CN116426983A - Aluminum-thorium alloy and preparation method and application thereof - Google Patents
Aluminum-thorium alloy and preparation method and application thereof Download PDFInfo
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- -1 Aluminum-thorium Chemical compound 0.000 title claims abstract description 95
- 229910001264 Th alloy Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 100
- 150000003839 salts Chemical class 0.000 claims abstract description 71
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910003452 thorium oxide Inorganic materials 0.000 claims abstract description 32
- MZQZQKZKTGRQCG-UHFFFAOYSA-J thorium tetrafluoride Chemical compound F[Th](F)(F)F MZQZQKZKTGRQCG-UHFFFAOYSA-J 0.000 claims abstract description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 27
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 20
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 18
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 15
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 15
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 14
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 14
- 229910001610 cryolite Inorganic materials 0.000 claims description 13
- IOXPXHVBWFDRGS-UHFFFAOYSA-N hept-6-enal Chemical compound C=CCCCCC=O IOXPXHVBWFDRGS-UHFFFAOYSA-N 0.000 claims description 13
- 150000004673 fluoride salts Chemical class 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 33
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052776 Thorium Inorganic materials 0.000 description 27
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 229910000838 Al alloy Inorganic materials 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 230000010287 polarization Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- CKYKNSRRNDUJPY-UHFFFAOYSA-N alumane;uranium Chemical compound [AlH3].[U] CKYKNSRRNDUJPY-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910012375 magnesium hydride Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides an aluminum-thorium alloy and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing aluminum oxide, thorium oxide and electrolyte to obtain mixed molten salt; (2) And (3) heating and melting the mixed molten salt in protective gas, and then electrolyzing to obtain the aluminum-thorium alloy. Compared with the traditional preparation method of the aluminum-thorium alloy, the preparation method of the aluminum-thorium alloy has the advantages of short flow, simple equipment, low cost and easy control of reaction conditions; the preparation method can be used in the existing aluminum electrolysis system, the existing 200-500KA aluminum electrolysis cell is utilized, thorium fluoride and thorium oxide are added according to a certain concentration, the aluminum-thorium alloy can be continuously produced on the premise of not changing the structure and facilities of the existing aluminum electrolysis cell, and industrial popularization and application are easy to realize.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal electrolysis, relates to an alloy, and particularly relates to an aluminum-thorium alloy, and a preparation method and application thereof.
Background
The aluminum alloy has the advantages of small density, high specific strength, excellent electric and heat conductivity, good processability and the like, and is widely applied to the fields of aerospace industry, electric power industry, automobile manufacturing industry, building industry, food industry, marine ship industry and the like. The aluminum alloy has low density, but has higher strength, is close to or exceeds that of high-quality steel, has good plasticity, can be processed into various profiles, has excellent electric conductivity, heat conductivity and corrosion resistance, is widely used in industry, and has the use amount which is inferior to that of steel. However, the existing aluminum alloy has to be improved in terms of hardness, toughness and heat resistance. The reserve of thorium resources in China is about 28 ten thousand tons, the abundance of the thorium resources in the crust is about half of that of lead, the uranium is 3 to 4 times of that of the lead, and the thorium can be used for manufacturing alloys so as to improve the strength and heat resistance of metals. If the aluminum-thorium alloy is obtained by smelting pure thorium metal and pure aluminum metal according to a certain proportion according to the traditional preparation flow, the pure thorium and the pure aluminum are required to be prepared firstly by adopting the method, the secondary smelting loss is large, and the process is complex. The price of thorium oxide and aluminum oxide is low, and the preparation of the aluminum thorium alloy by the molten salt electrolysis of the thorium oxide and the aluminum oxide is a good direction, but the melting point of the thorium oxide is 3220 ℃, and the melting point of the thorium is 1842 ℃, so that the preparation cost of the aluminum thorium alloy is high and the experimental condition requirement is high.
CN1936085a discloses a method for preparing aluminum and aluminum alloy by low-temperature molten salt electrolysis, which uses metal chloride or metal chloride mixture as electrolyte, requires melting point of electrolyte less than or equal to 800 ℃, graphite carbon material or inert electrode as anode, uses solid cathode electrolysis process to make intermittent electrolysis, places cathode at bottom of graphite electrolytic tank, places electrolyte at upper portion of cathode, electrifies and heats, after the electrolyte is melted, inserts anode into molten salt, and makes the melting point of electrolyte more than Al 2 O 3 Carrying out molten salt electrolysis at the conditions that the decomposition voltage is smaller than the electrolyte decomposition voltage, the polar distance is more than or equal to 0.1cm and the temperature is 600 ℃ until the current is lower than 1.0 ampere, taking out the cathode, putting the cathode into a smelting furnace, and smelting aluminum and then casting ingot at the temperature of more than or equal to 660 ℃; in liquid aluminum and Al 2 O 3 The mixture is cathode electrolysis, continuous electrolysis is carried out at a temperature of more than or equal to 660 ℃, aluminum is periodically taken out from the cathode, and Al is added 2 O 3 The electrolysis process is carried out continuously. However, the aluminum alloy prepared by the method has poor hardness and heat resistance, and the aluminum-thorium alloy cannot be prepared.
CN104694974A discloses a uranium-aluminum alloy and molten salt electrolysis preparation thereofThe preparation method comprises the following steps of: al, al 4 U、Al 3 U and Al 2 U, wherein the Al content is 24-70%; u, 30-76%. The invention also provides a molten salt electrolysis preparation method of the uranium-aluminum alloy, which heats LiCl-KCl molten salt to be molten; to UO 2 Powder and AlCl 3 Adding the powder into molten salt at the same time to make UO 2 Chlorination to form UCl 4 The method comprises the steps of carrying out a first treatment on the surface of the An aluminum sheet is used as a cathode, graphite is used as an anode, ag (I)/Ag is used as a reference electrode, and uranium-aluminum alloy is deposited on the cathode through a constant potential electrolysis method. However, the uranium is rare in the bottom shell, and the uranium-aluminum alloy is expensive and is not suitable for popularization and use.
CN105238942a discloses an aluminum alloy doped with thorium and a preparation method thereof. The thorium-doped aluminum alloy provided by the invention comprises the following components in parts by weight: 150 parts of aluminum, 5 parts of magnesium hydride, 5 parts of nickel, 1-2 parts of thorium and 0.6 part of sodium fluotitanate. The preparation method comprises the following steps: 1) Adding 150 parts by weight of aluminum into a smelting furnace, and heating until the aluminum is completely melted to form aluminum liquid; 2) Sequentially adding 5 parts by weight of magnesium hydride, 5 parts by weight of nickel, 1-2 parts by weight of thorium and 0.6 part by weight of sodium fluotitanate into the aluminum liquid in the step 1), heating until the magnesium hydride, the nickel, the thorium and the sodium fluotitanate are completely melted, and uniformly mixing to obtain mixed liquid; 3) And (3) standing the mixed liquid obtained in the step (2) at 560 ℃ for 11 hours, and transferring the mixed liquid into a casting mould for casting. However, the preparation difficulty and the preparation cost of the pure thorium metal are high, and the thorium-doped aluminum alloy cannot be popularized and used on a large scale.
The aluminum alloy disclosed at present has certain defects, has the problems of lower hardness and heat resistance, and has higher preparation cost and higher experimental condition requirements of the thorium alloy prepared by doping thorium. Therefore, it is important to develop a preparation method with low cost and simple experimental conditions to prepare the aluminum-thorium alloy with higher hardness and stronger heat resistance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the aluminum-thorium alloy and the preparation method and application thereof, and the aluminum-thorium alloy is prepared by adopting a fused salt electrolysis method, and compared with the traditional aluminum-thorium alloy preparation method, the preparation method has the advantages of short flow, simple equipment, low cost and easy control of reaction conditions; the preparation method can be used in the existing aluminum electrolysis system, the existing 200-500KA aluminum electrolysis cell is utilized, thorium oxide and electrolyte are added according to a certain concentration, the aluminum thorium alloy can be continuously produced on the premise of not changing the structure and facilities of the existing aluminum electrolysis cell, and industrial popularization and application are easy to realize.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a process for the preparation of an aluminium-thorium alloy, the process comprising the steps of:
(1) Mixing aluminum oxide, thorium oxide and electrolyte to obtain mixed molten salt;
(2) And (3) heating and melting the mixed molten salt in protective gas, and then electrolyzing to obtain the aluminum-thorium alloy.
The invention provides a preparation method of aluminum-thorium alloy, which adopts a molten salt electrolysis method to prepare the aluminum-thorium alloy, and compared with the traditional preparation method of the aluminum-thorium alloy, the preparation method has the advantages of short flow, simple equipment, low cost and easy control of reaction conditions; the preparation method can be used in the existing aluminum electrolysis system, the existing 200-500KA aluminum electrolysis cell is utilized, thorium oxide and electrolyte are added according to a certain concentration, the aluminum thorium alloy can be continuously produced on the premise of not changing the structure and facilities of the existing aluminum electrolysis cell, and industrial popularization and application are easy to realize.
Preferably, the electrolyte comprises sodium hexafluoroaluminate with a fluoride salt.
Preferably, the fluoride salt comprises a combination of at least two of aluminum fluoride, thorium fluoride, calcium fluoride, magnesium fluoride or lithium fluoride, for example, a combination of aluminum fluoride and thorium fluoride, a combination of thorium fluoride and calcium fluoride, a combination of calcium fluoride and magnesium fluoride, a combination of magnesium fluoride and lithium fluoride, a combination of aluminum fluoride, thorium fluoride and calcium fluoride, or a combination of aluminum fluoride, thorium fluoride, calcium fluoride and magnesium fluoride.
Preferably, the fluoride salt comprises thorium fluoride and at least one of aluminum fluoride, calcium fluoride, magnesium fluoride or lithium fluoride, for example, may be a combination of thorium fluoride and aluminum fluoride, a combination of thorium fluoride and calcium fluoride, a combination of thorium fluoride and magnesium fluoride, a combination of thorium fluoride and lithium fluoride, or a combination of thorium fluoride, aluminum fluoride and calcium fluoride.
Preferably, the mixed molten salt comprises, in parts by weight:
in the present invention, the content of alumina in the mixed molten salt is defined to be 2 to 15 parts, for example, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts or 15 parts, but not limited to the recited values, and other non-recited values in the range of the values are equally applicable; when the content of alumina is too low, the content of aluminum ions in the mixed molten salt is low, which causes difficulty in reduction of aluminum ions and reduces the cathode current efficiency; when the content of aluminum oxide is too high, the content of aluminum ions in the mixed molten salt is too high, thorium ions are difficult to deposit, and the content of thorium ions in the aluminum-thorium alloy is too low, so that the performance of the aluminum-thorium alloy is affected.
The content of thorium oxide in the mixed molten salt is defined to be 2-15 parts, for example, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts or 15 parts, but the invention is not limited to the recited values, and other non-recited values in the range of values are equally applicable; when the content of thorium oxide is too low, the content of thorium ions in the mixed molten salt is low, which can cause the content of thorium in the aluminum thorium metal to be too low, thereby affecting the performance of the aluminum thorium metal; when the content of thorium oxide is too high, it results in a decrease in the cathode current efficiency.
The content of sodium hexafluoroaluminate in the mixed molten salt is defined to be 60 to 85 parts, for example, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 85 parts, but the present invention is not limited to the recited values, and other non-recited values within the range are equally applicable.
The content of the fluoride salt in the mixed molten salt is limited to 4 to 40 parts, and may be, for example, 4 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts, but is not limited to the recited values, and other non-recited values within the range are equally applicable. When the content of fluoride salt is too low, the content of electrolyte in the mixed molten salt is low, which is unfavorable for the transmission of ions in the electrolysis process, and the cathode current efficiency is reduced; when the content of fluoride salt is too high, the content of aluminum oxide and thorium oxide in the mixed molten salt is low, which is unfavorable for the deposition of aluminum thorium metal.
Preferably, the mixed molten salt obtained in the step (1) is dried before being heated and melted.
Preferably, the temperature of the drying is 100-600 ℃ and the time is 1-20h.
The temperature for drying is defined as 100 to 600 ℃, and may be, for example, 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃ or 600 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The drying time is defined to be 1-20h, and may be, for example, 1h, 3h, 5h, 7h, 9h, 10h, 12h, 14h, 16h, 18h or 20h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the heating and melting in the step (2) comprises heating and heat-preserving treatments which are sequentially carried out.
Preferably, the heating rate is 1-10 ℃ per minute, and may be, for example, 1 ℃ per minute, 2 ℃ per minute, 3 ℃ per minute, 5 ℃ per minute, 7 ℃ per minute, 9 ℃ per minute, or 10 ℃ per minute, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The temperature of the temperature rise is preferably 900 to 1000 ℃, and may be 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, or 1000 ℃, for example, but the temperature rise is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are equally applicable.
Preferably, the temperature of the heat-retaining treatment is the end temperature of the temperature rise.
Preferably, the time of the heat-preserving treatment is 1-20h, for example, 1h, 3h, 5h, 7h, 9h, 10h, 12h, 14h, 16h, 18h or 20h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the protective gas comprises nitrogen and/or an inert gas.
Preferably, the electrolytic cathode comprises any one of tungsten, molybdenum or graphite.
Preferably, the anode of the electrolysis comprises an inert electrode.
Preferably, the inert electrode comprises graphite.
Preferably, the electrolysis uses a direct current power supply.
Preferably, the electrolytic current density is 0.5-5A/cm 2 For example, it may be 0.5A/cm 2 、0.8A/cm 2 、1A/cm 2 、2A/cm 2 、3A/cm 2 、4A/cm 2 Or 5A/cm 2 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
The current density of the electrolysis is defined to be 0.5-5A/cm 2 When the current density of electrolysis is too large, the overpotential of the cathode is increased, the polarization of the cathode is increased, the current efficiency of the cathode is reduced, the energy consumption is serious, the edge effect is easy to generate, and the performance of the aluminum-thorium alloy is deteriorated; when the current density of electrolysis is too small, the overpotential of the cathode is reduced, the polarization of the cathode is small, the electrolysis speed is slow, the crystallization of the aluminum-thorium alloy is coarse, the alloy performance is poor, and even the electrolysis process cannot be carried out.
The temperature of the electrolysis is preferably 900 to 1000 ℃, and may be, for example, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, or 1000 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The temperature of the electrolysis is 900-1000 ℃, when the temperature of the electrolysis is too high, the overpotential of the cathode is reduced, the polarization of the cathode is reduced, the precipitation of aluminum-thorium alloy is not facilitated, the energy consumption is high, and the energy-saving and environment-friendly requirements are not met; when the temperature of electrolysis is too low, the overpotential of the cathode becomes large, and the polarization of the cathode becomes large, but the too low temperature is unfavorable for the transmission of ions in the mixed molten salt, which can lead to the reduction of current efficiency, and the components of the aluminum-thorium alloy are uneven, if the temperature of electrolysis is insufficient to change the mixed molten salt into an ionic state, the electrolysis current is extremely low, and even the electrolysis cannot be performed.
Preferably, the electrolysis is carried out for a period of time ranging from 5 to 30 hours, for example, from 5 hours, 10 hours, 15 hours, 20 hours, 25 hours or 30 hours, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, as a preferred technical scheme of the preparation method according to the first aspect, the preparation method comprises the following steps:
(1) Mixing aluminum oxide, thorium oxide and electrolyte according to the formula amount to obtain mixed molten salt;
(2) In protective gas, the mixed molten salt is kept at 100-600 ℃ for 1-20h, the temperature is raised to 900-1000 ℃ at a heating rate of 1-10 ℃/min, the temperature is kept for 1-20h, tungsten, molybdenum or graphite is used as a cathode, graphite is used as an anode, direct current power supply is used for electrolysis, the electrolysis temperature is 900-1000 ℃, and the current density of electrolysis is 0.5-5A/cm 2 The electrolysis time is 5-30h, and the aluminum-thorium alloy is obtained.
In a second aspect, the present invention provides an aluminium-thorium alloy obtained by the preparation method of the first aspect.
In a third aspect, the invention provides the use of an aluminium-thorium alloy according to the second aspect for use in the aeronautical, marine or chemical industry.
Compared with the prior art, the invention has the beneficial effects that:
compared with the traditional preparation method of the aluminum-thorium alloy, the preparation method of the aluminum-thorium alloy has the advantages of short flow, simple equipment, low cost and easy control of reaction conditions; the preparation method can be used in the existing aluminum electrolysis system, the existing 200-500KA aluminum electrolysis cell is utilized, thorium oxide and electrolyte are added according to a certain concentration, the aluminum thorium alloy can be continuously produced on the premise of not changing the structure and facilities of the existing aluminum electrolysis cell, and industrial popularization and application are easy to realize.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In order to facilitate the understanding of the technical solution provided by the present invention by a person skilled in the art, the present invention exemplarily provides an apparatus suitable for a preparation method of an aluminum-thorium alloy, the apparatus comprising a molten salt electrolysis furnace;
a cathode, an anode, a heating device and an atmosphere protection device are arranged in the molten salt electrolysis furnace;
the molten salt electrolysis furnace is internally provided with mixed molten salt; the cathode and the anode realize electric conduction through mixed molten salt;
a charging port is arranged at the upper part of the molten salt electrolysis furnace;
when the mixed molten salt is electrolyzed, direct current is connected, and electrolytic raw materials are added into the electrolytic molten salt through a charging hole at the upper part of the electrolytic tank. Under the action of direct current, electrochemical reaction is carried out, aluminum-thorium alloy is obtained at the cathode, and CO are generated at the anode 2 And (3) gas.
Example 1
The embodiment provides a preparation method of an aluminum-thorium alloy, which comprises the following steps:
(1) Mixing aluminum oxide, thorium oxide, sodium hexafluoroaluminate, aluminum fluoride, thorium fluoride, calcium fluoride and magnesium fluoride according to the formula amount to obtain mixed molten salt, wherein the mixed molten salt comprises: 6 parts of aluminum oxide, 6 parts of thorium oxide, 70 parts of sodium hexafluoroaluminate, 4 parts of aluminum fluoride, 2 parts of thorium fluoride, 5 parts of calcium fluoride and 3 parts of magnesium fluoride;
(2) In argon atmosphere, the mixed molten salt is kept at 350 ℃ for 5 hours, heated to 950 ℃ and kept at 15 hours, tungsten is taken as a cathode, graphite is taken as an anode, direct current power supply is adopted for electrolysis, the electrolysis temperature is 950 ℃, and the electrolysis current density is 2A/cm 2 The electrolysis time is 15h, and the aluminum-thorium alloy is obtained.
Example 2
The embodiment provides a preparation method of an aluminum-thorium alloy, which comprises the following steps:
(1) Mixing aluminum oxide, thorium oxide, sodium hexafluoroaluminate, aluminum fluoride, calcium fluoride, thorium fluoride and lithium fluoride according to the formula amount to obtain mixed molten salt, wherein the mixed molten salt comprises: 6 parts of aluminum oxide, 8 parts of thorium oxide, 75 parts of sodium hexafluoroaluminate, 2 parts of aluminum fluoride, 8 parts of calcium fluoride, 3 parts of thorium fluoride and 4 parts of lithium fluoride;
(2) In nitrogen atmosphere, the mixed molten salt is preserved for 10 hours at 250 ℃, is heated to 975 ℃ and preserved for 5 hours, molybdenum is taken as a cathode, graphite is taken as an anode, direct current power supply is adopted for electrolysis, the electrolysis temperature is 975 ℃, and the electrolysis current density is 4A/cm 2 The electrolysis time is 10 hours, and the aluminum-thorium alloy is obtained.
Example 3
The embodiment provides a preparation method of an aluminum-thorium alloy, which comprises the following steps:
(1) Mixing aluminum oxide, thorium oxide, sodium hexafluoroaluminate, thorium fluoride, calcium fluoride and magnesium fluoride according to the formula amount to obtain mixed molten salt, wherein the mixed molten salt comprises: 3 parts of aluminum oxide, 6 parts of thorium oxide, 65 parts of sodium hexafluoroaluminate, 5 parts of thorium fluoride, 2 parts of calcium fluoride and 6 parts of magnesium fluoride;
(2) In nitrogen atmosphere, the mixed molten salt is preserved for 15 hours at 500 ℃, is heated to 1000 ℃ and preserved for 1 hour, graphite is taken as a cathode, graphite is taken as an anode, direct current power supply is adopted for electrolysis, the electrolysis temperature is 975 ℃, and the electrolysis current density is 5A/cm 2 The electrolysis time is 5 hours, and the aluminum-thorium alloy is obtained.
Example 4
The embodiment provides a preparation method of an aluminum-thorium alloy, which comprises the following steps:
(1) Mixing aluminum oxide, thorium oxide, sodium hexafluoroaluminate, calcium fluoride, magnesium fluoride, thorium fluoride and lithium fluoride according to the formula amount to obtain mixed molten salt, wherein the mixed molten salt comprises: 4 parts of aluminum oxide, 6 parts of thorium oxide, 85 parts of sodium hexafluoroaluminate, 2 parts of calcium fluoride, 2 parts of magnesium fluoride, 4 parts of thorium fluoride and 6 parts of lithium fluoride;
(2) In argon atmosphere, the mixed molten salt is kept at 600 ℃ for 1h, heated to 950 ℃ and kept at 20h, tungsten is taken as a cathode, graphite is taken as an anode, direct current power supply is adopted for electrolysis, the electrolysis temperature is 950 ℃, and the electrolysis current density is 3A/cm 2 The electrolysis time is 30 hours, and the aluminum-thorium alloy is obtained.
Example 5
The embodiment provides a preparation method of an aluminum-thorium alloy, which comprises the following steps:
(1) Mixing aluminum oxide, thorium oxide, sodium hexafluoroaluminate, aluminum fluoride and thorium fluoride according to the formula amount to obtain mixed molten salt, wherein the mixed molten salt comprises: 12 parts of aluminum oxide, 6 parts of thorium oxide, 70 parts of sodium hexafluoroaluminate, 4 parts of aluminum fluoride and 2 parts of thorium fluoride;
(2) In argon atmosphere, the mixed molten salt is preserved for 20 hours at 100 ℃, is heated to 950 ℃ and preserved for 10 hours, takes molybdenum as a cathode and graphite as an anode, adopts direct current power supply for electrolysis, the electrolysis temperature is 1000 ℃, and the electrolysis current density is 0.5A/cm 2 The electrolysis time is 25 hours, and the aluminum-thorium alloy is obtained.
Example 6
This example provides a process for the preparation of an aluminium-thorium alloy, the remainder being the same as example 1 except that the weight part of aluminium oxide in the mixed molten salt is 1 part.
Example 7
This example provides a process for the preparation of an aluminium-thorium alloy, the remainder being the same as in example 1 except that the weight part of aluminium oxide in the mixed molten salt is 17.
Example 8
This example provides a process for the preparation of an aluminium-thorium alloy, the remainder being the same as example 1 except that the weight part of thorium oxide in the mixed molten salt is 1 part.
Example 9
This example provides a process for the preparation of an aluminium-thorium alloy, the remainder being the same as in example 1 except that 17 parts by weight of thorium oxide is present in the mixed molten salt.
Example 10
This example provides a process for the preparation of an aluminium-thorium alloy with a current density of 0.2A/cm for electroless plating 2 Except for this, the procedure was the same as in example 1.
Example 11
The embodiment provides a preparation method of aluminum-thorium alloy, wherein the current density for removing electrolysis is 6A/cm 2 Except for the restThe same as in example 1.
Example 12
This example provides a process for the preparation of an aluminium-thorium alloy, the remainder being the same as in example 1, except that the electrolysis temperature is 700 ℃.
Example 13
This example provides a process for the preparation of an aluminium-thorium alloy, the remainder being the same as in example 1, except that the electrolysis temperature is 1100 ℃.
The tests were carried out on the aluminium-thorium alloys obtained by the preparation methods in examples 1-13, as follows:
(1) Elemental mass ratio: obtaining the element mass ratio of aluminum and thorium in the aluminum-thorium alloy through X-ray fluorescence spectrum analysis;
(2) Electrolytic current efficiency: calculating the current efficiencies of aluminum and thorium respectively, and calculating the sum of the current efficiencies of aluminum and thorium;
mass of actual metal = mass of product x mass ratio of elements in the alloy;
current efficiency of metal= (mass of actual metal/mass of metal obtained by faraday's law) ×100%;
metal mass = current intensity x power-on time x electrochemical equivalent of metal obtained by faraday's law;
electrochemical equivalent refers to the mass of metal produced by 1 coulomb of electricity.
The results obtained are shown in Table 1:
TABLE 1
From the data of table 1:
(1) The preparation method of the aluminum-thorium alloy in the embodiments 1-5 has the advantages that the thorium content of the aluminum-thorium alloy is high, the current efficiency is high, the aluminum-thorium alloy is prepared by adopting a molten salt electrolysis method, and compared with the traditional preparation method of the aluminum-thorium alloy, the preparation method has the advantages of short flow, simple equipment, low cost and easy control of reaction conditions.
(2) From a comparison of example 1 with examples 6 and 7, it is known that the content of alumina in the mixed molten salt affects the content of aluminum and thorium in the aluminum-thorium alloy and also affects the electrolysis current efficiency. When the content of alumina is too low, the content of aluminum ions in the mixed molten salt is low, which causes difficulty in reduction of aluminum ions and reduces the cathode current efficiency; when the content of aluminum oxide is too high, the content of aluminum ions in the mixed molten salt is too high, thorium ions are difficult to deposit, and the content of thorium ions in the aluminum-thorium alloy is too low, so that the performance of the aluminum-thorium alloy is affected.
(3) It is seen from a comparison of example 1 with examples 8 and 9 that the content of thorium oxide in the mixed molten salt affects the content of aluminum and thorium in the aluminum-thorium alloy and also affects the electrolysis current efficiency. When the content of thorium oxide is too low, the content of thorium ions in the mixed molten salt is low, which can cause the content of thorium in the aluminum thorium metal to be too low, thereby affecting the performance of the aluminum thorium metal; when the content of thorium oxide is too high, it results in a decrease in the cathode current efficiency.
(4) As is clear from comparison of example 1 with examples 10 and 11, the current density of electrolysis affects the contents of aluminum and thorium in the aluminum-thorium alloy, and also affects the electrolysis current efficiency, when the current density of electrolysis is too high, the cathode overpotential increases, the cathode polarization increases, the cathode current efficiency decreases, the energy consumption is serious, and the edge effect is easy to generate, resulting in the deterioration of the performance of the aluminum-thorium alloy; when the current density of electrolysis is too small, the overpotential of the cathode is reduced, the polarization of the cathode is small, the electrolysis speed is slow, the crystallization of the aluminum-thorium alloy is coarse, the alloy performance is poor, and even the electrolysis process cannot be carried out.
(5) As can be seen from comparison of the embodiment 1 with the embodiments 12 and 13, the invention has the advantages that the electrolysis temperature is 900-1000 ℃, when the electrolysis temperature is too high, the cathode overpotential becomes small, the cathode polarization is reduced, the precipitation of aluminum-thorium alloy is not facilitated, the energy consumption is higher, and the energy-saving and environment-friendly requirements are not met; when the temperature of electrolysis is too low, the overpotential of the cathode becomes large, and the polarization of the cathode becomes large, but the too low temperature is unfavorable for the transmission of ions in the mixed molten salt, which can lead to the reduction of current efficiency, and the components of the aluminum-thorium alloy are uneven, if the temperature of electrolysis is insufficient to change the mixed molten salt into an ionic state, the electrolysis current is extremely low, and even the electrolysis cannot be performed.
In conclusion, the method for preparing the aluminum-thorium alloy by adopting the molten salt electrolysis method has the advantages of short flow, simple equipment, low cost and easy control of reaction conditions compared with the traditional preparation method of the aluminum-thorium alloy; the preparation method can be used in the existing aluminum electrolysis system, the existing 200-500KA aluminum electrolysis cell is utilized, thorium oxide and electrolyte are added according to a certain concentration, the aluminum thorium alloy can be continuously produced on the premise of not changing the structure and facilities of the existing aluminum electrolysis cell, and industrial popularization and application are easy to realize.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. A method for preparing an aluminum-thorium alloy, which is characterized by comprising the following steps:
(1) Mixing aluminum oxide, thorium oxide and electrolyte to obtain mixed molten salt;
(2) And (3) heating and melting the mixed molten salt in protective gas, and then electrolyzing to obtain the aluminum-thorium alloy.
2. The method of claim 1, wherein the electrolyte comprises sodium hexafluoroaluminate with a fluoride salt;
preferably, the fluoride salt comprises a combination of at least two of aluminum fluoride, thorium fluoride, calcium fluoride, magnesium fluoride or lithium fluoride;
preferably, the fluoride salt comprises thorium fluoride and at least one of aluminum fluoride, calcium fluoride, magnesium fluoride or lithium fluoride.
3. The production method according to claim 2, characterized in that the mixed molten salt comprises, in parts by weight:
4. a method according to any one of claims 1 to 3, wherein the mixed molten salt obtained in step (1) is dried before being heated and melted;
preferably, the temperature of the drying is 100-600 ℃ and the time is 1-20h.
5. The method according to any one of claims 1 to 4, wherein the temperature-raising and melting in the step (2) includes sequentially performed temperature-raising and heat-preserving treatments;
preferably, the heating rate is 1-10 ℃/min;
preferably, the temperature of the heating end point is 900-1000 ℃;
preferably, the temperature of the heat preservation treatment is the end temperature of the temperature rise;
preferably, the time of the heat preservation treatment is 1-20h;
preferably, the protective gas comprises nitrogen and/or an inert gas.
6. The method of any one of claims 1-5, wherein the electrolytic cathode comprises any one of tungsten, molybdenum, or graphite;
preferably, the anode of the electrolysis comprises an inert electrode;
preferably, the inert electrode comprises graphite.
7. The method of any one of claims 1-6, wherein the electrolysis uses a direct current source;
preferably, the electrolytic current density is 0.5-5A/cm 2 ；
Preferably, the temperature of the electrolysis is 900-1000 ℃;
preferably, the electrolysis is carried out for a period of time ranging from 5 to 30 hours.
8. The preparation method according to any one of claims 1 to 7, characterized in that the preparation method comprises the steps of:
(1) Mixing aluminum oxide, thorium oxide and electrolyte according to the formula amount to obtain mixed molten salt;
(2) In protective gas, the mixed molten salt is kept at 100-600 ℃ for 1-20h, the temperature is raised to 900-1000 ℃ at a heating rate of 1-10 ℃/min, the temperature is kept for 1-20h, tungsten, molybdenum or graphite is used as a cathode, graphite is used as an anode, direct current power supply is used for electrolysis, the electrolysis temperature is 900-1000 ℃, and the current density of electrolysis is 0.5-5A/cm 2 The electrolysis time is 5-30h, and the aluminum-thorium alloy is obtained.
9. An aluminium-thorium alloy, characterized in that it is obtained according to the preparation method of any one of claims 1-8.
10. Use of an aluminium-thorium alloy according to claim 9 in the aeronautical industry, in the marine industry or in the chemical industry.
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