Method for preparing high purity zirconium by calcium in situ distillation-deoxidation

A high-purity, in-situ technology, applied in the field of metal smelting, can solve the problems of contaminated zirconium products, difficult to control uniformity, and unsatisfactory zirconium oxygen content of less than 0.14wt%, to achieve high solubility, reduce energy consumption, and reduce activity degree of effect

Inactive Publication Date: 2019-04-16
有研资源环境技术研究院(北京)有限公司
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Problems solved by technology

[0003] Chinese patent 200910300086.9 discloses a method for preparing low-oxygen metal zirconium. The method uses zirconium hydride powder or oxygen-containing metal zirconium powder as a raw material, and metal Ca as a deoxidizer. After reacting at ℃ for 2-8 hours, calcium reacts with oxygen in zirconium in the form of steam to form calcium oxide, thereby removing oxygen in zirconium; Calcium oxide will adhere to the surface of zirconium powder to block the progress of the reaction. There is no solvent that can dissolve calcium oxide in the reaction system, so that calcium oxide exists in the form of pure solid, and its thermodynamic activity is 1, so it is not conducive to the deep removal of zirconium. The oxygen in it is not suitable for the deoxidation of zirconium plates, zirconium wires and other special-shaped components after processing; in addition, the zirconium powder with calcium oxide attached to the surface will sinter at the reaction temperature, and it will be mixed in the small gaps in the zirconium powder. It is difficult to completely remove it only by pickling, so its oxygen content can only be reduced to 0.23-0.59%, which does not meet the standard requirement (YS / T397-2015) that the oxygen content in zirconium is less than 0.14wt%, let alone the quality of high-purity zirconium Requirements (O≤100ppm)
The first problem with this process is that during the packaging, storage and transportation of the high-purity calcium obtained by distillation, the high-purity calcium will introduce nitrogen and oxygen impurities due to the absorption of oxygen, nitrogen and water in the environment, and the nitrogen and oxygen impurities will Contamination of zirconium products; the second problem is that the distillation and deoxidation of the traditional process are completed in two equipments, and the energy consumption is high

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  • Method for preparing high purity zirconium by calcium in situ distillation-deoxidation

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Embodiment 1

[0034] Get 1 metal zirconium block 10g, the oxygen content in the metal zirconium block is 730ppm, press (CaCl 2 ): m(Zr) = 5:1 Weigh 50g of anhydrous calcium chloride (dehydrated at 500°C for 18 hours before use), and weigh 8g of high-purity calcium chips (at 900°C, calcium in anhydrous calcium chloride molten salt 2.5 times the saturation solubility), metal zirconium and anhydrous calcium chloride are filled in the zirconium crucible, high-purity calcium chips are filled in the gap between the zirconium crucible and the stainless steel crucible, and then the stainless steel crucible is sealed with a high-temperature sealing gasket. Specific as figure 1 shown.

[0035]Put the sealed crucible into a vacuum tank heated by a resistance furnace, cover the furnace cover, vacuumize to 0.1Pa, and then wash with argon. Under the protection of argon, heat up to 900°C at a heating rate of 5°C / min, and keep at 900°C for 44 hours. After the heat preservation is completed, the furnace i...

Embodiment 2

[0037] Get 1 metal zirconium block 15g, the oxygen content in the metal zirconium block is 720ppm, press (CaCl 2 ): m(Zr) = 25:1 Weigh 375g of anhydrous calcium chloride (dehydrated at 300°C for 36 hours before use), and weigh 120g of high-purity calcium chips (at 1000°C, calcium in anhydrous calcium chloride molten salt 5 times the saturation solubility), metal zirconium and anhydrous calcium chloride are filled in the zirconium crucible, high-purity calcium chips are filled in the gap between the zirconium crucible and the stainless steel crucible, and then the stainless steel crucible is sealed with a high-temperature sealing gasket. Specific as figure 1 shown.

[0038] Put the sealed crucible into a vacuum tank heated by a resistance furnace, cover the furnace cover, vacuumize to 0.5 Pa, and then wash with argon. Under the protection of argon, the temperature was raised to 1000°C at a rate of 5°C / min, and kept at 1000°C for 26 hours. After the heat preservation was compl...

Embodiment 3

[0040] Get 1 metal zirconium wire, quality is 12g, oxygen content 840ppm in the metal zirconium wire, press (CaCl 2 ): m(Zr)=30:1 Weigh 360g of anhydrous calcium chloride (dehydrated at 600°C for 12 hours before use), weigh 288g of industrial calcium chips (at 1300°C, calcium saturated in anhydrous calcium chloride molten salt 4 times the solubility), metal zirconium and anhydrous calcium chloride are filled in the zirconium crucible, industrial calcium chips are filled in the gap between the zirconium crucible and the high-temperature alloy crucible, and then the high-temperature alloy crucible is sealed with a high-temperature sealing gasket. Specific as figure 1 shown.

[0041] Put the sealed crucible into a high-temperature alloy vacuum tank heated by a resistance furnace, cover the furnace cover, evacuate to 0.2 Pa, and then wash with argon. Under the protection of argon, heat up to 1300°C at a heating rate of 5°C / min, and keep at 1300°C for 12 hours. After the heat pre...

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Abstract

The invention belongs to the technical field of metal smelting, and discloses a method for preparing high purity zirconium by calcium in situ distillation-deoxidation. The method includes the steps that a raw material system A and a calcium reducing agent are separately placed in a sealed reaction container and heated under an inert atmosphere, calcium in the calcium reducing agent is dissolved into molten salt in the raw material system A in the form of high pure calcium gas, deoxidation of a zirconium raw material is realized, and the high purity zirconium with the oxygen content less than or equal to 0.10 wt% is prepared; the raw material system A is a mixture of the zirconium raw material and anhydrous calcium chloride, the raw material system A contains or does not contain one or twoof an alkali metal halide and an alkali earth metal halide, and the zirconium raw material is zirconium metal, a zirconium alloy or zirconia; the calcium reducing agent is calcium metal or a calcium alloy; and separately placed separated regions are isolated from each other and communicate through the gas phase. The method for preparing the high purity zirconium by calcium in situ distillation-deoxidation is simple and practicable, has the good effect of oxygen removal, and can meet the use requirements of aerospace, nuclear industries and other fields.

Description

technical field [0001] The invention belongs to the technical field of metal smelting, in particular to a method for preparing high-purity zirconium by calcium in-situ distillation-deoxidation. Background technique [0002] Metal zirconium is an important strategic material. Zirconium and its alloys have good machinability, moderate mechanical strength, high corrosion resistance, and low neutron absorption cross section, so they are widely used in atomic energy industry, aerospace , weaponry and other high-end equipment manufacturing fields. However, the physical and chemical properties of metal zirconium are active, and it is very sensitive to interstitial atoms in metals such as oxygen, carbon, and nitrogen. Due to the nature of zirconium itself has a very strong affinity for these gas impurities, especially oxygen, therefore, zirconium is very easy to capture the external oxygen during smelting, processing, especially the cold and hot processing and welding of zirconium,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C22B34/14C22B5/04
CPCC22B5/04C22B34/14
Inventor 王力军马朝辉黄永章张顺利张建东闫国庆段锦
Owner 有研资源环境技术研究院(北京)有限公司
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