CN111364065A - Method for preparing uranium by utilizing uranium oxide - Google Patents

Method for preparing uranium by utilizing uranium oxide Download PDF

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Publication number
CN111364065A
CN111364065A CN202010146329.4A CN202010146329A CN111364065A CN 111364065 A CN111364065 A CN 111364065A CN 202010146329 A CN202010146329 A CN 202010146329A CN 111364065 A CN111364065 A CN 111364065A
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uranium
carbon
metal
oxide
reaction
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宋文臣
林如山
何辉
叶国安
孟照凯
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China Institute of Atomic of Energy
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China Institute of Atomic of Energy
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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
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • 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
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0213—Obtaining thorium, uranium, or other actinides obtaining uranium by dry processes
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention belongs to the technical field of chemical metallurgy, and relates to a method for preparing metal uranium by utilizing uranium oxide. The method comprises the following steps: (1) mixing uranium oxide, carbon and a binder uniformly and pressing into a mixed briquette with certain shape characteristics; (2) carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace to prepare a carbon-oxygen-uranium intermediate UC with metal conductivityxO1‑xWherein x is more than or equal to 0 and less than or equal to 1; (3) the intermediate UC of the carbon oxygen uraniumxO1‑xAnd as an anode, taking a metal material as a cathode, carrying out an electrolytic reaction in molten salt under the protection of inert atmosphere, and collecting a cathode electrolysis product as a metal uranium product. The method for preparing metal uranium by utilizing uranium oxideThe method can prepare the metal uranium by utilizing the uranium oxide with simple process, low cost and high uranium reduction rate.

Description

Method for preparing uranium by utilizing uranium oxide
Technical Field
The invention belongs to the technical field of chemical metallurgy, and relates to a method for preparing metal uranium by utilizing uranium oxide.
Background
The post-treatment of the spent fuel mainly comprises a wet treatment route and a dry treatment route, wherein the dry post-treatment has an advantage in treating the spent fuel with high fuel consumption. Typical dry post-processing technologies are an electrorefining process with a metal fuel as a processing object developed as typified by the united states and an oxide electrodeposition process with an oxide fuel as a processing object developed as typified by russia, among which the electrorefining technology is currently the most promising dry post-processing technology.
In order to apply the technology to the oxide spent fuel widely used by the fast reactor and the light water reactor, the oxide spent fuel needs to be converted into metal firstly. The main component of the oxide spent fuel is uranium oxide, and dry post-treatment technologies for converting the uranium oxide into metal mainly comprise two types of metal thermal reduction and molten salt electrochemical reduction. Among them, the metallothermic reduction is an oxide (Li) produced by replacing uranium with an active metal such as Li or Ca2O, CaO) will cover the surface of uranium oxide to prevent the further progress of the replacement reaction, and a large amount of molten salt is needed to dissolve the oxide layer to ensure the reaction to continue, and a large amount of waste salt is generated, so the technology is basically stopped to be researched abroad at present. Therefore, molten salt electrochemical reduction technology has been mainly developed abroad, and has been applied to many researches and successes. The molten salt electrochemical reduction is carried out by taking uranium oxide as a cathode and platinum as an anode at high temperature LiCl-Li2And carrying out electrolytic reduction in O molten salt to finally obtain a crude uranium metal simple substance, and carrying out electrolytic refining to obtain relatively pure uranium metal. However, in the current research situation, the electrolytic reduction process using uranium oxide as the cathode has the fatal problems of complex preparation process of the integrated cathode, high cost of the platinum anode material, low uranium reduction rate and the like.
Therefore, the existing technology for preparing metallic uranium by reducing uranium oxide is to be further improved.
Disclosure of Invention
The invention aims to provide a method for preparing metal uranium by utilizing uranium oxide, which is used for preparing the metal uranium by utilizing the uranium oxide and has the advantages of simple process, low cost and high uranium reduction rate.
To achieve this object, in a basic embodiment, the present invention provides a method for producing metallic uranium from uranium oxide, the method comprising the steps of:
(1) mixing uranium oxide, carbon and a binder uniformly and pressing into a mixed briquette with certain shape characteristics;
(2) carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace to prepare a carbon-oxygen-uranium intermediate UC with metal conductivityxO1-xWherein x is more than or equal to 0 and less than or equal to 1;
(3) the intermediate UC of the carbon oxygen uraniumxO1-xAnd as an anode, taking a metal material as a cathode, carrying out an electrolytic reaction in molten salt under the protection of inert atmosphere, and collecting a cathode electrolysis product as a metal uranium product.
The relevant principle of the present invention is as follows.
(1) Mixing the uranium oxide, the carbon and the binder to obtain a mixed material
The main component of uranium oxide can be uranium dioxide UO2Triuranium octoxide U3O8And uranium trioxide (UO)3One or a mixture of (1). Wherein the uranium dioxide UO2Is the main component of nuclear reaction spent fuel, and triuranium octoxide U3O8And uranium trioxide (UO)3Then uranium dioxide UO is used in the nuclear reaction spent fuel post-treatment process2And (4) obtaining a high-valence uranium oxide product after high-temperature oxidation and volatilization.
And (3) mixing the uranium oxide, the carbon and the binder to obtain a mixed material. The inventors have found that the conditions for shaping uranium oxide and carbon by themselves are not good, and that the addition of a binder to uranium oxide and carbon can assist in shaping the uranium oxide and carbon in subsequent processes. The binder can be one or a mixture of polyethylene glycol solution, PVB resin and polyvinyl alcohol solution. The inventor finds that the binder can obviously improve the strength of subsequent mixed blocks, thereby meeting the strength requirement of the anode material for subsequent electrolytic work.
The mixing ratio of the uranium oxide, the carbon and the binder is not particularly limited, and can be selected by those skilled in the art according to actual needs, and according to the specific embodiment of the present invention, the mixing ratio of the uranium oxide, the carbon and the binder can be determined according to the molar ratio of the uranium oxide to the carbon of 1: (1-10) blending, and then adding a bonding agent accounting for 5-20% of the total mass of the two. It should be noted that the amount of carbon added directly affects the end product UCxO1-xThe value of x in (x is more than or equal to 0 and less than or equal to 1), namely the content of carbon in the carbon-oxygen-uranium. The inventors found that when the amount of carbon blended is too small, UC does not occurxO1-x(x is 0-1) the formation of intermediates, only partial reduction of the higher uranium oxide, carbon with CO or CO2The form escapes without being in the crystal lattice of uranium oxide; when the amount of carbon is too large, the final product is UC and unreacted carbon, which results in waste of raw materials and energy. Meanwhile, the adhesive is used as an auxiliary material, the excellent effect cannot be achieved when the amount of the adhesive is too small or too much, and the cost burden is caused when the amount of the adhesive is too much.
The particle size of the uranium oxide and carbon is not particularly limited, and those skilled in the art can select the particle size according to actual needs, and according to a specific embodiment of the present invention, the particle size of the uranium oxide and carbon is not more than 0.074 micron. Thus, the inventor finds that materials in the particle size range can be fully mixed, so that the contact area between uranium oxide and carbon can be remarkably increased, and the reduction reaction and the formation of a carbon-oxygen-uranium intermediate can be promoted.
(2) Molding the mixed material under certain pressure to obtain mixed blocks
The mixed material is molded mainly to obtain a mixed briquette with certain strength, and the sufficient contact between uranium oxide and carbon is ensured, so that the subsequent vacuum reduction is smoothly carried out.
The pressure forming conditions are not particularly limited, and those skilled in the art can select the pressure according to actual needs, and according to the specific embodiment of the present invention, the forming pressure is 10 to 100 MPa. Thus, the inventors have found that the mixed briquette obtained at a molding pressure within this range has a high strength and can satisfy the requirements of the subsequent steps.
(3) Carrying out vacuum high-temperature reaction treatment on the mixed blocks to obtain a carbon-oxygen-uranium intermediate UCxO1-x
Carrying out vacuum high-temperature reaction treatment on the mixed block mass in a high-temperature vacuum furnace to obtain a carbon-oxygen-uranium intermediate UCxO1-x(0≤x≤1)，UCxO1-xCan be regarded as a solid solution of UO and UC, has good conductivity, and can be directly used as an anode for electrolysis.
The conditions of the vacuum high-temperature reaction are not particularly limited, and can be selected by those skilled in the art according to actual needs, and according to the specific embodiment of the present invention, the conditions of the vacuum reduction reaction are specifically: the reduction temperature is 1200-1800 ℃, the vacuum degree is 10-100Pa, and the reaction time is 1-6 h. Therefore, the intermediate UC of the carbon-oxygen-uranium with good conductivity can be prepared by utilizing the uranium oxide and the carbonxO1-x. It should be noted that, when the reduction temperature is too low or the vacuum degree is too low, the uranium oxide and the carbon do not undergo a reduction reaction or do not react sufficiently; if the reduction temperature is too high or the degree of vacuum is too high, the reduction reaction of uranium oxide and carbon proceeds sufficiently, but energy is wasted. Too long or too short a reaction time may not be optimal.
The vacuum reduction reaction of uranium oxide may include the following reactions:
UO2+(1+2x)C＝(1+x)CO+UCxO1-x(0≤x≤1)
U3O8+(5+6x)C＝(5+3x)CO+3UCxO1-x(0≤x≤1)
UO3+2(1+x)C＝(2+x)CO+UCxO1-x(0≤x≤1)
intermediate UC of uranylxO1-xIs not higher than 10 omega.m, thus obtaining the intermediate UC of the uranyl carbonatexO1-xHas good conductivity and can be used as an electrode material for electrolysis.
(4) Adding carbon to oxygenUranium intermediate UCxO1-xAs anode for molten salt electrolysis to obtain metallic uranium
Mixing C-O-U intermediate UCxO1-xAnd as an anode, a cathode is made of a metal material, electrolysis is carried out in molten salt under the protection of inert atmosphere, and a cathode product is collected after the electrolysis is finished and is a metal uranium product.
The cathode of the molten salt electrolysis is made of a metal material, the selection of the metal material is not particularly limited, and a person skilled in the art can select the metal material according to actual needs. Thus, the deposition of metallic uranium produced in the electrolytic process at the cathode can be achieved.
The molten salt used for molten salt electrolysis is an alkali metal or alkaline earth metal halide molten salt system, preferably fluoride or chloride, more preferably chloride.
The conditions of molten salt electrolysis include: the electrolysis temperature is 500-: 0.04-1.00A/cm of anode2Cathode 0.06-1.00A/cm2。
UCxO1-xThe molten salt electrolysis reaction of the intermediate may include the following reactions:
and (3) anode reaction: UCxO1-x→Un++CO+CO2+ ne (x is 0-1, n is 2 or 3)
And (3) cathode reaction: u shapen++ne→U
The treatment of the cathode product may further comprise: and the cathode product is taken down at normal temperature, and deionized water or ethanol is used for washing off molten salt on the surface of the metal uranium, so that purer uranium product can be ensured.
In a preferred embodiment, the invention provides a method for preparing metallic uranium by using uranium oxide, wherein in the step (1), the uranium oxide is one or more of uranium dioxide, triuranium octoxide and uranium trioxide.
In a preferred embodiment, the invention provides a method for preparing metallic uranium by using uranium oxide, wherein in the step (1), the binder is one or more of polyethylene glycol, PVB resin and polyvinyl alcohol.
In a preferred embodiment, the present invention provides a process for the production of metallic uranium from uranium oxide, wherein in step (1), the average particle size of the uranium oxide and carbon is in the range of 0.001 to 0.074 μm, whereby the uranium oxide and carbon can be brought into intimate contact to promote the reduction reaction.
In a preferred embodiment, the invention provides a method for preparing metallic uranium from uranium oxide, wherein in step (1), the molar ratio of uranium oxide to carbon is 1: (1-10) and adding 5-20% of binder based on total mass of uranium oxide and carbon, thereby promoting the production of uranium oxycarbide intermediate UCxO1-xIs performed.
In a preferred embodiment, the invention provides a method for preparing metallic uranium by using uranium oxide, wherein in the step (1), the pressing pressure is 10-100MPa, so that the mixed briquette has certain strength.
In a preferred embodiment, the invention provides a method for preparing metallic uranium by utilizing uranium oxide, wherein in the step (2), the temperature of the vacuum reduction reaction is 1200-1800 ℃, the vacuum degree is 10-100Pa, and the time is 1-6h, so that the uranium oxycarbide intermediate UC with good conductivity can be prepared by utilizing uranium oxide and carbonxO1-x(intermediate UC of uranyl carbonate)xO1-xIs not higher than 10 Ω. m).
In a preferred embodiment, the invention provides a method for preparing metallic uranium by utilizing uranium oxide, wherein in the step (3), the metallic material is one or more of carbon steel, molybdenum, tungsten and nickel (so that the metallic uranium generated in the electrolytic process can be deposited at a cathode); the molten salt is one or more of alkali metal halide and alkaline earth metal halide (preferably fluoride or chloride, more preferably chloride).
In a preferred embodiment, the invention provides a method for preparing metallic uranium by utilizing uranium oxide, wherein in the step (3), the electrolysis temperature of the electrolysis reaction is 500-1000 ℃, and the anode current density is 0.04-1.00A/cm2And the cathode current density was 0.06-1.00A/cm2。
In a preferred embodiment, the invention provides a method for preparing metallic uranium by utilizing uranium oxide, wherein in the step (3), the collected cathode electrolysis product is further washed away molten salt on the surface of the metallic uranium by deionized water or ethanol at normal temperature.
The method for preparing the metal uranium by utilizing the uranium oxide has the beneficial effects that the process is simple, the cost is low, and the uranium reduction rate is high.
The method can prepare the uranium oxide into a carbon-oxygen-uranium intermediate UC with metal conductivity through vacuum carbothermic reductionxO1-xThen, the intermediate of the carbon-oxygen-uranium is used as an anode to carry out electrolysis in molten salt, and carbon and oxygen contained in the intermediate of the anode carbon-oxygen-uranium are combined into carbon-oxygen gas (CO, CO) in the electrolysis process2) Or oxygen is changed to escape, and the contained uranium enters molten salt in the form of low-valence ions and is deposited at a cathode to obtain a metallic uranium product. Compared with the traditional electrolytic reduction technology taking uranium oxide as a cathode, the preparation method disclosed by the invention is simple, the electrode material cost is low, the process flow is short, the purity of the uranium product is high, and the method is a novel method for preparing metal uranium by utilizing uranium oxide.
Drawings
FIG. 1 is a flow chart of a method for preparing metallic uranium from uranium oxide in examples 1 to 8.
Detailed Description
The following description will further describe embodiments of the present invention with reference to the accompanying drawings.
Example 1:
mixing uranium dioxide and carbon according to the molar ratio of 1:2, adding polyethylene glycol 400 (average molecular weight 400) with the total mass of the uranium dioxide and the carbon being 5%, and uniformly mixing to obtain a mixed material. And (3) molding the mixed material under the pressure of 10MPa to obtain a cylindrical mixed block. Carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace, wherein the reaction conditions are as follows: the reduction temperature is 1200 ℃, the vacuum degree is 10Pa, the reaction time is 6h, and the intermediate UC of the carbon-oxygen-uranium is obtained after the reaction is finished0.5O0.5(resistivity 4 × 10-2Ω. m). Mixing C-O-U intermediate UC0.5O0.5As an anode, carbon steel is used as a cathode, and molten salt electrolysis is carried out under an LiCl-KCl molten salt system under the protection of inert gas, wherein the electrolysis conditions are as follows: the electrolysis temperature is 500 ℃, and the current density during electrolysis is respectively as follows: 0.04A/cm of anode2Cathode 0.10A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing away molten salt by using deionized water to obtain a metal uranium product, wherein the purity of the analyzed uranium is 99.2%.
Example 2:
mixing uranium dioxide and carbon according to the molar ratio of 1:1.5, adding PVB resin accounting for 10% of the total mass of the uranium dioxide and the carbon, and uniformly mixing to obtain a mixed material. And (3) molding the mixed material under the pressure of 20MPa to obtain a cylindrical mixed block. Carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace, wherein the reaction conditions are as follows: the reduction temperature is 1300 ℃, the vacuum degree is 20Pa, the reaction time is 5.5h, and the intermediate UC of the carbon-oxygen-uranium is obtained after the reaction is finished0.25O0.75(resistivity 5 × 10-3Ω. m). Mixing C-O-U intermediate UC0.25O0.75As an anode, a tungsten bar is used as a cathode, and molten salt electrolysis is carried out under the protection of inert gas in a LiF-KF-NaF molten salt system under the electrolysis conditions that: the electrolysis temperature is 650 ℃, and the current density during electrolysis is respectively as follows: 0.06A/cm of anode2Cathode 0.08A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing off molten salt by using ethanol to obtain a metal uranium product, wherein the purity of the analyzed uranium is 99.4%.
Example 3:
mixing triuranium octoxide and carbon according to a molar ratio of 1:8, adding a solution (the solution mass concentration is 5%) of polyving akohol 1788 (the average molecular weight is 77000) with the total mass of the triuranium octoxide and the carbon being 20%, and uniformly mixing to obtain a mixed material. And (3) molding the mixed material under the pressure of 30MPa to obtain a cylindrical mixed block. Carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace, wherein the reaction conditions are as follows: the reduction temperature is 1400 ℃, the vacuum degree is 30Pa, the reaction time is 5h, and the intermediate UC of the uranyl carbonate is obtained after the reaction is finished0.5O0.5(electric power)Resistivity 6 × 10-4Ω. m). Mixing C-O-U intermediate UC0.5O0.5As an anode, a molybdenum rod is used as a cathode, and molten salt electrolysis is carried out under the protection of inert gas in a NaCl-KCl molten salt system under the electrolysis conditions that: the electrolysis temperature is 1000 ℃, and the current density during electrolysis is respectively as follows: 0.10A/cm of anode2Cathode 0.10A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing away molten salt by using deionized water to obtain a metal uranium product, wherein the purity of the analyzed uranium is 99.0%.
Example 4:
mixing triuranium octoxide and carbon according to a molar ratio of 1:7, adding polyethylene glycol 400 (average molecular weight 400) with the total mass of triuranium octoxide and carbon being 8%, and uniformly mixing to obtain a mixed material. And (3) molding the mixed material under the pressure of 50MPa to obtain a cylindrical mixed block. Carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace, wherein the reaction conditions are as follows: the reduction temperature is 1500 ℃, the vacuum degree is 40Pa, the reaction time is 4h, and the intermediate UC of the uranyl carbonate is obtained after the reaction is finished0.33O0.67(resistivity 2 × 10-2Ω. m). Mixing C-O-U intermediate UC0.33O0.67As an anode, a nickel rod is used as a cathode, and molten salt electrolysis is carried out under the protection of inert gas in a NaCl-KCl molten salt system under the electrolysis conditions that: the electrolysis temperature is 900 ℃, and the current density during electrolysis is respectively as follows: 0.08A/cm of anode2Cathode 0.09A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing away molten salt by using deionized water to obtain a metal uranium product, wherein the purity of the analyzed uranium is 99.1%.
Example 5:
mixing uranium trioxide and carbon according to a molar ratio of 1:4, adding PVB resin accounting for 12% of the total mass of the uranium trioxide and the carbon, and uniformly mixing to obtain a mixed material. And (3) molding the mixed material under the pressure of 80MPa to obtain a cylindrical mixed briquette. Carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace, wherein the reaction conditions are as follows: the reduction temperature is 1600 ℃, the vacuum degree is 60Pa, the reaction time is 2h, and the intermediate UC of the carbon-oxygen-uranium is obtained after the reaction is finished0.75O0.25(resistivity 7 × 10-4Ω. m). Mixing carbon with oxygenIntermediate UC0.75O0.25As an anode, a nickel rod is used as a cathode, and molten salt electrolysis is carried out under the protection of inert gas in a NaCl-KCl-LiCl molten salt system under the electrolysis conditions that: the electrolysis temperature is 700 ℃, and the current density during electrolysis is respectively as follows: 0.07A/cm of anode2Cathode 0.08A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing away molten salt by using deionized water to obtain a metal uranium product, wherein the purity of the analyzed uranium is 98.7%.
Example 6:
mixing uranium trioxide and carbon according to a molar ratio of 1:3, adding polyethylene glycol 400 (average molecular weight 400) accounting for 17% of the total mass of the uranium trioxide and the carbon, and uniformly mixing to obtain a mixed material. And (3) molding the mixed material under the pressure of 100MPa to obtain the cylindrical mixed block. Carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace, wherein the reaction conditions are as follows: the reduction temperature is 1800 ℃, the vacuum degree is 100Pa, the reaction time is 1h, and the intermediate UC of the uranyl carbonate is obtained after the reaction is finished0.5O0.5(resistivity 4 × 10-5Ω. m). Mixing C-O-U intermediate UC0.5O0.5As an anode, a nickel rod is used as a cathode, and molten salt electrolysis is carried out under a KCl-LiCl molten salt system under the protection of inert gas, wherein the electrolysis conditions are as follows: the electrolysis temperature is 800 ℃, and the current density during electrolysis is respectively as follows: 0.05A/cm of anode2Cathode 0.06A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing away molten salt by using deionized water to obtain a metal uranium product, wherein the purity of the analyzed uranium is 98.9%.
Example 7:
mixing triuranium octoxide and carbon according to a molar ratio of 1:10, adding a solution (the mass concentration of the solution is 5%) of polyving akohol 1788 (the average molecular weight is 77700) with the total mass of the triuranium octoxide and the carbon being 16%, uniformly mixing to obtain a mixed material, forming the mixed material under the pressure of 80MPa to obtain a cylindrical mixed block, carrying out vacuum reduction reaction on the mixed block in a vacuum reaction furnace under the reaction conditions of the reduction temperature of 1700 ℃, the vacuum degree of 90Pa and the reaction time of 3h to obtain a carbon-oxygen-uranium intermediate UC (the resistivity is 3 × 10)-5Ω. m). Intermediate of carbon oxygen and uraniumTaking the body UC as an anode and carbon steel as a cathode, and carrying out molten salt electrolysis under a NaF-KF molten salt system under the protection of inert gas, wherein the electrolysis conditions are as follows: the electrolysis temperature is 650 ℃, and the current density during electrolysis is respectively as follows: 0.06A/cm of anode2Cathode 0.07A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing away molten salt by using deionized water to obtain a metal uranium product, wherein the purity of the analyzed uranium is 99.6%.
Example 8:
mixing uranium dioxide and carbon according to the molar ratio of 1:1, adding polyethylene glycol 400 (average molecular weight 400) accounting for 20% of the total mass of the uranium dioxide and the carbon, and uniformly mixing to obtain a mixed material. And (3) molding the mixed material under the pressure of 75MPa to obtain a cylindrical mixed block. Carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace, wherein the reaction conditions are as follows: the reduction temperature is 1750 ℃, the vacuum degree is 85Pa, the reaction time is 2.5h, and a carbon-oxygen-uranium intermediate UO (with the resistivity of 10 omega. m) is obtained after the reaction is finished. Taking a carbon-oxygen-uranium intermediate UO as an anode and carbon steel as a cathode, and carrying out molten salt electrolysis under the protection of inert gas in a NaCl-KCl molten salt system, wherein the electrolysis conditions are as follows: the electrolysis temperature is 550 ℃, and the current density during electrolysis is respectively as follows: 0.05A/cm of anode2Cathode 0.06A/cm2. And after the electrolysis is finished, taking down the cathode product at normal temperature, washing away molten salt by using deionized water to obtain a metal uranium product, wherein the purity of the analyzed uranium is 99.3%.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.

Claims (10)

1. A method for preparing metallic uranium by utilizing uranium oxide is characterized by comprising the following steps:
(1) mixing uranium oxide, carbon and a binder uniformly and pressing into a mixed briquette with certain shape characteristics;
(2) carrying out vacuum reduction reaction on the mixed lumps in a vacuum reaction furnace to prepare a carbon-oxygen-uranium intermediate UC with metal conductivityxO1-xWherein x is more than or equal to 0 and less than or equal to 1;
(3) the intermediate UC of the carbon oxygen uraniumxO1-xAnd as an anode, taking a metal material as a cathode, carrying out an electrolytic reaction in molten salt under the protection of inert atmosphere, and collecting a cathode electrolysis product as a metal uranium product.
2. The method of claim 1, wherein: in the step (1), the uranium oxide is one or more of uranium dioxide, triuranium octoxide and uranium trioxide.
3. The method of claim 1, wherein: in the step (1), the binder is one or more of polyethylene glycol, PVB resin and polyvinyl alcohol.
4. The method of claim 1, wherein: in step (1), the average particle size of uranium oxide and carbon is 0.001-0.074 μm.
5. The method of claim 1, wherein: in the step (1), the molar ratio of uranium oxide to carbon is 1: (1-10) mixing, wherein the addition amount of the binder is 5-20% of the total mass of the uranium oxide and the carbon.
6. The method of claim 1, wherein: in the step (1), the pressing pressure is 10-100 MPa.
7. The method of claim 1, wherein: in the step (2), the temperature of the vacuum reduction reaction is 1200-1800 ℃, the vacuum degree is 10-100Pa, and the time is 1-6 h.
8. The method of claim 1, wherein: in the step (3), the metal material is one or more of carbon steel, molybdenum, tungsten and nickel; the molten salt is one or more of alkali metal halide and alkaline earth metal halide.
9. The method of claim 1, wherein: in the step (3), the electrolysis temperature of the electrolysis reaction is 500-2The cathode current density is 0.06-1.00A/cm2。
10. The method of claim 1, wherein: and (3) washing the molten salt on the surface of the metal uranium by using deionized water or ethanol at normal temperature for the collected cathode electrolysis product.
CN202010146329.4A 2020-03-05 2020-03-05 Method for preparing uranium by utilizing uranium oxide Pending CN111364065A (en)

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