발명의지르코늄계금속의제조시스템은염소가스등이공정
과정에서발생하지않고산세폐액을재활용할수있어친환경적인장점이있다.
[35] 여기에명시적으로언급되지않은효과라하더라도,본발명의기술적특징에 의해기대되는이하의명세서에서기재된효과및그잠정적인효과는본발명의 명세서에기재된것과같이취급됨을첨언한다.
도면의간단한설명
[36] 도 1은본발명의일예에따른지르코늄계금속의제조시스템의각공정 및 공정들의순환시스템을도시한개략도이다.
[37] 도 2는실시예 1에따른최종화합물 (Ba2ZrF8)의주사전자현미경 이미지및 액스 -레이회절스펙트럼에관한데이터이다.
[38] 도 3은실시예 1에따른여액내잔존하는불순물의주사전자현미경이미지및 액스 -레이회절스펙트럼에관한데이터이다.
[39] 도 4는실시예 1및실시예 2에관한것으로， BaF2의입자크기에따른여액내 함유불순물의농도를유도결합플라즈마분광분석법으로측정하여나타낸 그래프이다.
[4이 도 5는본발명의일예에따른반웅로의개략도，실시예 3에따른 BaF2분말을 나타낸이미지및실시예 3에따른 ZrF4분말을나타낸이미지를도시한것이
[41] 도 6은실시예 3에따른 BaF2분말을확대하여나타낸이미지와,상기 BaF2분말 성분의중량비및원자비를나타낸표이다.
[42] 도 7은실시예 3에따른 BaF2분말을 X-선회절분석법으로측정한
스팩트럼이다
[43] 도 8은실시예 3에따른 ZrF4분말올확대하여나타낸이미지와，상기 ZrF4분말 성분의중량비및원자비를나타낸표이다.
[44] 도 9는실시예 3에따른 ZrF4분말을 X-선회절분석법으로측정한
스팩트럼이다.
[45] 도 10은실시예 3내지실시예 9에 대한것으로， BaF2분말의온도및시간에 따른무게감소율을나타낸그래프및표이다.
[46] 도 11은실시예 5에따른 ZrF4분말을 X-선회절분석법으로측정한
스팩트럼이다.
[47] 도 12는실시예 4에따른 ZrF4분말을 X-선회절분석법으로측정한
스백트럼이다，
[48] 도 13은실시예 10의순환전류법의공정원리를나타낸개략도이다.
[49] 도 14는실시예 10에따라제조되는지르코늄의산화환원거동을분석한 데이터이다.
[5이 도 15는실시예 10의전해제련공정중의 일예를나타낸이미지와，전해제련 공정시시간에따른전압을나타낸그래프이다.
[51] 도 16은실시예 10에따라수득된생성물을주사전자현미경및원소
분석기 (Energy Dispersive x-ray Spectroscopy, EDS)로측정한결과를나타낸 데이터이다.
[52] 도 17은실시예 10에따른생성물을 X-선회절분석법으로측정한
스팩트럼이다ᅳ
[53] 도 18은실시예 11에따라제조된지르코늄금속을 X-선회절분석법으로
측정한스팩트럼이다.
[54] 도 19는실시예 11에따라제조된 Zr금속을글로우방전질량분석법 (Glow
Discharge Mass Spectrometry: GDMS)으로측정한데이터이다.
[55] 도 20은실시예 12에따라제조된 Cu-Zr계금속의이미지이다.
[56] 도 21은실시예 12에따라제조된 Cu-Zr계금속을주사전자현미경및원소 분석기 (Energy Dispersive x-ray Spectroscopy, EDS)로측정한결과를나타낸 데이터이다.
[57] 도 22는실시예 12에따라제조된 Cu-Zr계금속을 X-선회절분석법으로측정한 스팩트럼이다.
발명의실시를위한형태
[58] 이하첨부한도면들을참조하여본발명의지르코늄계금속의제조시스템을 상세히설명한다.
[59] 본발명에기재되어 있는도면은당업자에게본발명의사상이층분히전달될 수있도록하기위해 예로서제공되는것이다.따라서본발명은제시되는 도면들에한정되지않고다른형태로구체화될수도있으며，상기도면들은본 발명의사상을명확히하기위해과장되어도시될수있다.
[6이 또한본발명에서사용되는기술용어및과학용어에 있어서다른정의가 없다면，이발명이속하는기술분야에서통상의지식을가진자가통상적으로 이해하고있는의미를가지며,하기의설명및첨부도면에서본발명의요지를 블필요하게흐릴수있는공지기능및구성에대한설명은생략한다.
[61] 또한본발명에서특별한언급없이불분명하게사용된 %의단위는증량 %를 의미한다.
[62] 본발명은지르코늄계금속의제조시스템에관한것이다.구체적으로，본
발명은도 1에서와같이지르코늄계금속의제조를위해수반되는다양한 공정들을일련의공정으로통합및적용하고，각공정들이재순환될수있도록 시스템화함으로써,경제적이고효율적이면서도고순도의지르코늄계금속의 제조가가능한시스템을제공하는것이다.
[63] 따라서본발명은 Zr함유산용액이용 Ba-Zr-F계전해질제조공정, Ba2ZrF8 분리공정및 /또는전해제련공정올포함하는것으로크게 3공정으로구분될수 있다.
[64] 본발명의일공정인 Zr함유산용액이용 Ba-Zr-F계전해질제조공정은 Zr 함유산용액에 BaF2를환원제로사용하여 Ba2ZrF8을제조하는단계를포함한다. 구체적으로， Zr함유산용액이용 Ba-Zr-F계전해질제조공정인 Ba2ZrF8의제조 방법은 a) Zr함유산용액을 8& 로환원및 Ba2ZrF8으로침전하는단계및 b)상기 a)단계에서침전된 Ba2ZrF8을수득하는단계를포함할수있다.
[65] 상기 Zr함유산용액은 Zr또는 Zr계화합물을포함하는산용액을의미하며， 경제적인측면및친환경적인측면에서바람직하게는산세폐액 (Pickling solution)일수있다.구체적인일예로, Zr함유산용액은사불화지르코늄 (ZrF4) 둥의 Zr계화합물과질산,염산，불산둥의산을포함할수있다.또한상기 Zr 함유산용액의일예로, Hf이제거된지르코니아를산용액으로용해시켜제조된 산용액일수있다.이때 Zr함유산용액은 Zr또는 Zr계화합물을 0.01~15중량 %， 구체적으로 0.1~10중량 %로포함할수있으나,소량또는과량포함하여도 무방하므로이에제한되지않는다.
[66] 일반적으로,원자로용연료어셈블리，특히경수원자로용연료어셈블리는 지르코늄관또는지르코늄합금관으로이루어진종방향가이드관과횡방향 스페이서그리드를포함하는골격을가지는다발형태의상호평행연로봉으로 구성된다.이러한복수개의지르코늄관또는지르코늄합금관을제조하는 데에는연속적인넁간압연공정과이후각각의열어닐링공정이필요하며, 각각의공정사이에는탈기및화학적산세공정등이필수적으로수행된다. 따라서상기산세공정둥에의해공정후회수되는산세폐액은불화수소산,물， 질산둥을포함하며，특히공정중반웅하여생성되는 ZrF4둥의 Zr계화합물을 포함할수있다.
[67] 상기 a)단계는 Zr함유산용액에 BaF2를투입하고환원반웅을유도하여 Ba2ZrF 8을침전시키는단계이다.이때 Zr함유산용액과 BaF2의혼합비는 Ba2ZrF^l 합성될수있을정도라면제한되지않으며,예컨대 Zr함유산용액 100중량부에 대하여 0.5~30중량부인것일수있다.
[68] 상기 b)단계는상기 a)단계에서합성된 Ba2ZrF8을수득하는단계로，예컨대 여과방법,여과후건조방법둥올통하여 a)단계에서수득된생성물을여액과 Ba2ZrF8으로분리하여 Ba2ZrF8을수득하는단계를포함할수있다.분리된 Ba2ZrF 8을건조할경우，건조은도및건조시간은제한되지않으며，예컨대 20~120°C및 1~20시간일수있다.
[69] 바람직한일예에있어서，상기 BaF2의평균입경은 0.1~50 /ffli,바람직하게는 0.1-10 ,보다바람직하게는 0.1~1 / Hi일수있다.이를만족할경우， Ba, Zr및 F의반웅율올현저히중가시킬수있어，합성되는 8 1^의수율이현저히 증가할뿐만아니라，특히반웅하지못한 Ba및 Zr등의미반웅물의농도가극히 감소됨으로써매우순도가높은 8 &^을수득할수있다.
[70] 따라서상기 BaF2의평균입경이 0.1~50 ,바람직하게는 0.1~10 ^m,보다
바람직하게는 0.1-1 을만족할경우,상기 b)단계에서수득된 Ba2ZrF8의 순도는 99.98%이상일수있다.특히상기평균입경을만족하는 BaF2가환원제로 사용될경우, NaF가환원제로사용되는경우와대비하여매우높은순도의 Ba2 ^을높은수율로제조할수있다.구체적으로,상기평균입경을만족하는 BaF2 가사용되는경우는상기 a)단계에서반웅하지않고불순물로서산과반옹하여 잔류할수있는 Ba(Na)둥의불순물의농도가 NaF가사용되는경우보다 10배 이상감소되는현저한효과가있다.
[71] 이렇게제조된 Ba2ZrI^^예컨대 10~500 nm범위의평균직경을가질수있다. 또한 8 ¾ 은다양한형태로존재할수있으며，예컨대상기평균직경올가지는 다수의입자들이합일되어폴리-미소결정형태로존재할수있다.
[72] 상술한 8 ¾^의제조방법을통해 Zr함유산용액으로부터 8 ¾을제조할 수있으며，상기 8 ¾^은지르코늄계금속의제조에사용될수있다.
[73] 즉，본발명의지르코늄계금속의제조방법은 Ba-Zr-F계전해질을전해하여 음극으로지르코늄계금속을환원및석출하는단계를포함하는전해제련 공정을포함할수있다.이때상기 Ba-Zr-F계전해질은 a) Zr함유산용액을 BaF2 로환원하여 Ba2ZrF8으로침전하는단계및 b)상기 a)단계에서침전된 Ba2ZrF8을 수득하는단계를포함하여제조되는 Ba2ZrF8일수있다.
[74] 상기지르코늄계금속의제조방법은 Ba-Zr-F계화합물을전해질로하여
전해제련함으로서,음극으로지르코늄계금속을환원및석출하는방법이다. 따라서상기지르코늄계금속의제조방법은 8 ¾^을전해질로사용하기위해 8 ¾^의용융점이상의온도로가열하여전해제련하는단계를포함하므로, 이를위한많은에너지를필요로한다.
[75] 한편， Ba2ZrF^] 1031°C의용융점을가지는반면 BaZrl^i 765°C의낮은
용융점을가진다.따라서상기 BaZrF6를합성하는단계에서 8 ¾^으로부터 전환된 BaZrFfi를전해질로하여지르코늄계금속을제조할경우，전해제련공정 시소비되는에너지를최소화할수있고,공정효율을현저히증가시킬수있다. 또한전해쩨련공정시사용되는장비의고은부식,열피로파괴를최소화할수 있다.
[76] 이에 ,에너지효율의극대화를위한,보다바람직한일예로,지르코늄계금속의 제조방법은 Ba2ZrF8과 ZrF4를흔합하고가열하여 BaZrF6를합성하는단계를더 포함할수있다.
[77] 상세하게 ,상기 BaZrF6를합성하는단계에서합성되는 8321¾는 ZrF4와 Ba2ZrF8 을반웅로에투입하고가열하여합성되는것일수있다.이때가열온도는 BaZrFfi 가합성될수있을정도라면제한되지않으며，예컨대 700~900oC,구체적으로 750~850oC일수있다.이때반웅분위기는부생성물의생성을최소화하기위한 측면에서아르곤，질소둥의불활성분위기인것이좋다.또한 8 를합성하는 단계는반웅로가밀봉된상태에서합성이수행될수있다.구체적으로， ZrF4는 1,000°C에서온도에서 5.29X101 atm의낮은증기압상태이므로,이를고려하여 밀봉상태의반웅로에서 BaZrF6가합성되는것이높을수율올보장할수있다. 또한상기 ZrF4는원활한반웅을위해파쇄단계등을거쳐 l~10O urn크기를 가지는것이좋다.
[78] 또한 BaZrF6의합성시， B ZrI ^ ZrF4의혼합비는 BaZrF6가합성될수있을 정도라면제한되지않으며，예컨대 Ba2ZrF8:ZrF4의몰비가 1:0.5~2,바람직하게는 1:1~1.5인것일수있으며，바람직한일실시예로 1:1일수있다.또한공정효율 측면에서 Ba2ZrF8이 ZrF4보다더낮은몰비로흔합되는것이흔합물의
용융온도가상대적으로더낮아지게되어바람직하다.
[79] 상기 83；^6를합성하는단계에서사용되는 ZrF4는다양한경로로부터
제조되는 ZrF4이어도무방하나，공정효율을극대화하기위해후술하는 c) Ba2 ZrF8을 BaF2및 ZrF4로분리하는단계를포함하는 Ba2ZrF8분리공정로부터 수득된 ZrF4인것이바람직하다.이는상기 c)단계에서 ZrF4와함께분리되어 수득되는 BaF2도상술한 a)단계에서다시사용될수있기때문이다.따라서상기 c)단계로부터수득되는 BaF^상기 a)단계에서의 BaF^다시사용될수있을 뿐만아니라,상기 c)단계에서분리및수득되는 ZrF4도상기 BaZrF<^합성하는 단계의 ZrF4로사용될수있으므로，공정효율이보다극대화될수있다.
[8이 따라서본발명의지르코늄계금속의제조방법은상기 a)단계및 b)단계와 함께， c) Ba2ZrF8을 BaF2및 ZrF4로분리하는단계를더포함할수있다.특히상기 c)단계의 8 ^는상기 BaF2를이용하여지르코늄계금속의제조에사용되는 Ba-Zr-F계화합물의제조방법에서제조되는 Ba2ZrF8으로부터사용될수있어， 공정효율을현저히증가시킬수있다.
[81] 구체적으로，상기 c)단계는 Ba2ZrI^:반웅로에투입하고가열하여상기
반웅로내하부공간에형성되는 BaF2및상기공간외부에웅축되어형성되는 ZrF4로서분리되는단계를포함할수있다.상기분리되는단계는 Ba2ZrF8을 반웅로에투입하고가열하여 BaF2와 ZrF4로상분리되는단계이다.
[82] 상기 c)단계의가열온도는 Ba2ZrF^l용융되어 BaF2와 ZrF4로존재할수있올 측면에서 1,000~1,200°C일수있다.
[83] 바람직한일예에있어서，상기 c)단게의가열은도는 1,000~1,150°C,보다
바람직하게는 1,000~1,100°C일수있으며，이를만족할경우， BaF2와 ZrF4가극히 높은순도로각각구분되어선택적으로분리될수있다.상세하게， Ba2Zrf^i 용융점이상의온도에서 BaF2와 ZrF4가혼재하며, BaF2는액상 (용융상태)으로 반웅로내하부공간에형성되고 ZrF4는기상 (증기상)으로반웅로내상부또는 상기공간외부에형성됨에따라,이후용융점이하의은도에서 BaF2는반웅로내 하부에형성되고, ZrF4는반웅로내상부또는상기공간외부에웅축되어분리될 수있다.이때가열온도가 U50 이상일경우， ZrF4의급속한증발로인한기류 상승에의해증기상에 BaF2가흔입되어 BaF^ ZrF4의분리가어려울수있다. 반면,가열온도가 1,000~1,150°C,바람직하게는 1,000~1,100°C일경우, BaF2와 ZrF 4가자동적으로반웅로내부에서각각다른공간으로구분되어분리될수있다.
[84] 상기 c)단계의가열시간은 Ba2ZrF 용융되어 Bai^f Ζι 로분리될수있을 정도라면크게제한되지않으며，예컨대 1~15시간，바람직하게는 5~13시간, 보다바람직하게는 5~11시간일수있다.이를만족할경우,분리되어수득되는 ZrF4의수율이현저히증가할수있다.
[85] 상술한바와같이，상기 c)단계의분리는 ZrF4가기상으로액상의 8^2와
분리되는것일수있으며，바람직하게는진공증류법에의해수행되는것일수 있다.이때반웅로내부는진공에근접한상태,바람직하게는진공상태일수 있으며，예컨대 lOHO"1 torr의압력인상태일수있다.
[86] 또한상기 c)단계에서 8 의용융점이상의온도에서는 ZrF4가기상으로 존재하므로， c)단계는기상의 ZrF4를웅축하는단계를더포함할수있다.
구체적인일예로,기상의 ZrF4는증기웅축기에서고상의 ZrF4분말로수득될수 있다ᅳ웅축기내에서의온도는크게제한되지않으며,예컨대 25~300°C, 구체적으로 50~200°C보다구체적으로 75~150°C일수있다.
[87] 상기 c)단계의반웅로는제한되지않고다양한것들이사용될수있으나， 효과적인분리를위해서다음의반웅로가사용되는것이좋다.바람직한일예에 있어서，상기반웅로는,반웅로내하부에구비되고, Ba2ZrF^l장입되도록 형성된상기공간인용기부 (12);및상기용기부 (12)외부에형성되어 ZrF4가 분리되어포획되는포획부 (11);를포함할수있다.상기용기부에서 Ba2ZrF8의 용융이진행될때，용기부에서 BaF2가용융되는동시에 ZrF4는기상으로 상승하게된다.따라서 BaF2는용기부에액상에서이후고상으로응고되어 잔존하며， ZrF4는기상으로용기부외의위치로이동하고이후웅축되어 분리되게된다.이에따라 BaF2와 ZrF4는상차이에의해매우높은순도로 효과적으로분리될수있다.
[88] 구체적으로,상기반웅로는반웅로내하부공간에구비되어용융점이상의 온도에서 ZrF4와분리되어 BaF2가잔존하여형성되는용기부 (12);및 ZrF4가 기상으로상승하고웅축되어 ZrF4가형성되는상기용기부 (12)를제외한공간인 포획부 (11);를포함할수있다.이때상기용기부 (12)는고상의 Ba2ZrF^l장입될 수있는공간을포함하며,용융점이상의온도에서 ZrF4가기상으로상승되어 분리될수있도록용기부 ( 12)상단과반웅로상면이이격되어형성된다.이의 이격거리는용기부 (12)에장입된 Ba2ZrF8이 BaF2및 ZrF4로상변환하여기상의 ZrF4가상기공간외부로이동될수있을정도라면무방하다.상기반웅로의 재질로는 BaF2및 ZrF4와부반웅하지않는것이좋으며,예컨대니켈올
주성분으로하는재질일수있다.구체적으로,상기반웅로에포함되는용기부로 니켈올주성분으로서제조된니켈도가니가예시될수있다.
[89] 상술한바와같이지르코늄계금속의제조방법은 Ba2ZrF8또는 BaZrF6둥의 Ba-Zr-F계화합물을전해질로하여전해제련함으로서,음극으로지르코늄계 금속을환원및석출하는단계를포함하는전해제련공정을포함할수있다. 이렇게석출된지르코늄계금속은고순도의지르코늄금속또는구리-지르코늄 합금일수있다.상기전해제련은도 14에도시된바와같은전해환원법을 이용할수있으며，음극에서지르코늄이온이전자를받아환원되어지르코늄 금속또는구리-지르코늄합금형태로석출되는원리로수행될수있다.
[90] 상기전해제련공정시사용되는양극은전해질과화학반웅이없는은 (Ag), 염화은 (AgCl),텅스텐,백금,탄소전극인것이높은순도의지르코늄계금속의 제조를위해서바람직하다.
[91] 상기음극은지르코늄계전극또는전해질과반웅도가높은구리계전극이 사용될수있다.
[92] 구체적인일예로，지르코늄금속의제조방법으로서，상기음극은지르코늄계 금속전극일수있으며，상기환원및석출되는지르코늄계금속은 Zr금속일수 있다.따라서지르코늄금속이상기지르코늄계음극으로환원및석출됨으로서， 고순도의지르코늄금속을수득할수있다.
[93] 또한구체적인일예로,구리-지르코늄합금의제조방법으로서 ,상기음극은 구리계금속전극일수있으며，상기환원및석출되는지르코늄계금속은 Cu-Zr계합금일수있다.즉,구리계음극과지르코늄이온이함께반웅하여상기 음극에 Cu-Zr계합금이상기음극으로환원및석출될수있다.석출된 Cu-Zr계 합금은구체적으로 CuZr, CuZr2, Cu5Zr, CugZr3, Cu10Zr7및 Cu5,Zr14등에서 선택되는조성의 Cu-Zr계화합물을하나또는둘이상포함할수있다.
[94] 특히상기방법으로 Cu-Zr계합금이제조될경우, 10-25중량 %의 Cu-Zr계
합금이제조될수있어,지르코늄을고농도로함유한 Cu-Zr계합금의제조가 가능한효과가있다.
[95] 전해제련공정시전류,전압둥의공정조건은통상의기술자가요구에따라 적절히채택하여조절할수있으므로제한되지않으나，높은환원율측면에서 1.17 V이상의환원전위에서환원이진행될수있도록하는것이바람직하다.
[96] 상술한바와같이，전해제련공정을통해지르코늄계금속을포함하는
생성물을수득할수있으나,상기생성물은지르코늄계금속과함께용융염 형태의전해질을포함할수있다.
[97] 따라서상기전해제련공정은전해제련이후에음극으로석출된생성물을
지르코늄계금속과용융염올분리하는단계를더포함할수있다.상기단계의 일예로，증류법을이용하여지르코늄계금속과용융염을분리하는단계가있다. 구체적으로，진공증류장치둥을이용할수있으며,생성물중용융염이증류될 수있을정도의은도,예컨대 700~l,200oC로가열하는과정올포함할수있다. 이때 ΐσ5~102 torr의압력에서 1~20시간동안증류가수행될수있다.하지만 이는바람직한일예로서설명한것일뿐，이에본발명이제한되지않음은 물론이다.
[98]
[99] 이하본발명을실시예를통해상세히설명하나，이들은본발명을보다
상세하게설명하기위한것으로,본발명의권리범위가하기의실시예에의해 한정되는것은아니다.
[100]
[101] [실시예 1]
[102] 사불화지르코늄 (ZrF4)을포함하는산세폐액 1,000 g을반웅기에넣고 23°C에서 2분동안교반한후，평균입경이 1 인 BaF250 g을투입하고 10분동안 교반하였으며，교반이진행되는동안흰색고체의침전이발생되었다.반웅이 완결된후침전된화합물을필터하고,상기화합물을 100°C에서 10시간동안 건조하여최종화합물을수득하였다.또한상기필터시분리된잔존불순물을 함유하는여액을건조하여수득하였다.
[103] 상기최종화합물과여액내함유불순물의 입자구조를확인하기위해，
주사전자현미경,엑스 -레이회절및입도분석을진행하였다.
[104] 그결과，도 2에서와같이,상기최종화합물은 20 의평균크기를갖는
폴리-미소결정형태를가지며， Ba2ZrF^해당하는특성피크만을가져 Ba2ZrF8 임을확인하였다.또한도 3에서와같이，여액내잔존하는불순물은폴리 -미소 결정형태를가지며, Sn, Zr, F, 0에해당하는특성피크를가짐을확인하였다.
[105] [비교예 1]
[106] 실시예 1에서 BaF2대신 NaF를사용한것올제의하고，실시예 1과동일하게 수행하였다.
[107] [실시예 2]
[108] 실시예 1에서평균입경이 1 /m인 BaF2대신평균입경이 45； c 인 BaF2및
평균입경이 120； ffli인 BaF2를각각사용한것올제외하고，실시예 1과동일하게 각각수행하였다.
[109] 또한 BaF2의입자크기에따른여액내함유된블순물의함량을분석하기위해, 실시예 1의평균입경이 1 인 BaF2인경우,상기평균입경이 45 m인 BaF2의 경우및상기평균입경이 120 인 BaF^경우로부터수득된각각의여액에 대한유도결합플라즈마분광분석 (ICP-OES)을진행하였다.
[110] 그결과도 4에서와같이,실시예 1의평균입경이 ffli(0.1~10 /zm)인 BaF2의경우 및평균입경이 45 l~ 5 /Di)인 BaF2의경우는불순물및환원제의농도가매우 낮음을확인하였으며,평균입경이 120卿 (120 이상)인 BaF2의경우는 상대적으로불순물및환원제의농도가높음을확인하였다.이는 BaF2의 입도가 감소함에따라비표면적이증가해산세폐액내 Zr과의반웅성이증가하는것에 따른것으로판단된다.즉, BaF2입도가커지면반웅에참여하지못한바륨 (Ba)이 여액내존재하는질산둥의산과결합하여질산바륨 (BaN03)둥올형성하므로, 보다낮은비표면적은갖는 BaF2입자가사용된경우가보다높은순도및수율을 가짐을알수있다.
[111] 특히평균입경이 45 /mi이하인 8^2를사용한실시예 1및실시예 2의여액은 반옹하지않은 Ba의농도가 250 ppm이하로매우낮은수준인반면， NaF를 사용한비교예 1의여액은질산나트륨 (NaN03)등으로전환될수있는 Na의 농도가 10,000 ppm이상으로매우높은수준이었다.
[112] 따라서 BaF2가 NaF보다환원제로서반웅율이매우높으며, Ba또는 Na둥의 산과반웅할수있는불순물의발생을최소화할수있고， Zr의반웅수율을 현저히향상시킬수있음을알수있다.
[113] [실시예 3]
[114] 도 5에서와같이 ,팔불화이바롬지르코늄 (Ba2ZrF8) 80 g을니켈도가니 (12)에 채운후 10"3 toir의진공상태의튜브 (11)에장입하여 1,000°C에서 10시간동안 유지하였다.이후니켈도가니에남은고상의잔존물 (BaF2) 50.73 g과류브의 외벽에생성된분말 (ZrF4) 3.89 g을수득하였다.
[115] 상기잔존물및상기분말의성분을분석하기위해，주사전자현미경및 X-선 회절분석법을이용하여측정하였다.
[116] 그결과，상기잔존물은도 6로부터폴리-미소결정형태를가지는것을확인할 수있으며，도 7의 X-선회절분석스펙트럼으로부터이불화바륨 (BaF2)의피크를 가짐을확인할수있다.또한상기분말은도 8로부터폴리 -미소형태를가지는 것을확인할수있으며,도 9의 X-선회절분석스펙트럼으로부터
사불화지르코늄 (ZrF4)및불화옥시지르코늄화합물 (ZrvO^F^)의피크를가짐을 확인할수있다.다만,상기도 9의스펙트럼에서삼불화알루미늄 (A1F3)의피크도 일부확인할수있는데,이는류브의재질이산화알루미늄인것에기인한것으로 판단된다.
[117] 또한상기잔존물에대한무게감소율을측정하였으며，이는도 10에도시되어 있다.상기무게감소율은 (초기 Ba2ZrF8내 BaF^이론적중량) /(초기 Ba2ZrF8의 증량)으로정의된다.
[118] [실시예 4]
[119] 실시예 3에서 1,000°C대신 1,100°C에서수행한것올제외하고，실시예 3과 동일하게수행하였다.
[120] [실시예 5]
[121] 실시예 3에서 l,000oC대신 1,200οΟ에서수행한것을제외하고,실시예 3과 동일하게수행하였다.
[122] [실시예 6]
[123] 실시예 3에서 10시간대신 13시간동안유지한것을제외하고，실시예 3과 동일하게수행하였다.
[124] [실시예 7]
[125] 실시예 4에서 10시간대신 13시간동안유지한것올제외하고，실시예 3과 동일하게수행하였다.
[126] [실시예 8]
[127] 실시예 5에서 10시간대신 5시간동안유지한것을제외하고,실시예 3과
동일하게수행하였다.
[128] [실시예 9]
[129] 실시예 5에서 10시간대신 7시간동안유지한것을제외하고,실시예 3과
동일하게수행하였다.
[130] 실시예 3내지실시예 9에서수득된상기잔존물및상기분말에대하여
X-선회절분석법으로측정한결과, 1,200°C에서수행된실시예 5의경우에는 BaF 2와 ZrF4가서로선택적으로분리되지않았다.이는도 11로부터확인할수 있으며，이러한결과는높은은도로인해 ZrF4의급속한증발로인한기류상승에 의해증기상에 BaF^ 혼입에의한것에기인하는것으로판단된다.반면, 1,000°C및 1,100°C에서수행한실시예 3및실시예 4와실시예 6및실시예 7의 경우는도 7，도 12에서와같이 , BaF2와 ZrF4가서로선택적으로분리되어각각 잔존물및분말에존재하는것을확인할수있었다.즉, BaF2와 ZrF4를
선택적으로분리하기 1,050 1, 150°C,보다바람직하게는 1,000~1,100°C은도 범위에서수행되어야함을알수있다.
[131] 또한수율측면에 있어서，도 10에서와같이 13시간이하，바람직하게는 11 시간이하로유지하는것이 ZrF4의높은수율을기대할수있어좋다.
[132] [실시예 1이
[133] 실시예 1의최종화합물인 Ba2ZrF8과실시예 3의외벽에생성된분말인 ZrF4를 1: 1몰비로흔합하여반웅기에투입하여밀봉한후,아르곤분위기에서 800oC로 가열하여 BaZrF6를합성하였다.
[134] 먼저적절한환원전위를알아보기위해，상기 8^^6를전해질로사용하여도 13에서와같이전해제련장치를이용하여순환전류법으로지르코늄금속함유 생성물의제조및지르코늄의산화환원거동을분석하였다.이때
양극 (기준전극)은텅스텐이사용되었으며,음극 (희생전극)은혹연봉이 사용되었다.그결과，도 14에서와같이 0.84 V에서 Ζ +2σ→Ζτ2+의반웅이 진행되었으나 , -U7 V에서는 Zr2++2e→Zr의반웅이진행되는환원거동이 나타났다.따라서 1.17 V이상의환원전위에서전해제련을실시하는것이 바람직한것으로판단된다.
[135] 상기 BaZrFfi를전해질로사용하여도 13에서와같이전해제련장치를이용하여 지르코늄금속을제조하였다.이때양극 (기준전극)은탄소봉이사용되었으며, 음극 (희생전극)은지르코늄금속전극이사용되었으며 , 200 mA/cm2의정전류로 전류를인가하여 180분동안지르코늄전해제련수행하였다. [136] 전해제련하여음극에환원석출된생성물을수득하여,이를도 16및도 17에서와같이원소분석기 (Energy Dispersive x-ray Spectroscopy, EDS), 주사전자현미경및엑스 -레이회절분석기를이용하여분석하였다.
[137] 그결과，상기생성물은금속은도 16에서와같이평균 2~5 mm의
크기이었으며 ,도 17에서와같이 Zr금속과 Ba2ZrF^l혼합되어 있음올알수 있다.
[138] [실시예 11]
[139] 실시예 10에서수득된생성물을분쇄하고，진공증류장치내니켈도가니에 장입하여염중류를진행하여 , Ba2ZrF8둥의잔류염이제거된지르코늄금속을 수득하였다.이때진공증류는아르곤분위기및 850oC에서 lC torr의압력으로 10시간동안진행하였다.
[140] 상기잔류염이제거된지르코늄금속을원소분석기 (Energy Dispersive x-ray Spectroscopy, EDS),주사전자현미경및액스 -레이회절분석기을이용하여 분석하였다.이의결과는도 18에도시되어 있다ᅳ
[141] 또한상기잔류염이제거된지르코늄금속을아크용해로에장입하여
지르코늄금속잉곳을제조하였으며，상기 잉곳을글로우방전질량분석을통해 잔존불순물분석을수행하였다.이의 결과는도 19에도시되어 있다.
[142] 그결과，도 18에서와같이,잔류염이제거된지르코늄금속은지르코늄에 해당하는특성피크만을가짐을확인하였다.또한도 19에서와같이，지르코늄 금속의순도가 99.98중량 %이상이었으며,이는원자로피복관에사용가능한 기준인 ASTM-B349기준을층분히상회하는결과이다.
[143] [실시예 I2]
[144] 실시예 10에서음극을흑연봉대신구리전극을사용한것을제외하고,또한 생성물을분쇄하지않고,실시예 10과동일하게수행하였다.
[145] 그결과,도 20및도 22에서와같이 Cu-Zr계합금이제조되었으며,도 21에서와 같이구리내지르코늄함량이 15 ~ 17중량 %인것을확인하였다.따라서본 발명의제조방법으로 Cu-Zr계합금을제조할경우,합금전체중량기준 지르코늄의함량이 15중량 %이상으로매우높은 Cu-Zr계합금을제조할수 있음을알수있다.
[146] [부호의설명]
[147] 11 :포획부
[148] 12 :용기부
[149] 20：가열부

Claims

청구범위
[청구항 1] a) Zr함유산용액을 BaF2로환원및 Ba2ZrF8으로침전하는단계및
b)상기 a)단계에서침전된 Ba2ZrFs을수득하는단계를포함하는 Ba2ZrF8 의제조방법.
[청구항 2】 제 1항에 있어서，
상기 BaF2의평균입경은 0.1~50 인 Ba2ZrF8의제조방법.
[청구항 3] 제 2항에있어서，
상기 b)단계에서수득된 Ba2ZrF8의순도는 99.98%이상인 Ba2ZrF^제조 방법.
[청구항 4] Ba2ZrF8또는 BaZrF6를전해질로서전해하여음극으로지르코늄계금속을 환원및석출하는단계를포함하는지르코늄계금속의제조방법 .
[청구항 5] 제 4항에 있어서，
상기 Ba2ZrF8은,
a) Zr함유산용액을 BaF2로환원하여 Ba2ZrF8으로침전하는단계및 b)상기 a)단계에서침전된 Ba2ZrFs을수득하는단계를포함하여 제조되는지르코늄계금속의제조방법.
[청구항 6] 제 4항에 있어서,
상기 BaZrF6는 8 &1; 8과 ZrF4를흔합하고가열하여 8 1; 6를합성하는 단계로부터제조되는지르코늄계금속의제조방법.
[청구항 7] 제 6항에있어서,
상기 BaZrF6를합성하는단계에서 Ba2ZrF8은，
a) Zr함유산용액을 BaF2로환원하여 Ba2ZrF8으로침전하는단계및 b)상기 a)단계에서침전된 8 ¾을수득하는단계로부터제조되는 지르코늄계금속의제조방법 .
[청구항 8] 제 5항에있어서,
' c) ¾2& 을 BaF2및 ZrF4로분리하는단계를더포함하며，
상기 a)단계의 Bal^^상기 c)단계에서분리된 BaF2가사용되는 지르코늄계금속의제조방법.
[청구항 9] 제 6항에 있어서,
c) Ba2ZrIVi— BaF2및 ZrF4로분리하는단계를더포함하며 , 상기 BaZrF6를합성하는단계의 ZrF4는상기 c)단계에서분리된 ZrF4가 사용되는지르코늄계금속의제조방법.
[청구항 10] 제 7항에있어서,
c) Ba2ZrF8을 BaF2및 ZrF4로분리하는단계를더포함하며， 상기 a)단계의 BaF2는상기 c)단계에서분리된 BaF2가사용되며， 상기 BaZrF6를합성하는단계의 ZrF4는상기 c)단계에서분리된 ¾ 가 . 사용되는지르코늄계금속의제조방법 .
[청구항 11】 제 8항내지제 10항에서선택되는어느한항에있어서， 상기 c)단계는 Ba2ZrF8을반웅로에투입하고진공상태에서 1~15시간 동안 l,000~l,150oC로가열하여 BaF2및 ZrF4로분리하는단계를포함하는 지르코늄계금속의제조방법 .
[청구항 12】 제 4항내지제 7항에서선택되는어느한항에있어서,
상기음극은지르코늄계금속전극이며,상기환원및석출되는 지르코늄계금속은 Zr금속인지르코늄계금속의제조방법 .
[청구항 13] 제 4항내지제 7항에서선택되는어느한항에 있어서，
상기음극은구리계금속전극이며，상기환원및석출되는지르코늄계 금속은 Cu-Zr계합금인지르코늄계금속의제조방법 .
PCT/KR2017/009999 2016-09-13 2017-09-12 지르코늄계 금속의 제조 시스템 WO2018052232A1 (ko)

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