CN104096847A - Preparing method of low-oxygen large-dimension high-purity hafnium powder - Google Patents
Preparing method of low-oxygen large-dimension high-purity hafnium powder Download PDFInfo
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Abstract
The invention relates to a preparing method of low-oxygen large-dimension high-purity hafnium powder. The purity of the low-oxygen large-dimension high-purity hafnium powder is as high as 99.99 weight percent, the oxygen content is less than 0.2 percent, and the granularity is greater than 1mu. m. A preparing process comprises the following steps that a, hafnium oxide powder, reducing agents and molten salt are contained into a crucible; b, the crucible is placed into a reaction tank, vacuum pumping is carried out after the device is sealed, then, argon gas is filled for washing, heating reduction is carried out, then, constant-temperature heat-insulation reduction is carried out, and cooling and furnace discharging are carried out after the reduction completion; c, obtained products are firstly washed by acid and are then washed by de-ionized water, then, sieving and drying are carried out, and the low-oxygen large-dimension high-purity hafnium powder can be obtained. The molten salt system adopted by the method provided by the invention has the advantages that the oxygen content in the hafnium powder can be effectively removed, meanwhile, the dimension of the hafnium powder can be controlled, the friction spontaneous combustion of the hafnium powder is prevented, and safety and controllability are realized.
Description
Technical field
The present invention relates to the preparation method of a kind of hypoxemia, the high-purity hafnium powder of large scale, reduce its metal oxide by means of molten salt solution and prepare hypoxemia, large-sized high-purity hafnium material, particularly relate to the preparation method of controlled, the quality controllable high-purity hafnium of a kind of granularity.
Background technology
The heat resistance of hafnium, excellent corrosion resistance; thermal neutron capture cross section large (115b); pure hafnium has plasticity, easily processes, is atomic energy industry important materials, can absorb the thermal neutron of nuclear reactor and control the reaction speed of reactor, for control rod and the protective device of atomic pile.Because hafnium has higher non-oxidizability, the Hao Alto heat conduction of Liang and electric conductivity and lower electron work functon, be used as the plasma emitter of plasma cutting electrode simultaneously.In addition the alloy of hafnium can be made the forward position protective layer of the aircraft that rocket nozzle and gliding type reentry, and Hf-Ta alloy can fabrication tool steel and resistance material.Hafnium is also applied to metallurgy, chemical industry, gunpowder and special refractories.
Past has proposed the method for many production hafniums and other metals, for referencial use at this referring to its disclosures such as such as CN1882711B, CN102528066A, CN1052148A, US3114611, US4668287, US4637831, US4613366, US4511399, US4242136, US3966460, US3175205.Generally speaking, these patents all disclose and have produced the flow process of hafnium and the concrete device of technique.But these existing methods have certain limitation, or technique is too complicated, or production efficiency is low, or in product impurity oxygen content higher than 0.2wt%.
Summary of the invention
The object of this invention is to provide a kind of purity up to 99.99wt%, oxygen content is less than 0.2%, and granularity is greater than the preparation method of the hafnium metal powder of 1 μ m.The present invention has adopted a kind of new method of preparing high-purity hafnium powder, adopts molten salt system to utilize metallothermic processes to overcome the shortcoming existing in prior art, prepares the controlled and quality controllable hafnium metal powder of granularity.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for hypoxemia, the high-purity hafnium powder of large scale, its preparation process comprises the steps:
A. hafnium oxide powder, reducing agent and fused salt are packed in crucible;
B. crucible is put into retort, vacuumize, be filled with argon gas washing after device sealing, heat reduction, then carries out constant temperature insulation reduction, and reduction finishes cooling coming out of the stove;
C. washing: the product obtaining is first carried out to pickling, then adopt deionized water washing, then sieve, dry, be hypoxemia, the high-purity hafnium powder of large scale product.
In step a, described reducing agent is Ca, CaH
2, Mg, LiH or their mixture, described reducing agent is block or Powdered.
Described fused salt adopts CaCl
2, NaCl, KCl and MgCl
2deng, or adopt binary fused salt mixt, LiCl-KCl, CsCl-KCl, KCl-NaCl, KCl-MgCl
2, CaCl
2-NaCl, NaCl-MgCl
2deng, or adopt ternary salt-mixture, KCl-NaCl-LiCl, LiCl-KCl-KF, LiCl-NaCl-MgCl
2, KCl-NaCl-CaCl
2deng.Described fused salt is Powdered, and its purity is more than or equal to 96w%, and granularity is less than or equal to 2mm.
The purity of described hafnium oxide powder is more than or equal to 99.9w%, and granularity is less than or equal to 1mm.
Described hafnium oxide and the mol ratio≤theoretical value of reducing agent, the i.e. mol ratio≤1:1 of hafnium oxide powder and reducing agent; Mol ratio≤the 1:1 of reducing agent and fused salt.
In step a, pack hafnium oxide powder, reducing agent and fused salt into crucible according to certain charging method, charging method adopts the mixture of fused salt, hafnium oxide powder and the reducing agent of 1/3 quality, and the order of the fused salt of 2/3 quality packs in crucible successively.The material of described crucible is Mo, Ta, Hf, W or Nb metal etc.
In step b, the temperature of described heat reduction is 850～1300 DEG C, and the heating-up time is 0.5～12 hour.Described constant temperature insulation reduction temperature is 850～1300 DEG C, and temperature retention time is 0.5～12 hour.Described heat reduction, constant temperature insulation reduction and coolingly all under argon shield, carry out.
In step c, the temperature of described pickling is room temperature to 100 DEG C, adopts hydrochloric acid, sulfuric acid, nitric acid or the washing of their mixed acid of 0.2M～10M, and the number of times of pickling is 1-15 time, adopts acid washing method to remove the impurity such as fused salt.Described deionized water washing, in room temperature to 100 DEG C, is washed by deionized water, and number of times is 1-15 time.
The purity of the high-purity hafnium powder of hypoxemia, large scale prepared by said method is up to 99.99wt%, and oxygen content is less than 0.2wt%, and granularity is greater than 1 μ m.Reduce the granularity of the hafnium powder that obtains much smaller than 1 μ m and do not add fused salt.
Advantage of the present invention:
1, the present invention adopts molten salt system, can effectively reduce the oxygen content in hafnium powder, can control the size of hafnium powder simultaneously.
The present invention adopts molten salt system to utilize metallothermic processes to prepare the controlled and quality controllable hafnium metal powder of granularity, adopts molten salt system to have the following advantages: (1) reaction heat spreads in salt bath, thus the hot-spot of avoiding; (2) can the dissolving in fuse salt by reducing agent, control its reduction potential; (3) avoid reducing agent directly to contact with hafnium source, reduce sintering and the hafnium powder that the restores inadequate possibility of growing; (4) can be by selecting the melt temperature fused salt suitable with reacting desirable temperature, thus control reaction temperature; (5) fused salt is soluble in water, easily reclaims the hafnium powder of so producing; (6) fused salt solubilizing reaction accessory substance, thus prevent the barrier effect of accessory substance between raw material and reducing agent; (7) do not need to use the reducing agent of powder state.
2, pickling of the present invention, washing impurity removal process, can effectively remove fused salt, metal impurities in product, is met the high pure metal hafnium powder of requirement.
3, method of the present invention, the hafnium powder tool of preparation has the dimensions, and prevents hafnium powder friction spontaneous combustion, and safety is controlled.
Method of the present invention, adopts argon shield, and 850～1300 DEG C of constant temperature 0.5～12 hour, can ensure that hafnium oxide reacts completely, and the present invention is cooling under the protection of the environment of argon gas can ensure that the hafnium restoring does not again be oxidized.
The high-purity hafnium powder of hypoxemia, large scale prepared by the inventive method, directly manufactures high pure metal hafnium target and powder metallurgy section bar applicable to powder metallurgy process; Can be used as iodide process and prepare hafnium crystal bar high-purity, low gap constituent content; Can be used as direct melting and prepare the raw material of high-purity hafnium ingot.
Below by detailed description of the invention, the invention will be further described, but and do not mean that the restriction to protection scope of the present invention.
Detailed description of the invention
Embodiment 1
Take purity 99.9wt%, granularity and be less than the hafnium oxide of 1mm and purity and be greater than 98wt%, block reducing agent calcium metal, the mol ratio 1:2 of its hafnium oxide and calcium metal, the purity that simultaneously takes certain mass is greater than 96.0wt%, and granularity is less than 2mm fused salt CaCl
2, and reducing agent and fused salt CaCl
2mol ratio be 1:1, according to the fused salt of 1/3 quality, hafnium oxide and calcium metal mixture, the fused salt of 2/3 quality packs in molybdenum crucible successively.Crucible is put into retort, build and be evacuated to 0.01Pa, argon gas washing after lid.Within 0.5 hour, be heated to 850 DEG C, and in 850 DEG C of constant temperature 12 hours, argon shield, and in argon atmosphere, be cooled to room temperature.By product with the hydrochloric acid of 0.2M room temperature washing 15 times, then for room temperature, deionized water is washed 1 time, and the product obtaining is sieved, and finally obtains hafnium opaque amount and is: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 8 μ m.
Embodiment 2
Taking purity 99.9wt%, granularity is less than the hafnium oxide of 1mm and purity and is greater than the reducing agent LiH powder that 98.9wt%, granularity are less than 1mm, the mol ratio 1:5 of its hafnium oxide and metal LiH powder, the purity that simultaneously takes certain mass is greater than 96.0wt%, granularity is less than 2mm fused salt NaCl, and the mol ratio of reducing agent and fused salt NaCl is 1:3, pack into successively in niobium crucible according to the fused salt of the mixture of the fused salt of 1/3 quality, hafnium oxide and LiH powder, 2/3 quality.Crucible is put into retort, build and be evacuated to 0.04Pa, argon gas washing after lid.Within 6 hours, be heated to 1300 DEG C, and in 1300 DEG C of constant temperature 10 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 10 times at 70 DEG C with the hydrochloric acid of 0.2M, then at 70 DEG C with deionized water washing 1 time, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 3 μ m.
Embodiment 3
Taking purity 99.9wt%, granularity is less than the hafnium oxide of 1mm and purity and is greater than the reducing agent Mg powder that 98.9wt%, granularity are less than 1mm, the mol ratio 1:2 of its hafnium oxide and metal M g powder, the purity that simultaneously takes certain mass is greater than 96.0wt%, and granularity is less than 2mm fused salt MgCl
2, and reducing agent and fused salt MgCl
2mol ratio be 1:3, pack into successively in molybdenum crucible according to the mixture of the fused salt of 1/3 quality, hafnium oxide and metal M g powder, the fused salt of 2/3 quality.Crucible is put into retort, build and be evacuated to 0.03Pa, argon gas washing after lid.Within 2 hours, be heated to 900 DEG C, and in 900 DEG C of constant temperature 5 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 7 times at 40 DEG C with the nitric acid of 0.2M, then for room temperature, deionized water is washed 10 times, and the product obtaining is sieved, and finally obtains hafnium opaque amount and is: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 5 μ m.
Embodiment 4
Taking purity 99.9wt%, granularity is less than the hafnium oxide of 1mm and purity and is greater than 98.9wt%, block reducing agent calcium metal, the mol ratio 1:3 of its hafnium oxide and calcium metal, the purity that simultaneously takes certain mass is greater than 96.0wt%, granularity is less than 2mm fused salt NaCl-KCl, and the mol ratio of reducing agent and fused salt NaCl-KCl is 1:5, the mass ratio of NaCl:KCl is 1:1, packs into successively in tungsten crucible according to the fused salt of the mixture of the fused salt of 1/3 quality, hafnium oxide and calcium metal, 2/3 quality.Crucible is put into retort, build and be evacuated to 0.05Pa, argon gas washing after lid.Within 1 hour, be heated to 850 DEG C, and in 850 DEG C of constant temperature 3 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 8 times at 70 DEG C with the hydrochloric acid of 0.5M, then at 50 DEG C with deionized water washing 10 times, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 15 μ m.
Embodiment 5
Take that hafnium oxide and the purity that purity 99.9wt%, granularity be less than 1mm is greater than 98.9wt%, granularity is less than 1mm reducing agent CaH
2powder, its hafnium oxide and metal CaH
2the mol ratio 1:2 of powder, the purity that simultaneously takes certain mass is greater than 96.0wt%, and granularity is less than 2mm fused salt CaCl
2-NaCl, and reducing agent and fused salt CaCl
2the mol ratio of-NaCl is 1:4, CaCl
2: the mass ratio of NaCl is 3:1, according to the fused salt of 1/3 quality, hafnium oxide and CaH
2the mixture of powder, the fused salt of 2/3 quality pack in tantalum crucible successively.Crucible is put into retort, build and be evacuated to 0.07Pa, argon gas washing after lid.Within 5 hours, be heated to 1050 DEG C, and in 1050 DEG C of constant temperature 8 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 9 times at 60 DEG C with the sulfuric acid of 0.5M, then at 60 DEG C with deionized water washing 8 times, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 30 μ m.
Embodiment 6
Taking purity 99.9wt%, granularity is less than the hafnium oxide of 1mm and purity and is greater than the reducing agent metal CaH that 98.9wt%, granularity are less than
2with the mixture of LiH, CaH
2: the mol ratio of LiH is 1:1, the mol ratio 1:5 of its hafnium oxide and reducing agent, the purity that simultaneously takes certain mass is greater than 96.0wt%, granularity is less than 2mm fused salt LiCl-KCl, and the mol ratio of reducing agent and fused salt is 1:8, the mass ratio of LiCl:KCl is 3:1, and according to the mixture of the fused salt of 1/3 quality, hafnium oxide, reducing agent, the fused salt of 2/3 quality packs in niobium crucible successively.Crucible is put into retort, build and be evacuated to 0.08Pa, argon gas washing after lid.Within 4 hours, be heated to 1000 DEG C, and in 1000 DEG C of constant temperature 6 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 6 times at 50 DEG C with the hydrochloric acid of 0.2M and the mixed acid of nitric acid, then at 50 DEG C with deionized water washing 7 times, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 20 μ m.
Embodiment 7
Taking purity 99.9wt%, granularity is less than the hafnium oxide of 1mm and purity and is greater than 98.9wt%, block reducing agent calcium metal, the mol ratio 1:4 of its hafnium oxide and calcium metal, the purity that simultaneously takes certain mass is greater than 96.0wt%, and granularity is less than 2mm fused salt NaCl-MgCl
2, and reducing agent and fused salt NaCl-MgCl
2mol ratio be 1:4, NaCl:MgCl
2mass ratio be 1:1, pack into successively in molybdenum crucible according to the fused salt of the mixture of the fused salt of 1/3 quality, hafnium oxide and calcium metal, 2/3 quality.Crucible is put into retort, build and be evacuated to 0.06Pa, argon gas washing after lid.Within 2 hours, be heated to 850 DEG C, and in 850 DEG C of constant temperature 10 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 12 times at 60 DEG C with the hydrochloric acid of 0.5M, then at 60 DEG C with deionized water washing 9 times, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 25 μ m.
Embodiment 8
Taking purity 99.9wt%, granularity is less than the hafnium oxide of 1mm and purity and is greater than 98.9wt%, block reducing agent calcium metal, the mol ratio 1:5 of its hafnium oxide and calcium metal, the purity that simultaneously takes certain mass is greater than 96.0wt%, and granularity is less than 2mm fused salt KCl-NaCl-CaCl
2, and reducing agent and fused salt KCl-NaCl-CaCl
2mol ratio be 1:5, KCl:NaCl:CaCl
2mass ratio be 1:1:5, pack into successively in molybdenum crucible according to the fused salt of the mixture of the fused salt of 1/3 quality, hafnium oxide and calcium metal, 2/3 quality.Crucible is put into retort, build and be evacuated to 0.02Pa, argon gas washing after lid.Within 3 hours, be heated to 1100 DEG C, and in 1100 DEG C of constant temperature 5 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 9 times at 40 DEG C with the nitric acid acid of 0.2M, then at 40 DEG C with deionized water washing 9 times, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 35 μ m.
Embodiment 9
Taking purity 99.9wt%, granularity is less than the hafnium oxide of 1mm and purity and is greater than 98.9wt%, block reducing agent calcium metal, the mol ratio 1:4 of its hafnium oxide and calcium metal, the purity that simultaneously takes certain mass is greater than 96.0wt%, granularity is less than 2mm fused salt KCl-NaCl-LiCl, and the mol ratio of reducing agent and fused salt KCl-NaCl-LiCl is 1:1, the mass ratio of KCl:NaCl:LiCl is 1:3:1, packs into successively in hafnium crucible according to the fused salt of the mixture of the fused salt of 1/3 quality, hafnium oxide and calcium metal, 2/3 quality.Crucible is put into retort, build and be evacuated to 0.09Pa, argon gas washing after lid.Within 3 hours, be heated to 900 DEG C, and in 900 DEG C of constant temperature 7 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 8 times at 80 DEG C with the hydrochloric acid of 0.2M, then at 80 DEG C with deionized water washing 8 times, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 50 μ m.
Embodiment 10
Take purity 99.9wt%, granularity and be less than the hafnium oxide of 1mm and purity and be greater than 98.9wt%, block reducing agent calcium metal, the mol ratio 1:2 of its hafnium oxide and calcium metal, the purity that simultaneously takes certain mass is greater than 96.0wt%, and granularity is less than 2mm fused salt CaCl
2, and reducing agent and fused salt CaCl
2mol ratio be 1:10, pack into successively in molybdenum crucible according to the fused salt of the mixture of the fused salt of 1/3 quality, hafnium oxide and calcium metal, 2/3 quality.Crucible is put into retort, build and be evacuated to 0.1Pa, argon gas washing after lid.Within 12 hours, be heated to 1300 DEG C, and in 1300 DEG C of constant temperature 12 hours, argon shield, and in argon atmosphere, be cooled to room temperature.Product is washed 15 times at 100 DEG C with the hydrochloric acid of 10M, then at 100 DEG C with deionized water washing 15 times, the product obtaining is sieved, finally obtain hafnium opaque amount and be: the purity of hafnium powder is 99.99wt%, oxygen content is less than 0.2wt%, and particle mean size is 80 μ m.
The molten salt system that method of the present invention adopts, can effectively remove the oxygen content in hafnium powder, can control the size of hafnium powder simultaneously, prevents hafnium powder friction nature, and safety is controlled.The high-purity hafnium powder of hypoxemia, large scale prepared by the inventive method, purity is up to 99.99wt%, and oxygen content is less than 0.2%, and granularity is greater than 1 μ m.
Claims (10)
1. a preparation method for hypoxemia, the high-purity hafnium powder of large scale, comprises the steps:
A. hafnium oxide powder, reducing agent and fused salt are packed in crucible;
B. crucible is put into retort, vacuumize, be filled with argon gas washing after device sealing, heat reduction, then carries out constant temperature insulation reduction, and reduction finishes cooling coming out of the stove;
C. the product obtaining is first carried out to pickling, then adopt deionized water washing, then sieve, dry, be hypoxemia, the high-purity hafnium powder of large scale.
2. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, is characterized in that: described reducing agent is Ca, CaH
2, Mg, LiH or their mixture, described reducing agent is block or Powdered.
3. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, is characterized in that: described fused salt is CaCl
2, NaCl, KCl or MgCl
2, or be binary fused salt mixt LiCl-KCl, CsCl-KCl, KCl-NaCl, KCl-MgCl
2, CaCl
2-NaCl or NaCl-MgCl
2, or be ternary salt-mixture KCl-NaCl-LiCl, LiCl-KCl-KF, LiCl-NaCl-MgCl
2or KCl-NaCl-CaCl
2.
4. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, is characterized in that: the purity >=99.9w% of described hafnium oxide powder, granularity≤1mm; Described fused salt is Powdered, purity >=96w%, granularity≤2mm.
5. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, is characterized in that: described hafnium oxide powder and the mol ratio≤1:1 of reducing agent, the mol ratio≤1:1 of reducing agent and fused salt.
6. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, it is characterized in that: the mode that described hafnium oxide powder, reducing agent and fused salt packs crucible into is by the mixture of the fused salt of 1/3 quality, hafnium oxide powder and reducing agent, and the fused salt of 2/3 quality packs in crucible in order successively.
7. the preparation method of hypoxemia according to claim 6, the high-purity hafnium powder of large scale, is characterized in that: the material of described crucible is Mo, Ta, Hf, W or Nb.
8. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, is characterized in that: the temperature of described heat reduction is 850～1300 DEG C, the heating-up time is 0.5～12 hour.Described constant temperature insulation reduction temperature is 850～1300 DEG C, and temperature retention time is 0.5～12 hour; Described heat reduction, constant temperature insulation reduction and coolingly all under argon shield, carry out.
9. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, is characterized in that: described pickling is hydrochloric acid, sulfuric acid, nitric acid or the washing of their mixed acid that adopts 0.2M～10M, and the number of times of pickling is 1-15 time; The number of times of described employing deionized water washing is 1-15 time.
10. the preparation method of hypoxemia according to claim 1, the high-purity hafnium powder of large scale, it is characterized in that: the purity >=99.99wt% of gained hypoxemia, the high-purity hafnium powder of large scale, oxygen content < 0.2wt%, granularity > 1 μ m.
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| CN109317691A (en) * | 2018-10-15 | 2019-02-12 | 中南大学 | A kind of preparation method of the rod-shaped purple tungsten of high dispersive |
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| CN112095022A (en) * | 2020-01-21 | 2020-12-18 | 有研资源环境技术研究院(北京)有限公司 | Method for deeply removing oxygen in metal hafnium by using super-oxophilic metal-calcium synergistic method |
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