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CN112301379B - Method for preparing metal zirconium by using zirconium dioxide as raw material - Google Patents

Method for preparing metal zirconium by using zirconium dioxide as raw material Download PDF

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CN112301379B
CN112301379B CN202011096017.3A CN202011096017A CN112301379B CN 112301379 B CN112301379 B CN 112301379B CN 202011096017 A CN202011096017 A CN 202011096017A CN 112301379 B CN112301379 B CN 112301379B
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zirconium
carbon
nitrogen
zirconium dioxide
metal
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CN112301379A (en
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宋建勋
李少龙
车玉思
杨斌
何季麟
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Zhengzhou University
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium

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Abstract

The method for preparing metal zirconium by using zirconium dioxide as a raw material comprises the following steps: (1) mixing zirconium dioxide and carbon according to a set proportion, and pressing and molding the obtained mixture under a set pressure; (2) reacting the mixture subjected to compression molding with nitrogen at a set temperature to obtain a zirconium-carbon-oxygen-nitrogen solid solution; (3) and performing constant current electrolysis by using the zirconium-carbon-oxygen-nitrogen solid solution as an anode, alkali metal or alkaline earth metal chloride fused salt as an electrolyte and a metal rod or plate as a cathode to obtain a deposition product, namely the metal zirconium on the cathode.

Description

Method for preparing metal zirconium by using zirconium dioxide as raw material
Technical Field
The application belongs to the technical field of electrochemical metallurgy, and particularly relates to a method for preparing metal zirconium by using zirconium dioxide as a raw material.
Background
The metal zirconium has excellent nuclear performance, corrosion resistance, biocompatibility, mechanical property and processability, and is widely applied to the fields of petroleum, energy, chemical industry, nuclear field, medical apparatus and the like.
The Kroll process is a pyrometallurgical industrial process for producing metallic titanium, can also be used for preparing metallic zirconium, and is the mainstream method for preparing metallic zirconium at present. The process uses zirconium dioxide as a raw material, firstly, zirconium tetrachloride is chloridized, then, zirconium tetrachloride is reduced by using magnesium to obtain zirconium sponge, and the generated magnesium chloride obtains metal magnesium through electrolysis for recycling. The whole process comprises zirconium dioxide chlorination, magnesium thermal reduction of calcium chloride and magnesium chloride electrolysis. The steps are complicated, the energy consumption is large, and the generation efficiency is low.
In recent years, a number of people have proposed new methods for the production of metallic zirconium, the more influential being the FFC method proposed by cambridge university, which was also used initially for the production of metallic titanium, and which was later gradually applied to the production of other refractory metals, including also metallic zirconium. The FFC process is an electrochemical method, and takes an oxide as a cathode to electrolyze and remove oxygen in molten salt to obtain metal. The method has simple operation and short flow. But the current efficiency is low and the product quality is difficult to control.
Disclosure of Invention
In view of this, the technical solution disclosed in the embodiments of the present application is a method for preparing zirconium metal by using zirconium dioxide as a raw material, the method comprising:
(1) mixing zirconium dioxide and carbon in a set proportion to obtain a mixture of zirconium dioxide and carbon, and pressing and molding the obtained mixture under a set pressure;
(2) reacting the mixture subjected to compression molding with nitrogen at a set temperature to obtain a zirconium-carbon-oxygen-nitrogen solid solution;
(3) and performing constant current electrolysis by using the zirconium-carbon-oxygen-nitrogen solid solution as an anode, alkali metal or alkaline earth metal chloride fused salt as an electrolyte and a metal rod or plate as a cathode to obtain a deposition product, namely the metal zirconium on the cathode.
Further, some examples disclose methods for preparing zirconium metal using zirconium dioxide as a raw material, wherein the molar ratio of zirconium dioxide to carbon is set to 1: 2.0-3.0.
In some embodiments, disclosed is a method for preparing zirconium metal from zirconium dioxide, wherein a mixture of zirconium dioxide and carbon is pressed and molded under 50-100 Mpa.
Some examples disclose a method for preparing zirconium metal by using zirconium dioxide as a raw material, wherein the reaction temperature of the mixture formed by pressing and nitrogen is set to be 1600-1800 ℃.
In some embodiments, the reaction of the mixture formed by pressing with nitrogen is performed in a nitrogen flow, and the flow rate of the nitrogen is set to be 20-100 mL/min.
Some examples disclose methods for preparing zirconium metal from zirconium dioxide, the molten salt of an alkali or alkaline earth metal chloride including NaCl-KCl, LiCl-KCl, CaCl2-KCl。
Some examples disclose methods for preparing metallic zirconium from zirconium dioxide as a starting material, wherein a set amount of a zirconium salt is added to the electrolyte.
Further, some examples disclose methods for preparing zirconium metal from zirconium dioxide as a raw material, wherein the zirconium salt added to the electrolyte comprises K2ZrF6The content thereof is not more than 20% by mass of the total mass of the electrolyte.
Some examples disclose methods for preparing zirconium metal from zirconium dioxide, wherein the temperature of the electrolyte is set to 400-1000 ℃ in constant current electrolysis.
Some examples disclose methods for preparing zirconium metal from zirconium dioxideIn the constant current electrolysis process, the cathode current density is set to be 0.1-1.0A/cm2The current density of the anode is set to 0.05-1.0A/cm2
The method for preparing the metal zirconium by using the zirconium dioxide as the raw material disclosed by the embodiment of the application comprises the steps of preparing the zirconium dioxide and carbon into a zirconium-carbon-oxygen-nitrogen solid solution by using the zirconium dioxide as the raw material, using the zirconium dioxide and the carbon as an anode of an electrolytic reaction, carrying out constant current electrolysis in chloride molten salt of alkali metal or alkaline earth metal, and obtaining high-purity metal zirconium at a cathode.
Drawings
FIG. 1 XRD pattern of solid solution of zirconium dioxide and activated carbon mixture
FIG. 2 XRD pattern of solid solution of zirconium dioxide and graphite mixture
FIG. 3 XRD patterns of solid solutions of zirconium dioxide and graphite in example 1
FIG. 4 XRD pattern of metallic zirconium product of example 1
FIG. 5 SEM photograph of metallic zirconium of example 1 product
Detailed Description
The word "embodiment" as used herein, is not necessarily to be construed as preferred or advantageous over other embodiments, including any embodiment illustrated as "exemplary". Performance index tests in the examples of this application, unless otherwise indicated, were performed using routine experimentation in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly employed by those of ordinary skill in the art.
The terms "substantially" and "about" are used herein to describe small fluctuations. For example, they may mean less than or equal to ± 5%, such as less than or equal to ± 2%, such as less than or equal to ± 1%, such as less than or equal to ± 0.5%, such as less than or equal to ± 0.2%, such as less than or equal to ± 0.1%, such as less than or equal to ± 0.05%. Numerical data represented or presented herein in a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of "1 to 5%" should be interpreted to include not only the explicitly recited values of 1% to 5%, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values, such as 2%, 3.5%, and 4%, and sub-ranges, such as 1% to 3%, 2% to 4%, and 3% to 5%, etc. This principle applies equally to ranges reciting only one numerical value. Moreover, such an interpretation applies regardless of the breadth of the range or the characteristics being described.
In this document, including the claims, all conjunctions such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" containing, "and the like are to be understood as being open-ended, i.e., to mean" including but not limited to. Only the conjunctions "consisting of … …" and "consisting of … …" are closed conjunctions.
In the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, apparatuses, etc. known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application.
On the premise of no conflict, the technical features disclosed in the embodiments of the present application may be combined arbitrarily, and the obtained technical solution belongs to the content disclosed in the embodiments of the present application.
In some embodiments, the method for preparing metallic zirconium by using zirconium dioxide as a raw material comprises:
(1) mixing zirconium dioxide and carbon according to a set proportion, and pressing and molding the obtained mixture under a set pressure; zirconia is usually mixed with carbon to form a mixture in which carbon is uniformly distributed in the zirconia, and the mixture is pressed into a block with a certain shape to participate in the subsequent reaction; the mixture block is reacted with nitrogen to form a zirconium-carbon-oxygen-nitrogen solid solution, and is further used as an electrode for electrochemical reaction, so the shape of the mixture block can be generally set according to the requirement of being used as an electrochemical electrode; carbon generally refers to a carbon material, generally refers to a carbonaceous material used in the related art, and for example, activated carbon or graphite can be selected, and generally the carbon material is mixed with zirconium dioxide powder in a powder state, so that the carbon material and the zirconium dioxide powder are distributed in the mixture more uniformly, the subsequent reaction is facilitated to be performed uniformly, and a zirconium-carbon-oxygen-nitrogen solid solution with a uniform structure is realized;
(2) reacting the mixture subjected to compression molding with nitrogen at a set temperature to obtain a zirconium-carbon-oxygen-nitrogen solid solution; generally, a mixture of zirconium dioxide and carbon is pressed and formed, and reacts with nitrogen to form a zirconium-carbon-oxygen-nitrogen solid solution, and the reaction is generally carried out by placing a mixture block in a nitrogen atmosphere at a set temperature to obtain the zirconium-carbon-oxygen-nitrogen solid solution with a certain shape and size;
(3) carrying out constant current electrolysis by taking a zirconium-carbon-oxygen-nitrogen solid solution as an anode, an alkali metal or alkaline earth metal chloride fused salt as an electrolyte and a metal rod or plate as a cathode to obtain a deposition product, namely metal zirconium on the cathode; the prepared zirconium-carbon-oxygen-nitrogen solid solution has the shape and the size suitable for serving as an anode in an electrochemical electrolysis process, is placed in an electrolysis device, is positioned in an electrolyte, participates in the electrochemical electrolysis process, and is subjected to constant-current electrolysis; wherein, the electrolyte is alkali metal or alkaline earth metal chloride fused salt, the fused salt electrolyte is heated to a set temperature and is completely melted into liquid electrolyte, and the zirconium-carbon-oxygen-nitrogen solid solution anode is arranged in the liquid electrolyte; as the cathode of the electrochemical electrolysis process, a metal bar or plate suitable for the cathode is usually selected, so that zirconium ions released from the anode during the electrolysis process are deposited and separated on the cathode to obtain pure metal zirconium.
Alternatively, the molar ratio of zirconium dioxide to carbon is set to 1:2.0 to 3.0. Usually, the carbon material is selected from activated carbon or graphite, mixed with zirconium dioxide, and then pressed into a shape. Generally, it is necessary to set a suitable ratio of zirconium dioxide and carbon so as to obtain a structurally stable and uniform solid solution of zirconium-carbon-oxygen-nitrogen in the subsequent nitriding reaction, and during the compression molding of the mixture of zirconium dioxide and carbon, it is necessary to control a suitable pressure so as to have a structure with a suitable density and suitable voids so that nitrogen can sufficiently and effectively enter the mixture bulk to participate in the nitriding reaction to form the desired solid solution of zirconium-carbon-oxygen-nitrogen, and when the density is too low, the structural strength is insufficient, and when the density is too low, the function of the solid solution in the electrolytic process is difficult to effectively exert, and when the density is too high, nitrogen molecules are not easily entered into the internal structure of the mixture bulk, so that the nitriding reaction is incomplete and non-uniform, and the structurally stable and uniform solid solution of zirconium-carbon-oxygen-nitrogen cannot be obtained.
Generally, when zirconium dioxide is mixed with activated carbon to prepare a zirconium-carbon-oxygen-nitrogen solid solution, the molar ratio of the zirconium dioxide to the activated carbon is set to 1:2.0 to 3.0. Mixing zirconium dioxide and activated carbon in a ratio of 1:1, 1:1.8, 1:2, 1:2.6 and 1:3 to obtain a mixture, then the mixture is pressed and molded under the pressure of 50Mpa to form a mixture block, then the mixture block reacts with nitrogen with the flow rate of 20mL/min at the temperature of 1600 ℃ to obtain the zirconium-carbon-oxygen-nitrogen solid solution, the structural characteristics of the obtained solid solution are as follows, as shown in the XRD diagram of the solid solution of the mixture of zirconium dioxide and activated carbon in FIG. 1, when the molar ratio of zirconium dioxide to activated carbon is 1:1 and 1:1.8, when a certain amount of diffraction peaks of zirconium dioxide exist in the structure of the product and the molar ratio of the diffraction peaks to the diffraction peaks is 1:2 and 1:2.6, the zirconium dioxide diffraction peak height existing in the product structure is very small, when the molar ratio of the zirconium dioxide diffraction peak height to the zirconium dioxide diffraction peak height is 1:3, the diffraction peak of the zirconium dioxide does not exist in the structure of the product, which indicates that the product is a single-structure zirconium-carbon-oxygen-nitrogen solid solution. In an alternative embodiment, the molar ratio of zirconium dioxide to activated carbon is set to 1:2.0 to 3.0, in a more preferred embodiment, 1:2.6 to 3.0, and in a more preferred embodiment, 1: 3.
Generally, when zirconium dioxide is mixed with graphite to prepare a zirconium-carbon-oxygen-nitrogen solid solution, the molar ratio of the zirconium dioxide to the graphite is set to 1:2.0 to 3.0. Mixing zirconium dioxide and graphite in a ratio of 1:1, 1:1.8, 1:2, 1:2.32 and 1:2.6 to obtain a mixture, then the mixture is pressed and molded under the pressure of 50Mpa to form a mixture block, and then the mixture block reacts with nitrogen with the flow rate of 20mL/min at the temperature of 1600 ℃ to obtain the zirconium-carbon-oxygen-nitrogen solid solution, the structural characteristics of the obtained solid solution are as follows, as shown in the XRD diagram of the solid solution of the mixture of zirconium dioxide and graphite in FIG. 2, when the molar ratio of zirconium dioxide to graphite is 1:1 and 1:1.8, when a certain amount of diffraction peaks of zirconium dioxide exist in the structure of the product and the molar ratio of the two is 1:2, the product structure only has the diffraction peak of the zirconium-carbon-oxygen-nitrogen, and the result shows that the product is a zirconium-carbon-oxygen-nitrogen solid solution with a single structure, and when the molar ratio of the two is 1:2.32 and 1:2.6, the diffraction peak of the zirconium-carbon-oxygen-nitrogen and a trace amount of graphite diffraction peaks exist in the product structure. In an alternative embodiment, the molar ratio of zirconium dioxide to graphite is set to 1:2 to 2.6, in a more preferred embodiment, 1:2 to 2.32, and in a still more preferred embodiment, 1:2.
According to an optional embodiment, the mixture of zirconium dioxide and carbon is pressed and molded under 50-100 Mpa.
As an alternative embodiment, the reaction temperature of the mixture of the compression-molded zirconium dioxide and carbon with nitrogen is set to be 1600 to 1800 ℃.
Typically, a bulk mixture of zirconium dioxide and carbon is reacted with nitrogen gas, the following reaction taking place:
ZrO2+C+N2→ZrCxOyNz+ CO (a) or
2ZrO2+4C+N2=2ZrN+4CO (b)
In the reaction formula (a), the sum of x, y and z is usually equal to or slightly less than 1, and represents the relative content of the three elements respectively.
If the reaction proceeds according to equation (b), the product is ZrN, reaction (b) is endothermic, and the Gibbs free energy at 1700 ℃ is-29.6 kJ/mol, indicating that the reaction can occur at this temperature and that the reaction proceeds more readily as the temperature increases. If the reaction is carried out according to reaction formula (a), ZrC is obtainedxOyNzThe reaction temperature is suitably lowered. For example, pure ZrC can be obtained at 1600 ℃xOyNz
The reaction temperature is usually selected to be 1600-1800 ℃, a proper proportion of the reaction raw materials is selected, a required zirconium-carbon-oxygen-nitrogen solid solution can be obtained within a proper reaction time, and the reaction is carried out according to the reaction formula (a).
Alternatively, the reaction of the mixture of the press-molded zirconium dioxide and carbon with nitrogen is carried out in a nitrogen flow, and the flow rate of the nitrogen is set to 20 to 100 mL/min. In order to ensure that the reaction atmosphere has a sufficient amount of nitrogen, the mixture is usually placed in a flowing nitrogen gas flow for reaction, and the nitrogen flow rate is properly selected to complete the reaction between the nitrogen and the zirconium dioxide and the carbon mixture block, for example, the flow rate of the nitrogen is set to be 20 to 100 mL/min.
As an alternative embodiment, the alkali or alkaline earth metal chloride molten salt includes NaCl-KCl, LiCl-KCl, CaCl2-KCl. Usually NaCl-KCl, LiCl-KCl, CaCl2Any one of-KCl can be used as a molten salt electrolyte of metallic zirconium.
As an alternative embodiment, a set amount of zirconium salt is added to the electrolyte. The zirconium salt added to the electrolyte generally increases a certain content of zirconium ions in the electrolyte, which is beneficial to the constant current electrolysis process. If the initial potential of constant current electrolysis without zirconium ions in the electrolyte is higher, alkali metal and alkaline earth metal can be precipitated at the cathode, the purity of metal zirconium precipitated and precipitated at the cathode is reduced, and if proper zirconium ions are added into the alkali metal or alkaline earth metal chloride molten salt, the alkali metal or alkaline earth metal can be prevented from being precipitated at the cathode.
As an alternative embodiment, the zirconium salt added to the electrolyte comprises K2ZrF6The content thereof is not more than 20% by mass of the total mass of the electrolyte, i.e., 20 wt.%. The zirconium salt is usually added to the electrolyte to contain a certain amount of zirconium ions, taking into account the temperature of the electrolyte during electrolysis, e.g. when the added zirconium salt is in the liquid state of the molten salt electrolyteHas appropriate stability and can prevent volatilization. As an alternative embodiment, K may be selected in general2ZrF6
As an alternative embodiment, the cathode material may be selected from zirconium, stainless steel, molybdenum, etc., and fabricated into the cathode in a suitable bar or plate shape.
In an alternative embodiment, the electrolyte temperature is set to 400-1000 ℃ in constant current electrolysis. The temperature of the electrolyte is the temperature of the total molten salt electrolyte in a proper liquid state in the constant current electrolysis process, generally, the temperature is determined according to the electrolyte type, for example, the temperature of eutectic salt electrolyte LiCl-KCl can be selected to be 400-500 ℃; the temperature of the eutectic salt electrolyte NaCl-KCl can be selected to be 700-800 ℃. Generally, the temperature of the electrolyte is set to 400 to 1000 ℃.
As an optional embodiment, in the constant current electrolysis process, the cathode current density is set to be 0.1-1.0A/cm2The current density of the anode is set to 0.05-1.0A/cm2. Generally, the electrolysis rate of a galvanostatic electrolysis process is related to the current density, and the electrolysis rate can be controlled by controlling the current density. The cathode current density is controlled to be 0.1-1.0A/cm2The form of the metal zirconium precipitated by the cathode can be controlled to be powder or branch crystal; influence of Anode Current Density ZrCxOyNzThe valence of zirconium in the zirconium oxide is 0.05-1.0A/cm2In this case, the valence may be 2 to 4.
Usually, after the electrolysis is finished, a metallic zirconium deposit is obtained on the cathode, and the deposit is taken out at normal temperature, washed to remove the electrolyte attached to the deposit, dried at a proper temperature, and removed of the detergent to obtain metallic zirconium. For example, the metallic zirconium deposit can be washed with deionized water and then dried at 60 to 80 ℃. Generally, the metal zirconium obtained by electrolysis is powder or dendritic crystal, oxygen is easy to absorb, and in order to reduce oxidation and reduce absorbed oxygen, the drying temperature is not too high, so that the temperature is selected to be 60-80 ℃, the moisture can be removed in the temperature range, and the oxygen content of the product is not increased.
The technical details are further illustrated in the following examples.
Example 1
Preparation of metallic zirconium
The zirconium dioxide is used as a raw material, and the process for preparing the metal zirconium is as follows:
(1) mixing zirconium dioxide and graphite in a molar ratio of 1:2, and pressing and molding the obtained mixture under the pressure of 100 Mpa;
(2) reacting the mixture subjected to compression molding with nitrogen with the flow rate of 25mL/min at 1600 ℃ to obtain a zirconium-carbon-oxygen-nitrogen solid solution;
(3) taking a zirconium-carbon-oxygen-nitrogen solid solution as an anode and NaCl-KCl as an electrolyte, wherein 10 wt.% of K is added2ZrF6The metal molybdenum rod is used as a cathode, the electrolyte temperature is set to 750 ℃, the constant current electrolysis is carried out in the argon atmosphere, and the current density of the cathode is 0.4A/cm2Anode current density 0.2A/cm2(ii) a The deposit product metal zirconium is obtained on the cathode.
And washing and drying the electrolysis product to obtain the metal zirconium.
XRD test and SEM test are respectively carried out on zirconium-carbon-oxygen-nitrogen solid solution formed by zirconium dioxide and graphite and metal zirconium, the XRD diagram of the silicon dioxide and graphite solid solution is shown in figure 3, the XRD diagram of the product metal zirconium is shown in figure 4, and the SEM diagram of the product metal zirconium is shown in figure 5.
The results in fig. 3 show that only a uniform structure of zirconium carbon oxygen nitrogen is present in solid solution, and zirconium dioxide and graphite are absent. The results in fig. 4 show that the product metallic zirconium is high purity metallic zirconium. The results in FIG. 5 show that the product is irregularly shaped particles with dimensions between 2 and 20 μm.
The method for preparing the metal zirconium by using the zirconium dioxide as the raw material disclosed by the embodiment of the application comprises the steps of preparing the zirconium dioxide and carbon into a zirconium-carbon-oxygen-nitrogen solid solution by using the zirconium dioxide as the raw material, using the zirconium dioxide and the carbon as an anode of an electrolytic reaction, carrying out constant current electrolysis in chloride molten salt of alkali metal or alkaline earth metal, and obtaining high-purity metal zirconium at a cathode.
The technical solutions and the technical details disclosed in the embodiments of the present application are only examples to illustrate the inventive concept of the present application, and do not constitute limitations on the technical solutions of the present application, and all the inventive changes, substitutions, or combinations that are made to the technical details disclosed in the present application without creativity are the same as the inventive concept of the present application and are within the protection scope of the claims of the present application.

Claims (1)

1. The method for preparing metal zirconium by using zirconium dioxide as a raw material is characterized by comprising the following steps:
(1) mixing zirconium dioxide and carbon according to a set proportion to obtain a mixture of zirconium dioxide and carbon, and pressing and molding the mixture under a set pressure of 50-100 Mpa; if the carbon is activated carbon, the molar ratio of zirconium dioxide to activated carbon is 1: 2.6-3.0, and if the carbon is graphite, the molar ratio of zirconium dioxide to graphite is 1: 2-2.32;
(2) reacting the mixture subjected to compression molding with nitrogen at a set temperature of 1600-1800 ℃, wherein the reaction is carried out in a nitrogen flow, and the flow rate of the nitrogen is set to be 20-100 mL/min, so as to obtain the zirconium-carbon-oxygen-nitrogen solid solution;
(3) performing constant current electrolysis by using a zirconium-carbon-oxygen-nitrogen solid solution as an anode, an alkali metal or alkaline earth metal chloride fused salt as an electrolyte and a metal rod or plate as a cathode to obtain a deposition product, namely metal zirconium, on the cathode, wherein the temperature of the electrolyte is set to be 400-1000 ℃, and the current density of the cathode is set to be 0.1-1.0A/cm2The current density of the anode is set to 0.05-1.0A/cm2The alkali metal or alkaline earth metal chloride fused salt is NaCl-KCl, LiCl-KCl or CaCl2-KCl; adding zirconium salt K with the content not exceeding 20 percent of the total mass of the electrolyte into the electrolyte2ZrF6
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