CN110453084B - Preparation method of atomic-level sponge zirconium - Google Patents
Preparation method of atomic-level sponge zirconium Download PDFInfo
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- CN110453084B CN110453084B CN201910720695.3A CN201910720695A CN110453084B CN 110453084 B CN110453084 B CN 110453084B CN 201910720695 A CN201910720695 A CN 201910720695A CN 110453084 B CN110453084 B CN 110453084B
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- 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
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- C—CHEMISTRY; METALLURGY
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- C22B5/02—Dry methods smelting of sulfides or formation of mattes
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
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Abstract
The invention relates to a preparation method of atomic-level sponge zirconium, which comprises the following steps: (1) heating a mixture of zirconium tetrachloride and hafnium tetrachloride at a temperature of 331 ℃ or higher to obtain a mixed gas; (2) mixing the obtained mixed gas with the heated protective gas, condensing zirconium tetrachloride in the mixed gas under the condition of a constant-temperature oil bath at 317-330 ℃, and then separating to obtain solid zirconium tetrachloride and the residual mixed gas; (3) purifying the obtained solid zirconium tetrachloride at least once to obtain zirconium tetrachloride with atomic level and enriched crude hafnium tetrachloride; (4) and reducing the obtained zirconium tetrachloride with the atomic level to obtain the sponge zirconium with the atomic level. The preparation method of the atomic-level sponge zirconium has the advantages of short process flow, no reagent consumption in the separation process, environmental friendliness and low production cost.
Description
Technical Field
The invention relates to a preparation process of rare metals, in particular to a preparation method of atomic-level sponge zirconium.
Background
Zirconium and hafnium are two rare metals with very similar properties, usually associated together. Zirconium and hafnium are important nuclear industrial materials, but the specific application is different, the thermal neutron capture cross section of zirconium is small, and the zirconium is an indispensable material for developing atomic energy industry and can be used as a reactor core structural material; hafnium has a large thermal neutron-capturing cross section, is an ideal neutron absorber, and can be used as a control rod and a protector for a nuclear reactor, and therefore, it is necessary to separate zirconium and hafnium for use.
However, separation of zirconium and hafnium is difficult, and the main separation methods fall into two broad categories: wet separation and pyrogenic separation. The wet separation method mainly comprises a fractional crystallization method and a solvent extraction method, and the industrial production mainly adopts the solvent extraction method, including a MIBK method, a TBP method, an N235 method, a P204 method, a TOA method, a DIBK method and the like. The pyrogenic separation mainly comprises a fused salt rectification method, a fused salt electrolysis method and the like, wherein the fused salt rectification method mainly utilizes the difference of saturated vapor pressures of zirconium tetrachloride and hafnium tetrachloride in a molten KCl-AlCl 3 fused salt system for separation.
The existing solvent extraction method has the advantages of realizing effective separation of zirconium and hafnium and has the disadvantages of more reagent consumption, long flow, higher production cost and difficult pollutant treatment. The fused salt rectification method has the advantages of less reagent consumption, short flow, less three-waste pollution and the like, and has the defects of high working temperature and high requirements on equipment materials and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in view of the above disadvantages of the prior art, a method for preparing atomic-level zirconium sponge is provided, which can effectively reduce reagent consumption and shorten the process.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of atomic-level sponge zirconium comprises the following steps:
(1) heating a mixture of zirconium tetrachloride and hafnium tetrachloride at a temperature of 331 ℃ or higher to obtain a mixed gas;
(2) mixing the mixed gas obtained in the step (1) with the heated protective gas, condensing zirconium tetrachloride in the mixed gas under the condition of a constant-temperature oil bath at 317-330 ℃, and then separating to obtain solid zirconium tetrachloride and the residual mixed gas;
(3) purifying the solid zirconium tetrachloride obtained in the step (2) at least once to obtain zirconium tetrachloride with atomic energy level and enriched crude hafnium tetrachloride;
(4) and (4) reducing the zirconium tetrachloride with the atomic energy level obtained in the step (3) to obtain sponge zirconium with the atomic energy level.
The invention has the beneficial effects that:
according to the preparation method of the atomic-level zirconium sponge, through the design of the integral preparation process, the mixture of zirconium tetrachloride and hafnium tetrachloride is separated by adopting a physical method, and the preparation method has the advantages of short process flow, no reagent consumption in the separation process, environmental friendliness and low production cost.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The most key concept of the invention is as follows: the method comprises the steps of firstly heating a mixture of zirconium tetrachloride and hafnium tetrachloride to enable the mixture to be sublimated into a gaseous state, then placing the gaseous state and the heated protective gas into a constant-temperature oil bath condition, and adjusting the temperature of 317-330 ℃ through accurate temperature control to enable the zirconium tetrachloride to be condensed into solid powder.
The invention provides a preparation method of atomic-level sponge zirconium, which comprises the following steps:
(1) heating a mixture of zirconium tetrachloride and hafnium tetrachloride at a temperature of 331 ℃ or higher to obtain a mixed gas;
(2) mixing the mixed gas obtained in the step (1) with the heated protective gas, condensing zirconium tetrachloride in the mixed gas under the condition of a constant-temperature oil bath at 317-330 ℃, and then separating to obtain solid zirconium tetrachloride and the residual mixed gas;
(3) purifying the solid zirconium tetrachloride obtained in the step (2) at least once to obtain zirconium tetrachloride with atomic energy level and enriched crude hafnium tetrachloride;
(4) and (4) reducing the zirconium tetrachloride with the atomic energy level obtained in the step (3) to obtain sponge zirconium with the atomic energy level.
The preparation method of atomic level zirconium sponge comprises the steps of taking a mixture of zirconium tetrachloride and hafnium tetrachloride as raw materials, firstly heating to sublimate the mixture into a gaseous state, then placing the mixture into a 317-330 ℃ constant-temperature oil bath condition along with heated protective gas (such as hot nitrogen), adjusting the temperature between 317-330 ℃ through precise temperature control to condense the zirconium tetrachloride into solid powder, discharging the hafnium tetrachloride in a gaseous form, filtering and separating the hafnium tetrachloride under the constant-temperature condition, collecting crude zirconium tetrachloride powder, repeating the process for many times to purify the zirconium tetrachloride to obtain an atomic level zirconium tetrachloride raw material, and reducing the atomic level zirconium tetrachloride (such as metal magnesium and the like) to obtain the atomic level zirconium sponge.
From the above description, the beneficial effects of the present invention are:
according to the preparation method of the atomic-level zirconium sponge, through the design of the integral preparation process, the mixture of zirconium tetrachloride and hafnium tetrachloride is separated by adopting a physical method, and the preparation method has the advantages of short process flow, no reagent consumption in the separation process, environmental friendliness and low production cost.
Further, the purification in the step (3) is specifically as follows: repeating the step (1) to the step (2); and (4) reducing the zirconium tetrachloride with the atomic energy level obtained in the step (3).
Furthermore, the purification times are 3-20.
Further, in the step (4), metal magnesium is adopted for reduction.
Further, in the step (2), the heated shielding gas is added at a flow rate of 0.5 to 30m/s to be mixed with the mixed gas obtained in the step (1).
Further, in the step (1), the mixture of zirconium tetrachloride and hafnium tetrachloride is placed in a heating kettle for heating, and a venturi three-way pipe with one end communicated with the heating kettle is arranged on the heating kettle; in the step (2), heated protective gas is sprayed from one end of the Venturi three-way pipe at the flow speed of 0.5-30m/s, the protective gas enters a thermostatic pipe from the other end of the Venturi three-way pipe, the mixed gas obtained in the step (1) is sucked into the thermostatic pipe through the Venturi three-way pipe under the action of negative pressure generated by the Venturi three-way pipe, and the mixed gas obtained in the step (1) and the protective gas are mixed in the thermostatic pipe.
Further, placing the constant temperature tube in an oil bath device filled with a heat transfer oil medium; the length of the constant temperature tube is 10-300m, and the diameter of the tube is 10-200 cm.
Further, in the step (3), the obtained atomic level zirconium tetrachloride is reduced by using magnesium metal.
Further, the residual mixed gas obtained in the step (2) is sequentially cooled and filtered for separation, and the enriched crude hafnium tetrachloride solid is obtained.
Further, cooling the residual mixed gas obtained in the step (2) by adopting a water cooling or air cooling mode.
Further, the temperature of the gas remaining after the filtration and separation is raised, and the protective gas is obtained by recovery.
Further, the mixed gas is discharged and condensed into a mixture of hafnium tetrachloride and zirconium tetrachloride, and the mixture is returned to be used as a raw material for re-separation.
The embodiment of the invention is concretely as follows:
example 1
The preparation method of the atomic-level zirconium sponge of the embodiment comprises the following specific steps:
(1) the mixture of zirconium tetrachloride and hafnium tetrachloride is added into a heating kettle (made of corrosion-resistant materials) for heating, the temperature is controlled at 347 ℃, and the zirconium tetrachloride and the hafnium tetrachloride are sublimated into gas.
(2) The upper part of the heating kettle is provided with a Venturi three-way pipe device, one end of the Venturi three-way pipe is communicated with the heating kettle, the other end of the Venturi three-way pipe is communicated with a constant temperature pipe, and the remaining last end of the Venturi three-way pipe is communicated with a nitrogen inlet. After nitrogen is heated to 319 ℃ through a heating device, the nitrogen is sprayed from one end of a Venturi tube, enters a constant temperature tube from the other end (made of corrosion-resistant materials), the flow speed is controlled to be 8m/s, mixed gas in a heating kettle is sucked into the constant temperature tube under the action of negative pressure generated by the Venturi tube and is mixed with the nitrogen, the length of the constant temperature tube is 50 meters, the diameter of the constant temperature tube is 20 centimeters, the constant temperature tube is embedded into a sealed oil bath device, a high-temperature heat conducting oil medium is selected, the temperature is accurately controlled and heated to 322 ℃, and heat conduction oil conducts and keeps heat. And gradually cooling the temperature of the mixed gas to be close to 322 ℃ in the process of passing through the constant temperature tube, condensing the zirconium tetrachloride into solid powder, and discharging the hafnium tetrachloride in a gaseous form.
(3) And (3) passing the discharged solid and gas mixture through a constant-temperature filtering separator, controlling the temperature within the range of 320-324 ℃, separating the powdery zirconium tetrachloride, discharging the powdery zirconium tetrachloride from a bottom outlet to obtain crude zirconium tetrachloride solid, periodically heating and removing part of the solid adhered to the tube wall, and discharging the hafnium tetrachloride gas and part of the zirconium tetrachloride gas from an upper outlet of the filtering separator.
(4) And (3) cooling the discharged hafnium tetrachloride mixed gas into a solid in a collection tower, collecting the solid to obtain a crude hafnium tetrachloride solid, cooling the collection tower in a water cooling mode, and supplementing heat and heating the remaining nitrogen for reuse.
(5) Continuous production can be realized by continuously feeding materials at the feed inlet of the heating kettle.
(6) And regulating the temperature and the air flow speed of the heating kettle and the oil bath, and repeatedly purifying the crude zirconium tetrachloride product for 3 times to obtain the atomic-level zirconium tetrachloride raw material and the enriched crude hafnium tetrachloride raw material.
(7) And reducing the zirconium tetrachloride with atomic level by using magnesium metal to prepare the sponge zirconium with atomic level.
The preparation method of atomic-level sponge zirconium has the advantages of simple process flow, low equipment requirement (the existing fused salt rectification process needs higher temperature and additional treatment on fused salt, and has higher requirements on equipment and materials), no reagent consumption in the separation process, environmental friendliness and low production cost.
Example 2
The preparation method of the atomic-level zirconium sponge of the embodiment comprises the following specific steps:
(1) the mixture of zirconium tetrachloride and hafnium tetrachloride is added into a heating kettle (made of corrosion-resistant materials) for heating, the temperature is controlled at 368 ℃, and the zirconium tetrachloride and the hafnium tetrachloride are sublimated into gas.
(2) The venturi three-way pipe device is installed on the upper portion of the heating kettle, nitrogen is heated to 310 ℃ through the heating device and then sprayed into the constant temperature pipe from one end of the venturi pipe, the nitrogen enters the constant temperature pipe from the other end (made of corrosion-resistant materials for use), the flow speed is controlled to be 6m/s, mixed gas in the heating kettle is sucked into the constant temperature pipe under the action of negative pressure generated by the venturi pipe and is mixed with the nitrogen, the length of the constant temperature pipe is 80 m, the pipe diameter is 30 cm, the constant temperature pipe is embedded into a sealed oil bath device, high-temperature heat conducting oil media are selected for use, accurate temperature control heating is carried out. And gradually reducing the temperature of the mixed gas to nearly 323 ℃ in the process of passing through the thermostatic tube, so that the zirconium tetrachloride is condensed into solid powder, and the hafnium tetrachloride is discharged in a gaseous form.
(3) And (3) passing the discharged solid and gas mixture through a constant-temperature filtering separator, controlling the temperature within the range of 322-324 ℃, separating the powdery zirconium tetrachloride, discharging the powdery zirconium tetrachloride from a bottom outlet to obtain crude zirconium tetrachloride solid, periodically heating and removing part of the solid adhered to the tube wall, and discharging the hafnium tetrachloride gas and part of the zirconium tetrachloride gas from an upper outlet of the filtering separator.
(4) And (3) cooling the discharged hafnium tetrachloride mixed gas into a solid in a collection tower, collecting the solid to obtain a crude hafnium tetrachloride solid, cooling the collection tower in an air cooling mode, and supplementing heat and heating the residual nitrogen and returning to the system for reuse.
(5) Continuous production can be realized by continuously feeding materials at the feed inlet of the heating kettle.
(6) And regulating the temperature and the air flow speed of the heating kettle and the oil bath, and repeatedly purifying the crude zirconium tetrachloride product for 5 times to obtain the atomic-level zirconium tetrachloride raw material and the enriched crude hafnium tetrachloride raw material.
(7) And reducing the zirconium tetrachloride with atomic level by using magnesium metal to prepare the sponge zirconium with atomic level.
Example 3
The preparation method of atomic-level zirconium sponge in this example is different from example 1 only in that "nitrogen flow rate is 0.5m/s, length of the thermostatic tube is 10 m, tube diameter is 10 cm, and temperature is precisely controlled to 317 ℃" and the other steps are the same as example 1.
Example 4
The preparation method of atomic-level zirconium sponge in this example is different from example 1 only in that "nitrogen flow rate is 30m/s, thermostatic tube length is 300m, tube diameter is 200cm, and temperature is precisely controlled and heated to 330 ℃" and the other steps are the same as example 1.
Example 5
The preparation method of atomic-level zirconium sponge in this example is different from example 1 only in that "the nitrogen flow rate is 20m/s, the length of the thermostatic tube is 150 m, the tube diameter is 150 cm, and the temperature is accurately controlled and heated to 323 ℃" and the other steps are the same as example 1.
In conclusion, the preparation method of atomic-level sponge zirconium provided by the invention has the advantages of short process flow, no reagent consumption in the separation process, environmental friendliness and low production cost.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (6)
1. The preparation method of the atomic-level sponge zirconium is characterized by comprising the following steps of:
(1) heating a mixture of zirconium tetrachloride and hafnium tetrachloride at a temperature of 331 ℃ or higher to obtain a mixed gas;
(2) mixing the mixed gas obtained in the step (1) with the heated protective gas, condensing zirconium tetrachloride in the mixed gas under the condition of a constant-temperature oil bath at 317-330 ℃, and then separating to obtain solid zirconium tetrachloride and the residual mixed gas;
(3) purifying the solid zirconium tetrachloride obtained in the step (2) at least once to obtain zirconium tetrachloride with atomic energy level and enriched crude hafnium tetrachloride;
(4) reducing the atomic-level zirconium tetrachloride obtained in the step (3) to obtain atomic-level sponge zirconium;
wherein, the purification in the step (3) is specifically as follows: repeating the step (1) to the step (2); reducing the zirconium tetrachloride with the atomic energy level obtained in the step (3);
wherein, in the step (2), the heated protective gas is added at the flow rate of 0.5-30m/s to be mixed with the mixed gas obtained in the step (1);
in the step (1), the mixture of zirconium tetrachloride and hafnium tetrachloride is placed in a heating kettle for heating, and a Venturi three-way pipe with one end communicated with the heating kettle is arranged on the heating kettle; in the step (2), heated protective gas is sprayed from one end of the Venturi three-way pipe at the flow speed of 0.5-30m/s, the protective gas enters a thermostatic pipe from the other end of the Venturi three-way pipe, the mixed gas obtained in the step (1) is sucked into the thermostatic pipe through the Venturi three-way pipe under the action of negative pressure generated by the Venturi three-way pipe, and the mixed gas obtained in the step (1) and the protective gas are mixed in the thermostatic pipe.
2. The method for preparing atomic level zirconium sponge according to claim 1, wherein in step (4), magnesium metal is used for reduction.
3. The method for preparing atomic level zirconium sponge according to claim 1, characterized in that the thermostatic tube is placed in an oil bath device filled with heat transfer oil medium; the length of the constant temperature tube is 10-300m, and the diameter of the tube is 10-200 cm.
4. The method for preparing atomic level zirconium sponge according to claim 2, wherein the residual mixed gas obtained in step (2) is cooled by water cooling or air cooling.
5. The method for preparing atomic level zirconium sponge according to claim 4, wherein the temperature of the gas remaining after the filtration and separation is raised, and the protective gas is recovered.
6. The method for preparing atomic level zirconium sponge according to claim 1, wherein in the step (2), the remaining mixed gas is condensed into a mixture of hafnium tetrachloride and zirconium tetrachloride, and returned as a raw material for re-separation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA1171664A (en) * | 1980-07-30 | 1984-07-31 | Hiroshi Ishizuka | Process for separation of zirconium- and hafnium tetrachlorides from a mixture comprising such chlorides and apparatus therefor |
| JPS589819A (en) * | 1981-07-06 | 1983-01-20 | Hiroshi Ishizuka | Separation of zirconium tetrachloride from hafnium tetrachloride |
| US5009866A (en) * | 1989-11-16 | 1991-04-23 | Westinghouse Electric Corp. | Fused salt process for purifying zirconium and/or hafnium tetrachlorides |
| CN1052148A (en) * | 1989-11-29 | 1991-06-12 | 泰利达因工业有限公司 | High-purity zirconium and Hf metals and method for making thereof |
| CN101638249B (en) * | 2009-09-04 | 2010-10-27 | 石政君 | Zirconium tetrachloride purification method |
| CN101705376A (en) * | 2009-11-30 | 2010-05-12 | 石政君 | Process for producing sponge zirconium by using reduction and distillation combination method |
| FR2963339B1 (en) * | 2010-08-02 | 2012-09-14 | Centre Nat Rech Scient | PROCESS FOR SEPARATING ZIRCONIUM AND HAFNIUM TETRACHLORIDES FROM THEIR MIXTURES |
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