CN116837421A - Method for preparing high-purity beryllium through electrochemical purification of primary beryllium - Google Patents
Method for preparing high-purity beryllium through electrochemical purification of primary beryllium Download PDFInfo
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- 229910052790 beryllium Inorganic materials 0.000 title claims abstract description 137
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000746 purification Methods 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 80
- 238000007670 refining Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001805 chlorine compounds Chemical group 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- PPYIVKOTTQCYIV-UHFFFAOYSA-L beryllium;selenate Chemical compound [Be+2].[O-][Se]([O-])(=O)=O PPYIVKOTTQCYIV-UHFFFAOYSA-L 0.000 claims description 3
- 229910002056 binary alloy Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 30
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 10
- 238000010276 construction Methods 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 8
- JZKFIPKXQBZXMW-UHFFFAOYSA-L beryllium difluoride Chemical compound F[Be]F JZKFIPKXQBZXMW-UHFFFAOYSA-L 0.000 description 8
- 229910001633 beryllium fluoride Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910001423 beryllium ion Inorganic materials 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 229910001627 beryllium chloride Inorganic materials 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical group 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a method for preparing high-purity beryllium by electrochemical purification of primary beryllium, which adopts the technical scheme that a molten salt system containing beryllium is firstly constructed, then electrochemical refining is carried out by taking the primary beryllium as an anode in a protective gas atmosphere to obtain a cathode product, and finally salt inclusion of the cathode product is removed to obtain high-purity metal beryllium. The invention is based on the amplification effect of the Nernst equation and the particularity of the element electrode potential, impurities which are more positive than beryllium cannot be electrochemically dissolved, impurities which are more negative than beryllium are dissolved in molten salt in the form of ions or complexes along with the beryllium and are more positive than beryllium, and the impurities cannot be separated out on a cathode before the beryllium is separated out, so that the deep separation of impurity elements is realized. The invention is especially aimed at typical impurities Fe and Si in primary beryllium, the potential of the impurities is more than that of beryllium, the impurities are insoluble in molten salt in the form of anode mud, and the separation effect is good. The method is simple, a complicated two-electrolysis system is not needed, and the operation is convenient; the raw materials do not need pretreatment such as deoiling, acid washing, drying and the like.
Description
Technical Field
The invention relates to a method for preparing high-purity beryllium by electrochemical purification of primary beryllium, belonging to the field of beryllium smelting and high purification.
Background
Beryllium is an indispensable material for national defense, aerospace and nuclear industries, particularly high-purity beryllium, is the only object for selecting the materials of the first wall of the artificial sun, the space telescope and the space strategic defending device system of nuclear energy at present, is a typical strategic and critical engineering material, and directly relates to the development of national defense tip technology and strategic emerging industry.
The preparation technology of the metal beryllium in China is still a magnesian reduction method, the purity of the obtained primary beryllium is low (less than or equal to 98 percent), even if the primary beryllium is purified by a vacuum distillation method and is limited by vapor pressure, impurities such as Fe, si and the like are difficult to remove, and the purity cannot be further improved. Although other methods of beryllium production, such as molten salt electrolysis, have been developed by the skilled artisan, similar problems exist. Therefore, the development of a novel preparation method of high-purity beryllium has important significance. CN 115786982A discloses a method for purifying beryllium waste based on molten salt electrolytic refining, which takes "beryllium alloy waste" as a raw material, adopts a double-system twice electrolytic idea to recover the beryllium waste, has complex electrolytic system and complex process, and limits the application of the method. And the raw materials are different, the material components are beryllium-containing alloys, namely copper, aluminum, nickel, titanium, silicon and the like which are not beryllium, and the multi-metal potential difference needs to be comprehensively considered. Therefore, the invention aims to design and develop a method for preparing high-purity beryllium by taking primary beryllium as a raw material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing high-purity beryllium by electrochemical purification of primary beryllium, which aims at preparing high-purity metal beryllium by deeply removing typical impurities Fe and Si which are difficult to remove based on the specific electrochemical selectivity of a Nernst equation by taking the primary beryllium as a raw material.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the method for preparing the high-purity beryllium by electrochemical purification of the primary beryllium comprises the following steps:
(1) Constructing a beryllium-containing molten salt system;
(2) Electrochemical refining is carried out by taking primary beryllium as an anode in the atmosphere of protective gas to obtain a cathode product;
(3) And (5) removing salt of the cathode product to obtain high-purity metal beryllium.
Further, the beryllium-containing molten salt is one or more of fluoride and chloride.
Further, when the beryllium-containing molten salt is fluoride, the beryllium-containing molten salt contains BeF 2 And at least one other fluoride; when the beryllium-containing molten salt is chloride, the beryllium-containing molten salt contains BeCl 2 And at least one other chloride; when the beryllium-containing molten salt is fluoride and chloride,
(1) Beryllium-containing molten salt containing BeF 2 And at least one other chloride, or at least one other chloride and at least one other fluoride;
(2) Beryllium-containing molten salt containing BeCl 2 And at least one other fluoride, or at least one other fluoride and at least one other chloride;
(3) Beryllium-containing molten salt containing BeF 2 、BeCl 2 Or, contain BeF 2 、BeCl 2 And at least one other chloride and/or other fluoride.
Preferably, the other fluoride is LiF, naF, KF, mgF 2 、CaF 2 、BaF 2 Other chlorides LiCl, naCl, KCl, mgCl 2 、CaCl 2 、BaCl 2 。
Preferably, the beryllium-containing molten salt is fluoride or fluoride and chloride; the beryllium-containing molten salt system is a binary system or a ternary system.
Further, the beryllium salt containing beryllium accounts for more than or equal to 10at.% of the molten salt system. Preferably, the beryllium salt comprises 10-80 at% of the molten salt system
Further, the primary beryllium is one or more of metal beryllium (beryllium beads) prepared by thermal reduction, metal beryllium (flake beryllium) prepared by molten salt electrolysis and beryllium ingots prepared by smelting the metal beryllium.
Further, the cathode material used for electrochemical refining is one of high-purity metal, high-entropy alloy, titanium boride and titanium carbide; the high-purity metal is one or more of Be, ni, fe, co, mo, cu, pt, au, ti, W.
Further, the shielding gas is one or more of helium, argon and neon; the temperature of electrochemical refining is 300-1000 ℃; the cathode current density of the electrochemical refining is 0.01-3.0A/cm 2 . The cathodic current density is preferably 0.01-1.8A/cm 2 。
Further, the mode of removing the salt is one or more of water washing, acid washing, alkali washing and distillation. When the beryllium-containing molten salt contains fluoride, distillation is preferred as a mode of removing the salt.
The invention has the beneficial effects that:
1. based on the amplification effect of the Nernst equation and the particularity of the element electrode potential, impurities which are more positive than beryllium cannot be electrochemically dissolved, impurities which are more negative than beryllium are dissolved in molten salt along with beryllium in the form of ions or complexes at the bottom of the molten salt, but cannot be separated out on a cathode before the beryllium, so that the deep separation of impurity elements is realized.
2. Unlike the cutting of material in CN 115786982A, the material of the present invention may be used directly as anode without needing titanium basket to hold, so that there is no simultaneous dissolving of titanium and beryllium and precipitation of titanium and beryllium in the cathode to raise the impurity of titanium in beryllium product (with titanium potential of-1.76V and beryllium of-1.80V vs Cl) -1 Cl, very close to each other); meanwhile, the method has poor capability of removing impurity Al (-1.70V).
3. Particularly for typical impurities Fe and Si in primary beryllium, the potentials of the impurities are-1.10V and-1.09V respectively, which are more positive than beryllium (-1.80V), the impurities are insoluble in molten salt in the form of anode mud, and the separation effect is good.
4. Unlike conventional electrolytic refining, the molten salt system for electrochemical refining contains beryllium ions with a certain concentration (more than or equal to 10 at.%), the balance of beryllium in the molten salt system is very easy to establish in the electrochemical refining process, the beryllium ions can be directly and instantaneously nucleated and separated out on a cathode, the beryllium ions which are electrochemically dissolved on an anode do not need to be diffused to the cathode, and the beryllium ions can generate electronic reaction when the beryllium ions are only diffused to the cathode. Otherwise, non-target beryllium ions on the cathode are easily deposited at the beginning of conventional electrorefining, adding impurities, and this problem needs to be solved by replacing the new cathode.
5. The chloride molten salt system is adopted, and has the following advantages: the operation temperature is lower, and the energy consumption is low; (2) The corrosiveness of the molten salt is relatively weak, and experimental auxiliary materials are easy to obtain; (3) The fused salt has good water solubility, and is convenient for removing the salt by water washing and other methods.
6. When the fluoride fused salt system is adopted, the volatility is small in operation and the component change of the fused salt is small because the vapor pressure of the fluoride fused salt is low, so that the electrochemical purification can be stably carried out for a long time.
7. Chloride is properly added into fluoride molten salt to form a chlorofluoro molten salt system, and the potential of beryllium and impurity elements is further differentiated by means of the difference of combining or complexing capability of the elements with chlorine and fluorine, so that the deep separation of elements with similar potential, such as Mn, is realized.
8. Because fluoride, especially lithium fluoride and beryllium fluoride, has poor water solubility and poor effect when the product salt is removed by water washing, acid washing and alkali washing, the salt is preferably removed by distillation when fluoride is contained in the fused salt system.
9. When chloride molten salt is adopted, a beryllium-containing binary system is preferable, the molten salt system is simple, and the electrochemical purification process is convenient to control compared with a quaternary system.
10. The method is simple, a complicated two-electrolysis system is not needed, and the operation is convenient; the raw materials do not need pretreatment such as deoiling, acid washing, drying and the like.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples.
Example 1
Construction of BeF with 70at.% beryllium fluoride and 30at.% lithium fluoride 2 Mixing LiF molten salt system, heating to 600deg.C, taking beryllium beads (purity 98.8%, fe is 490ppm, si is 95 ppm) as anode, beryllium plate as cathode, performing electrochemical refining under argon atmosphere, and controlling cathode current density to 0.15A/cm 2 And (3) obtaining a cathode product at a cathode, and removing salt by vacuum distillation to obtain the metallic beryllium with the purity of 99.91%, wherein the impurities Fe is 38ppm and Si is 15ppm.
Example 2
Construction of BeF with 76at.% beryllium fluoride and 24at.% potassium fluoride 2 Mixing with KF molten salt system, heating to 500 deg.C, taking beryllium beads (purity 98.6%, fe is 930ppm, si is 450 ppm) as anode, nickel rod as cathode, performing electrochemical refining under argon atmosphere, and controlling cathode current density to 0.8A/cm 2 And (3) obtaining a cathode product at a cathode, and removing salt by vacuum distillation to obtain the metallic beryllium with the purity of 99.93 percent, wherein the impurities Fe is 78ppm and Si is 35ppm.
Example 3
Construction of BeF with 50at.% beryllium fluoride and 50at.% sodium fluoride 2 Mixing NaF molten salt system, placing into beryllium oxide crucible, heating to 780 deg.C, taking flake beryllium (purity 99.5%, fe 30ppm, si 30 ppm) as anode, platinum sheet as cathode, performing electrochemical refining under argon atmosphere, controlling cathode current density 1.8A/cm 2 And (3) obtaining a cathode product at a cathode, and removing salt by vacuum distillation to obtain the metallic beryllium with the purity of 99.98%, wherein the impurity Fe is 15ppm and the impurity Si is 10ppm.
Example 4
Construction of BeF with 20at.% beryllium fluoride and 80at.% barium fluoride 2 -BaF 2 Molten salt system, mixing uniformly, placing into tungsten crucible, heating to 950 deg.C, vacuum casting beryllium ingot (purity 98.0%, fe is 630ppm, si is 90 ppm) as anode, tungsten plate as cathode, electrochemical refining under argon atmosphere, controlling cathode current density to 1.3A/cm 2 And (3) obtaining a cathode product at the cathode, washing with acid, washing with water, and then distilling in vacuum to remove salt to obtain the metallic beryllium with the purity of 99.9%, wherein the impurities Fe is 56ppm and Si is 25ppm.
Example 5
Construction of BeF with 60at.% beryllium fluoride, 30at.% sodium fluoride and 10at.% calcium chloride 2 -NaF-CaCl 2 Molten salt system, mixing, heating to 700 deg.c, taking beryllium bead (purity 98.4%, fe 1150ppm, si 700 ppm) as anode, molybdenum plate as cathode, electrochemical refining under argon atmosphere, controlling cathode current density to 1.7A/cm 2 And (3) obtaining a cathode product at a cathode, washing with water, adding vacuum distillation to remove salt, and obtaining the metallic beryllium with the purity of 99.92%, wherein the impurities of Fe is 95ppm and Si is 40ppm.
Example 6
Construction of BeF with 2at.% beryllium fluoride, 8at.% beryllium chloride and 90at.% sodium chloride 2 -BeCl 2 Mixing with NaCl molten salt system, heating to 700 deg.c, casting beryllium ingot with purity of 97.9%, fe of 790ppm and Si of 100ppm as anode, electrochemical refining in argon atmosphere, and controlling cathode current density of 1.0A/cm 2 And (3) obtaining a cathode product at a cathode, and removing salt by vacuum distillation to obtain the metallic beryllium with the purity of 99.96%, wherein the impurities Fe is 58ppm and Si is 28ppm.
Example 7
Construction of BeF with 20at.% beryllium fluoride and 80at.% beryllium chloride 2 -BeCl 2 Molten salt system, mixing, heating to 450 deg.c in a platinum crucible, casting beryllium ingot with purity of 95.3%, fe of 2700ppm and Si of 1300ppm as anode, electrochemical refining in argon atmosphere with titanium carbide plate as cathode current density of 0.1A/cm 2 And (3) obtaining a cathode product at the cathode, washing with acid, washing with water, and then distilling in vacuum to remove salt to obtain the metallic beryllium with the purity of 99.90%, wherein the impurities Fe is 123ppm and Si is 85ppm.
Example 8
Construction of BeCl with 50at.% beryllium chloride and 50at.% sodium chloride 2 NaCl meltThe salt system is mixed uniformly and then put into a corundum crucible, heated to 300 ℃, beryllium (purity 99.9%, fe 27ppm and Si 23 ppm) flake is taken as an anode, beryllium plate is taken as a cathode, electrochemical refining is carried out under argon atmosphere, and the current density of the cathode is controlled to be 1.0A/cm 2 And (3) obtaining a cathode product at the cathode, and washing to remove salt, thereby obtaining the metallic beryllium with the purity of 99.99%, wherein the impurities Fe is 13ppm and Si is 10ppm.
Example 9
Construction of BeCl with 45at.% beryllium chloride and 55at.% lithium chloride 2 LiCl molten salt system, mixing uniformly, placing into a quartz crucible, heating to 400 ℃, taking a cast beryllium ingot epidermis layer (purity 95.8%, fe is 2200ppm, si is 980 ppm) as an anode, taking a titanium plate as a cathode, performing electrochemical refining under neon atmosphere, and controlling the current density of the cathode to be 0.5/cm 2 And (3) obtaining a cathode product at the cathode, washing with water after pickling to remove salt, and obtaining the metallic beryllium with the purity of 99.92%, wherein the impurities Fe is 115ppm and Si is 63ppm.
Example 10
Construction of BeCl with 50at.% beryllium chloride and 50at.% potassium chloride 2 The KCl molten salt system is put into a molybdenum crucible after being evenly mixed, heated to 700 ℃, and the ingot head (purity 96.3%, fe 1500ppm and Si 850 ppm) of a cast beryllium ingot is taken as an anode, a titanium boride plate is taken as a cathode, electrochemical refining is carried out under helium atmosphere, and the current density of the cathode is controlled to be 1.5A/cm 2 And (3) obtaining a cathode product at the cathode, and washing with alkali and then water to remove salt to obtain the metallic beryllium with the purity of 99.94%, wherein the impurities of Fe of 100ppm and Si of 43ppm.
Claims (10)
1. The method for preparing the high-purity beryllium by electrochemical purification of the primary beryllium is characterized by comprising the following steps of:
(1) Constructing a beryllium-containing molten salt system;
(2) Electrochemical refining is carried out by taking primary beryllium as an anode in the atmosphere of protective gas to obtain a cathode product;
(3) And (5) removing salt of the cathode product to obtain high-purity metal beryllium.
2. The method for preparing high-purity beryllium by electrochemical purification of primary beryllium according to claim 1, wherein the molten salt containing beryllium is one or more of fluoride and chloride.
3. The method for preparing high purity beryllium by electrochemical purification of primary beryllium according to claim 2, wherein when the beryllium-containing molten salt is fluoride, the beryllium-containing molten salt contains BeF 2 And at least one other fluoride; when the beryllium-containing molten salt is chloride, the beryllium-containing molten salt contains BeCl 2 And at least one other chloride; when the beryllium-containing molten salt is fluoride and chloride,
(1) Beryllium-containing molten salt containing BeF 2 And at least one other chloride, or at least one other chloride and at least one other fluoride;
(2) Beryllium-containing molten salt containing BeCl 2 And at least one other fluoride, or at least one other fluoride and at least one other chloride;
(3) Beryllium-containing molten salt containing BeF 2 、BeCl 2 Or, contain BeF 2 、BeCl 2 And at least one other chloride and/or other fluoride.
4. A method for preparing high purity beryllium by electrochemical purification of primary beryllium according to claim 3, wherein the other fluoride is LiF, naF, KF, mgF 2 、CaF 2 、BaF 2 Other chlorides LiCl, naCl, KCl, mgCl 2 、CaCl 2 、BaCl 2 。
5. The method for preparing high-purity beryllium by electrochemical purification of primary beryllium according to claim 2, wherein the molten salt containing beryllium is fluoride or fluoride and chloride; the beryllium-containing molten salt system is a binary system or a ternary system.
6. The method for preparing high-purity beryllium by electrochemical purification of primary beryllium according to claim 1, wherein beryllium salt containing beryllium accounts for not less than 10at.% of molten salt system.
7. The method for preparing high-purity beryllium by electrochemical purification of primary beryllium according to claim 1, wherein the primary beryllium is one or more of metal beryllium prepared by thermal reduction, metal beryllium prepared by molten salt electrolysis and beryllium ingot prepared by smelting.
8. The method for preparing high-purity beryllium by electrochemical purification of primary beryllium according to claim 1, wherein the cathode material used in the electrochemical refining is one of high-purity metal, high-entropy alloy, titanium boride and titanium carbide; the high-purity metal is one or more of Be, ni, fe, co, mo, cu, pt, au, ti, W.
9. The method for preparing high-purity beryllium by electrochemical purification of primary beryllium according to claim 1, wherein the shielding gas is one or more of helium, argon and neon; the temperature of electrochemical refining is 300-1000 ℃; the cathode current density of the electrochemical refining is 0.01-3.0A/cm 2 。
10. The method for preparing high purity beryllium by electrochemical purification of primary beryllium according to any of claims 1-9, wherein the means for removing salt is one or more of water washing, acid washing, alkali washing, and distillation.
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