CN111235603B - Method for preparing metal beryllium by molten salt electro-deoxidation - Google Patents
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Abstract
The invention discloses a method for preparing metal beryllium by molten salt electro-deoxidation, and belongs to the field of electrochemical metallurgy. The preparation method comprises the steps of taking BeO as a raw material, uniformly mixing the BeO with a pore-forming agent and a conductive agent, pressing and sintering to prepare a cathode sheet, and then performing electro-deoxidation in chloride molten salt to obtain the cathode sheet. The invention overcomes the problem that the production of metal beryllium in the prior art easily causes environmental pollution, and aims to provide the method for preparing the metal beryllium by molten salt electro-deoxidation.
Description
Technical Field
The invention relates to the technical field of electrochemical metallurgy, in particular to a method for preparing metal beryllium by molten salt electro-deoxidation.
Background
Beryllium has small density, high rigidity, strong heat absorption capacity, small heat neutron absorption capacity and high scattering capacity, and is widely applied to the fields of aerospace, national defense and military industry, nuclear energy and the like as a special functional and structural material. Because beryllium has great significance to national safety and development of emerging industries, the production and utilization amount of beryllium also becomes one of important indexes for measuring the national high-tech level.
Currently, there are two methods for industrially producing metallic beryllium: BeF2Magnesiothermic reduction process and BeCl2Molten salt electrolysis. BeF2The magnesium thermal reduction method firstly uses ammonium bifluoride to convert the raw material BeO into ammonium beryllium fluoride, and the ammonium beryllium fluoride is thermally decomposed at the temperature of 900-1100 ℃ to obtain BeF2And then adding magnesium to BeF at the temperature of 900-2Reduced to metallic beryllium. The metallic beryllium beads produced by the method have the defects that the slag and the beryllium beads are difficult to separate due to the poor fluidity of magnesium fluoride, and the purity of the obtained beryllium beads is low. BeCl2The molten salt electrolysis method is that the raw material BeO and carbonaceous reducing agent are pressed into lumps firstly, and then the lumps are chloridized into BeCl at high temperature2Then, a nickel crucible was used as a cathode and a graphite rod was used as an anode, and approximately equal amounts of BeCl were added2And mixing and melting the copper powder and sodium chloride, and electrolyzing to finally obtain scaly metallic beryllium on the inner wall of the nickel crucible. But due to BeCl2Of beryllium in BeCl2The solubility in the molten salt is high, so that the current efficiency of the molten salt electrolysis method for producing crystalline flake beryllium is low; in addition, since BeCl2Low and high boiling point ofBeCl which is extremely easy to volatilize and has extremely strong toxicity at low temperature2Steam, and BeCl2The anode gas generated by electrolysis is Cl2And the environmental pollution is serious. Currently, the industry is continuously pursuing how to produce metallic beryllium more effectively.
Through retrieval, the Chinese patent application number: 2018111211926, the name of invention creation is: the application discloses a method for preparing metal beryllium by beryllium chloride reduction, which can realize the preparation of high-purity metal beryllium by two steps of reduction, fractionation and purification; the used raw material is beryllium chloride obtained by chloridizing metallurgy, metal beryllium obtained by reaction and reduction of alkali metal without adding any auxiliary agent has high purity, the chloride of the alkali metal can be directly electrolyzed to reach metal and chlorine, and the raw material can be efficiently recycled; no water is used in the whole preparation process, and no wastewater pollution exists. Likewise, the application still uses the traditional beryllium chloride directly as a raw material, so that the problem of gas pollution mentioned above is difficult to avoid, and further optimization space is provided.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problem that the production of metal beryllium in the prior art easily causes environmental pollution, and provides a method for preparing metal beryllium by molten salt electro-deoxidation, which is a beryllium production method with simple process and environmental friendliness. The method directly uses BeO as the raw material, omits the complex raw material pretreatment process in the prior art, greatly simplifies the beryllium production process, reduces the production cost, has good environmental benefit in the whole production process, and obtains the product with high purity.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a method for preparing metal beryllium by molten salt electro-deoxidation, which is characterized in that BeO is used as a raw material, the BeO, a pore-forming agent and a conductive agent are uniformly mixed, then the mixture is pressed and sintered to prepare a cathode sheet, and then the cathode sheet is electro-deoxidized in chloride molten salt to obtain the metal beryllium.
Further, the steps are as follows:
s1, mixing and tabletting: uniformly mixing BeO serving as a raw material with a pore-forming agent and a conductive agent, and pressing the uniformly mixed mixture into a mixture tablet;
s2, tabletting and sintering: the mixture is pressed into sheets to be sintered under the protective atmosphere, and mixture sintered sheets are obtained;
s3, molten salt electro-deoxidation: and assembling the mixture sintered sheet and a molybdenum rod into a cathode, taking a graphite rod as an anode, inserting the graphite rod into an electrolytic tank containing chloride fused salt for electro-deoxidation, introducing protective gas in the electrolytic process, taking out an electrolytic product after the electrolysis is finished, and removing the fused salt attached to the surface to obtain the solid metal beryllium.
Further, the pore-forming agent is NH4HCO3(ii) a The conductive agent is metal beryllium powder.
Further, the chloride is CaCl2、BaCl2One or two of LiCl, NaCl and KCl.
Further, BeO, NH4HCO3The purity of the metal beryllium powder and the metal beryllium powder is more than 99 percent, NH4HCO3The granularity of the powder and the beryllium powder is below 0.5 mm.
Further, the mixed material, NH, in the step S14HCO3The mass percent of the beryllium powder is 5-50%, and the mass percent of the beryllium powder is 5-20%.
Further, in step S1, the pressure for pressing the mixture is 10-50 MPa.
Furthermore, the sintering temperature in step S2 is 900-1300 ℃, and the sintering time is 2-6 h.
Furthermore, the electrolysis temperature in step S3 is 600-900 ℃, the electrolysis voltage is 2.8-3.4V, and the electrolysis time is 3-10 h.
Further, the sintered mixture sheet is wrapped with a nickel mesh and then connected to a molybdenum rod to assemble a cathode in step S3.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) the method for preparing metal beryllium by molten salt electro-deoxidation directly takes BeO as a raw material, evenly mixes the BeO with a pore-forming agent and electricity, presses and sinters the mixture to prepare a cathode, and carries out electro-deoxidation in molten salt to obtain solid metal beryllium, thereby saving the prior BeF2Magnesiothermic reduction and BeCl2The complex raw material pretreatment process in the molten salt electrolysis process greatly simplifies the process flow of metallic beryllium production.
(2) The method for preparing metal beryllium by molten salt electro-deoxidation does not use BeF in the whole production process2And BeCl2The pollution problem of a series of beryllium-containing waste materials caused by the pollution is avoided; the anode gas produced at the same time is CO2Rather than Cl as in conventional chloride electrolysis2Thus being more environment-friendly.
(3) The method for preparing the metal beryllium by molten salt electro-deoxidation has the advantages that the adopted molten salt is stable, the conductivity is good, the solubility to products is low, the current efficiency in the production process is high, and the principle pretreatment process is omitted, so that the economic benefit is higher.
(4) According to the method for preparing the metal beryllium by the molten salt electro-deoxidation, the purity of the obtained product metal beryllium can reach more than 99% by controlling the performance of the BeO cathode and the electro-deoxidation process.
Detailed Description
The present invention will be described in detail for further understanding of the present invention.
The invention provides a method for preparing metal beryllium by molten salt electro-deoxidation, which is characterized in that BeO is directly used as a raw material, is uniformly mixed with a pore-forming agent and a conductive agent, is pressed and sintered to prepare a cathode sheet, and is subjected to electro-deoxidation in chloride molten salt to prepare the metal beryllium. Wherein the pore-forming agent is NH4HCO3(ii) a The conductive agent is metal beryllium powder; the chloride is CaCl2、BaCl2One or two of LiCl, NaCl and KCl, and BeO and NH in the invention4HCO3The purity of the metal beryllium powder and the metal beryllium powder is over 99 percent, and NH is added4HCO3The granularity of the powder and the beryllium powder is below 0.5 mm.
Specifically, the steps are as follows:
s1, mixing and tabletting: uniformly mixing BeO serving as a raw material with a pore-forming agent and a conductive agent according to a certain mass percentage, and pressing the uniformly mixed mixture into a mixture tablet; wherein NH4HCO3The mass percentage of the beryllium powder is 5-50 percent, and the mass percentage of the beryllium powder is 5-20 percent; the pressure of the pressing forming is 10-50 MPa;
s2, tabletting and sintering: the mixture is pressed into sheets to be sintered under the protective atmosphere, and mixture sintered sheets are obtained; specifically, the mixture is pressed into sheets to be sintered in an argon atmosphere, the sintering temperature is 900-1300 ℃, and the sintering time is 2-6h, so that mixture sintered sheets are obtained;
s3, molten salt electro-deoxidation: assembling the mixture sintering sheet and a molybdenum rod into a cathode, and specifically, connecting the mixture sintering sheet and the molybdenum rod after the mixture sintering sheet is wrapped by a nickel net to assemble the cathode; taking a high-purity graphite rod as an anode, inserting the high-purity graphite rod into an electrolytic cell containing chloride fused salt for electro-deoxidation, introducing protective gas argon in the electrolytic process, wherein the electrolytic temperature is 600-900 ℃, the electrolytic voltage is 2.8-3.4V, and the electrolytic time is 3-10 h; and after the electrolysis is finished, taking out the electrolysis product and removing the molten salt attached to the surface to obtain the solid metal beryllium. It should be noted that the chloride powder used in the present invention is dried at 200-220 deg.C before use to remove the adsorbed water.
Compared with the traditional metal beryllium production method, the method of the invention has the following obvious advantages: 1) the conventional beryllium production process requires conversion of BeO to BeF2Or BeCl2In the invention, BeO can be directly used as a raw material, so that the raw material conversion treatment process is omitted; 2) the invention does not use volatile toxic halide BeF2Or BeCl2And the anode gas is CO2Instead of Cl generated during conventional chloride electrolysis2The process is more environment-friendly; 3) the metal beryllium can be produced by BeO through the one-step procedure of molten salt electro-deoxidation, the process is simple, and the production cost of the beryllium is reduced; 4) the current efficiency of producing metal beryllium by electro-deoxidation is high, the purity of the obtained product is high, and the beryllium is enhancedEconomic benefit of production.
The present invention will be further described with reference to the following examples.
Example 1
The method for preparing metallic beryllium by molten salt electro-deoxidation comprises the following steps:
s1, mixing and tabletting: BeO is taken as a raw material, and the BeO and a pore-forming agent NH are mixed4HCO3Adding the conductive agent beryllium powder into a ball milling tank according to the mass percentage of 78%, 12% and 10% to mix for 5 hours, putting the uniformly mixed mixture into a steel mould, and pressing and molding under the pressure of 20MPa to obtain a tablet with the thickness of 4 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at the sintering temperature of 1000 ℃ for 5 hours to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. firstly weighing CaCl according to the mass percent of 67 percent to 33 percent2And NaCl powder, drying at 200 deg.C for 24 hr, and heating to 800 deg.C to obtain CaCl2-NaCl mixed molten salt; it should be noted that, when preparing the molten salt, the mixing ratio of the chloride powders and the drying and heating processes can be adjusted by operators according to actual requirements, but not all of them;
b. wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; using a high-purity graphite rod as an anode, and using the CaCl obtained in the step a2Carrying out electro-deoxidation reaction for 6h at 800 ℃ by using NaCl mixed molten salt as electrolyte, introducing argon for protection in the electrolysis process, and controlling the cell pressure to be 3.1V;
c. and after the electrolysis is finished, separating an electrolysis product from the molten salt, and removing the molten salt attached to the surface of the electrolysis product to obtain the metal beryllium.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.3 percent by using a chemical analysis method.
Example 2
The method for preparing metallic beryllium by molten salt electro-deoxidation comprises the following steps:
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3Adding the conductive agent beryllium powder into a ball milling tank according to the mass percentages of 79%, 16% and 5% to mix for 5 hours, and placing the uniformly mixed mixture into a steel mould to be pressed and molded under the pressure of 12MPa to obtain a tablet with the thickness of 3 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at the sintering temperature of 900 ℃ for 3 hours to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. firstly, weighing NaCl and KCl powder according to the mass percent of 44% to 56%, drying at 220 ℃ for 24 hours, and then heating to 720 ℃ to obtain NaCl-KCl mixed molten salt;
b. wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; taking a high-purity graphite rod as an anode, taking the NaCl-KCl mixed molten salt obtained in the step a as electrolyte, carrying out electro-deoxidation reaction for 8 hours at 720 ℃, introducing argon for protection in the electrolytic process, and controlling the cell pressure to be 3.2V;
c. and after the electrolysis is finished, separating an electrolysis product from the molten salt, and removing the molten salt attached to the surface of the electrolysis product to obtain the metal beryllium.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.2 percent by using a chemical analysis method.
Example 3
The method for preparing metallic beryllium by molten salt electro-deoxidation comprises the following steps:
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3Adding 72 percent, 8 percent and 20 percent of conductive agent beryllium powder into a ball milling tank according to the mass percent for mixing for 5 hours, putting the uniformly mixed material into a steel mould, and pressing and molding under the pressure of 45MPa to obtain a tablet with the thickness of 6 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at 1300 ℃ for 5h to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. weighing CaCl2Drying at 220 deg.C for 24h, and heating to 880 deg.C to obtain CaCl2Melting a salt; herein CaCl2BaCl can also be used as the powder2Or LiCl or NaCl or KCl powder, not to be exhaustive.
b. Wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; using a high-purity graphite rod as an anode, and using the CaCl obtained in the step a2Taking molten salt as electrolyte, carrying out electro-deoxidation reaction for 10h at 880 ℃, introducing argon gas for protection in the electrolysis process, and controlling the cell pressure to be 2.8V;
c. and after the electrolysis is finished, separating an electrolysis product from the molten salt, and removing the molten salt attached to the surface of the electrolysis product to obtain the metal beryllium.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.3 percent by using a chemical analysis method.
Example 4
The method for preparing metallic beryllium by molten salt electro-deoxidation comprises the following steps:
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3Adding 75% by mass, 15% by mass and 10% by mass of beryllium powder serving as a conductive agent into a ball milling tank, mixing for 5 hours, putting the uniformly mixed materials into a steel mould, and pressing and molding under the pressure of 25MPa to obtain a tablet with the thickness of 4 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at the sintering temperature of 1100 ℃ for 4 hours to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. weighing BaCl according to the mass percent of 84 percent to 16 percent2And LiCl powder, dried at 220 ℃ for 24h, and then heated to 760 ℃ to obtain BaCl2-LiCl mixed molten salt;
b. wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; taking a high-purity graphite rod as an anode, and obtaining BaCl in the step a2-LiCl mixed molten salt as electrolyte, carried out at 760 DEG CPerforming electro-deoxidation reaction for 10 hours, introducing argon gas for protection in the electrolytic process, and controlling the bath pressure to be 3.2V;
c. and after the electrolysis is finished, separating an electrolysis product from the molten salt, and removing the molten salt attached to the surface of the electrolysis product to obtain the metal beryllium.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.1 percent by a chemical analysis method.
Example 5
The method for preparing metallic beryllium by molten salt electro-deoxidation comprises the following steps:
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3Adding 67 percent, 18 percent and 15 percent of conductive agent beryllium powder into a ball milling tank according to the mass percentage to mix for 5 hours, putting the uniformly mixed materials into a steel mould to be pressed and molded under the pressure of 40MPa, and obtaining a pressed sheet with the thickness of 3 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at the sintering temperature of 1200 ℃ for 2h to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. weighing CaCl according to the mass percent of 83 percent to 17 percent2And LiCl powder, drying at 220 deg.C for 24h, and heating to 660 deg.C to obtain CaCl2-LiCl mixed molten salt;
b. wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; using a high-purity graphite rod as an anode, and using the CaCl obtained in the step a2Performing electro-deoxidation reaction for 10 hours at 660 ℃ by using LiCl mixed molten salt as electrolyte, introducing argon for protection in the electrolysis process, and controlling the cell pressure to be 3.0V;
c. and after the electrolysis is finished, separating an electrolysis product from the molten salt, and removing the molten salt attached to the surface of the electrolysis product to obtain the metal beryllium.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.2 percent by using a chemical analysis method.
Example 6
The method for preparing metallic beryllium by molten salt electro-deoxidation comprises the following steps:
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3Adding 72 percent, 8 percent and 20 percent of conductive agent beryllium powder into a ball milling tank according to the mass percent for mixing for 5 hours, putting the uniformly mixed material into a steel mould, and pressing and molding under the pressure of 30MPa to obtain a tablet with the thickness of 3 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at the sintering temperature of 1100 ℃ for 3 hours to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. weighing LiCl and KCl powder according to the mass percent of 43 percent to 57 percent, drying at 210 ℃ for 24 hours, and then heating to 600 ℃ to obtain LiCl-KCl mixed molten salt;
b. wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; taking a high-purity graphite rod as an anode, taking the LiCl-KCl mixed molten salt obtained in the step a as electrolyte, carrying out electro-deoxidation reaction for 10 hours at 600 ℃, introducing argon for protection in the electrolysis process, and controlling the cell pressure to be 3.4V;
c. and after the electrolysis is finished, separating an electrolysis product from the molten salt, and removing the molten salt attached to the surface of the electrolysis product to obtain the metal beryllium.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.2 percent by using a chemical analysis method.
Example 7
The method for preparing metallic beryllium by molten salt electro-deoxidation is basically the same as the method in the previous embodiment, except that,
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3Adding 35% by mass, 45% by mass and 20% by mass of beryllium powder serving as a conductive agent into a ball milling tank, mixing for 5 hours, putting the uniformly mixed materials into a steel mould, and pressing and molding under the pressure of 50MPa to obtain a tablet with the thickness of 3 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at the sintering temperature of 900 ℃ for 6 hours to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. weighing CaCl2Powder and BaCl2Drying and heating to obtain CaCl2-BaCl2Mixing molten salt;
b. wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; using a high-purity graphite rod as an anode, and using the CaCl obtained in the step a2-BaCl2The mixed molten salt is used as electrolyte, the electro-deoxidation reaction is carried out for 10h at 800 ℃, argon is introduced for protection in the electrolysis process, and the cell pressure is controlled to be 2.8V.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.1 percent by a chemical analysis method.
Example 8
The method for preparing metallic beryllium by molten salt electro-deoxidation is basically the same as the method in the previous embodiment, except that,
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3Adding 45 mass percent of conductive agent beryllium powder, 50 mass percent of conductive agent beryllium powder and 5 mass percent of conductive agent beryllium powder into a ball milling tank to be mixed for 5 hours, and putting the uniformly mixed materials into a steel mould to be pressed and molded under the pressure of 10MPa to obtain a tablet with the thickness of 6 mm;
s2, tabletting and sintering: sintering the obtained pressed sheet in an argon atmosphere at 1300 ℃ for 2h to obtain a mixture sintered sheet;
s3, molten salt electro-deoxidation: the method specifically comprises the following steps:
a. weighing CaCl2Drying and heating the powder and KCl powder to obtain CaCl2-KCl mixed molten salt;
b. wrapping the mixture sintered sheet obtained in the step S2 with a nickel net, and connecting the nickel net with a molybdenum rod to assemble a cathode; using a high-purity graphite rod as an anode, and using the CaCl obtained in the step a2And (3) taking the-KCl mixed molten salt as electrolyte, carrying out electro-deoxidation reaction for 5h at 800 ℃, introducing argon for protection in the electrolysis process, and controlling the cell pressure to be 3.4V.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.1 percent by a chemical analysis method.
Example 9
This example is a molten salt electro-deoxidation method for producing metallic beryllium, which is essentially the same as that described in example 8 above, except that,
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3The conductive agent beryllium powder is mixed according to the mass percent of 90 percent, 5 percent and 5 percent respectively and is pressed into tablets;
s3, BaCl is used as electrolyte in molten salt electro-deoxidation2-NaCl mixed molten salt.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.1 percent by a chemical analysis method.
Example 10
This example is a molten salt electro-deoxidation method for producing metallic beryllium, which is essentially the same as that described in example 8 above, except that,
s1, mixing and tabletting: BeO and a pore-forming agent NH4HCO3The conductive agent beryllium powder is mixed according to the mass percent of 75 percent, 5 percent and 20 percent respectively, and is pressed into tablets;
s3, BaCl is adopted in molten salt electro-deoxidation2-KCl mixed molten salt.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.2 percent by using a chemical analysis method.
Example 11
This example is a molten salt electro-deoxidation method for producing metallic beryllium, which is essentially the same as that described in example 8 above, except that,
s3, LiCl-NaCl mixed molten salt is adopted in molten salt electro-deoxidation.
By adopting the method of the embodiment, the purity of the metallic beryllium is over 99.3 percent by using a chemical analysis method.
The invention and its embodiments have been described above schematically, without this being limitative. Therefore, if the person skilled in the art should be informed by the teachings of the present invention, without any deviation from the spirit of the present invention, the structural modes and embodiments similar to the above technical solutions should be designed without any inventive step, and shall fall into the protection scope of the present invention.
Claims (1)
1. A method for preparing metal beryllium by molten salt electro-deoxidation is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing and tabletting: uniformly mixing BeO serving as a raw material with a pore-forming agent and a conductive agent, and pressing the uniformly mixed mixture into a mixture tablet; the pore-forming agent is NH4HCO3(ii) a The conductive agent is metal beryllium powder; NH in the mixture4HCO3The mass percent of the beryllium powder is 5-50 percent, and the mass percent of the beryllium powder is 5-20 percent; pressing the mixed material to form under the pressure of 10-50 MPa; BeO, NH4HCO3The purity of the metal beryllium powder and the metal beryllium powder is more than 99 percent, NH4HCO3The granularity of the powder and the beryllium powder is below 0.5 mm;
s2, tabletting and sintering: the mixture is pressed into sheets to be sintered under the protective atmosphere, and mixture sintered sheets are obtained; the sintering temperature is 900-1300 ℃, and the sintering time is 2-6 h;
s3, molten salt electro-deoxidation: the mixture sintered sheet is wrapped by a nickel net and then assembled with a molybdenum rod to form a cathode, a graphite rod is taken as an anode and inserted into an electrolytic cell containing chloride fused salt for electro-deoxidation, the electrolysis temperature is 600-900 ℃, the electrolysis voltage is 2.8-3.4V, and the electrolysis time is 3-10 h; introducing protective gas in the electrolysis process, taking out an electrolysis product and removing molten salt attached to the surface after the electrolysis is finished, thereby obtaining solid metal beryllium; the chloride is CaCl2、BaCl2One or two of LiCl, NaCl and KCl.
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| CN112981461B (en) * | 2021-02-05 | 2022-05-27 | 西藏智材新材料有限公司 | High-purity metal beryllium and preparation process thereof |
| CN115305504A (en) * | 2021-05-08 | 2022-11-08 | 中南大学 | Method for preparing metal beryllium by fused salt electrolysis |
| CN114182301B (en) * | 2021-12-20 | 2023-06-16 | 郑州大学 | Method for preparing metallic beryllium by electrolyzing beryllium oxide through fluoride molten salt |
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| WO2006007863A1 (en) * | 2004-07-16 | 2006-01-26 | Cathingots Limited | Electrolysis apparatus with solid electrolyte electrodes |
| JP2009019250A (en) * | 2007-07-13 | 2009-01-29 | Osaka Titanium Technologies Co Ltd | Method and apparatus for producing metal |
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