CN117802330A - Tantalum-niobium alloy and smelting method and application thereof - Google Patents
Tantalum-niobium alloy and smelting method and application thereof Download PDFInfo
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- CN117802330A CN117802330A CN202311682868.XA CN202311682868A CN117802330A CN 117802330 A CN117802330 A CN 117802330A CN 202311682868 A CN202311682868 A CN 202311682868A CN 117802330 A CN117802330 A CN 117802330A
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- tantalum
- sodium
- niobium
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- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910001257 Nb alloy Inorganic materials 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000003723 Smelting Methods 0.000 title claims abstract description 42
- 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 claims abstract description 80
- 239000011734 sodium Substances 0.000 claims abstract description 80
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 80
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 69
- 239000000126 substance Substances 0.000 claims abstract description 52
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 40
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002386 leaching Methods 0.000 claims abstract description 35
- 238000009853 pyrometallurgy Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000011575 calcium Substances 0.000 claims abstract description 29
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 25
- 229910052715 tantalum Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000292 calcium oxide Substances 0.000 claims description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910000528 Na alloy Inorganic materials 0.000 claims description 6
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims 1
- 239000011885 synergistic combination Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 58
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 20
- 229910052721 tungsten Inorganic materials 0.000 description 20
- 239000010937 tungsten Substances 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052758 niobium Inorganic materials 0.000 description 13
- 239000010955 niobium Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 230000009467 reduction Effects 0.000 description 11
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 10
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910000484 niobium oxide Inorganic materials 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910001936 tantalum oxide Inorganic materials 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 206010024769 Local reaction Diseases 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- -1 CO or CO 2 ) Also Chemical compound 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The application provides a tantalum-niobium alloy, a smelting method and application thereof, wherein the method comprises the following steps: sodium roasting the tantalum-niobium waste material, and washing with water to obtain leaching residues; mixing leaching slag, a reducing agent and an auxiliary agent, then carrying out pyrometallurgy, and casting after smelting to obtain tantalum-niobium alloy; the reducing agent comprises at least one of active metal and carbon simple substance; the auxiliary agent comprises at least one of a sodium source and a calcium source; the temperature of the pyrometallurgy is 2800-3500 ℃. The tantalum-niobium alloy with high purity is prepared by the synergistic combination of the pyrometallurgy temperature, the reducing agent and the auxiliary agent.
Description
Technical Field
The application relates to the technical field of metal smelting, in particular to a tantalum-niobium alloy and a smelting method and application thereof.
Background
Tantalum-niobium alloys, typically alloys composed of two metallic elements, tantalum and niobium, have excellent properties and a wide range of applications. The tantalum-niobium alloy has the following characteristics:
1. high melting point and high melting point: the melting point of tantalum is about 2996 ℃ and the melting point of niobium is about 2468 ℃, so that the tantalum-niobium alloy has a higher melting point, and is excellent in high-temperature environment;
2. excellent corrosion resistance: the tantalum-niobium alloy has good corrosion resistance, can resist the corrosion of corrosive media such as acid, alkali and the like, and is widely applied to corrosive environments such as chemical industry and the like;
3. excellent mechanical properties: the alloy has excellent mechanical properties including high strength, high hardness and good ductility, and is suitable for various engineering applications.
The preparation method of the tantalum-niobium alloy in the related art comprises the following steps:
1. the metallurgical method is as follows: mixing tantalum and niobium in proportion through smelting, casting, heat treatment and other processes, and carrying out chemical reaction at a specific temperature to finally obtain tantalum-niobium alloy;
2. powder metallurgy preparation: tantalum and niobium powder are mixed according to a certain proportion, and the tantalum-niobium alloy is obtained through processes such as pressing and sintering.
The method comprises the steps of firstly preparing high-purity metal tantalum and metal niobium from alloy scraps, tantalum ore or niobium ore; and then the tantalum and the niobium are mixed in a certain mode to prepare the tantalum-niobium alloy, and the tantalum-niobium alloy cannot be directly prepared from alloy scraps by one-step reduction.
Content of the application
The present invention has been made in view of the above problems, and an object thereof is to provide a method for smelting a tantalum-niobium alloy, which can produce a high-purity tantalum-niobium alloy by one-step reduction.
Specifically, the first aspect of the application provides a smelting method of tantalum-niobium alloy, which comprises the following steps:
sodium roasting the tantalum-niobium waste material, and washing with water to obtain leaching residues;
mixing leaching slag, a reducing agent and an auxiliary agent, then carrying out pyrometallurgy, and casting after smelting to obtain tantalum-niobium alloy;
the reducing agent comprises at least one of active metal and carbon simple substance;
the auxiliary agent comprises at least one of a sodium source and a calcium source;
the temperature of the pyrometallurgy is 2800-3500 ℃.
The tantalum-niobium scrap in the application contains tantalum element and niobium element; also contains tungsten element, silicon element, etc. In order to prepare the high-purity tantalum-niobium alloy, firstly, sodium roasting is carried out on tantalum-niobium scraps to convert silicon element into sodium silicate and tungsten element into sodium tungstate; removing tungsten element and silicon element in the tantalum-niobium scraps by water washing by utilizing the water solubility of sodium silicate and sodium tungstate; and the tantalum element and the niobium element are primarily reduced, so that the tungsten element, the silicon element and other soluble impurities are removed by washing after sodium roasting.
The leaching slag, the reducing agent and the auxiliary agent are mixed and then subjected to pyrometallurgy to prepare the high-purity tantalum-niobium alloy; under the action of a reducing agent, the tantalum oxide is converted into metal tantalum, and the niobium oxide is converted into metal niobium; at the pyrometallurgical temperatures of the present application, the niobium metal will be converted to a liquid; and forming a tantalum-niobium alloy with the metallic tantalum; the active metal is in a gaseous state at the temperature of the application, so that the residual quantity in the formed tantalum-niobium alloy is low; meanwhile, as the reactivity of the active metal is high, the concentration of the active metal needs to be reduced by an auxiliary agent to prevent the reaction from being too severe; while the carbon element reduces the metal oxide (tantalum oxide and niobium oxide) to metal, and then part of the metal oxide is converted into gaseous carbon oxide (such as CO or CO 2 ) The alloy can not be remained in a large amount in the tantalum-niobium alloy, namely, the tantalum-niobium alloy with high purity is prepared by the synergistic combination of the pyrometallurgy temperature, the reducing agent and the auxiliary agent.
The tantalum-niobium alloy prepared by the scheme can be further applied to the preparation of tantalum metal, and the tantalum metal has excellent physical properties and chemical properties (excellent corrosion resistance, excellent high temperature resistance and high strength) and has wide application fields; the tantalum-niobium alloy prepared by the scheme has wide application prospect in the aerospace industry, capacitors and communication equipment (5G and above).
Optionally, the active metal includes at least one of elemental sodium, a sodium alloy, elemental calcium, and a calcium alloy.
The sodium simple substance, the sodium alloy, the calcium simple substance and the calcium alloy have low boiling points and high activity, and can fully reduce tantalum oxide and niobium oxide.
Optionally, the sodium source comprises at least one of sodium hydroxide and sodium carbonate.
By adding sodium hydroxide or sodium carbonate as an auxiliary agent, the contact area between materials can be reduced, and local reaction is prevented from being too severe.
Optionally, the calcium source comprises at least one of calcium hydroxide, calcium oxide, and calcium carbonate.
By adding calcium hydroxide, calcium oxide and calcium carbonate as auxiliary agents, the contact area between materials can be reduced, and local reaction is prevented from being too severe.
Optionally, the pyrometallurgy time is 1-3 h.
The pyrometallurgy time is too short, and the reaction is insufficient, so that the purity of the tantalum-niobium alloy is affected; and the smelting time is too long and the energy consumption is too high.
Optionally, the mass ratio of the leaching residue to the auxiliary agent is 100: (15-25).
If the addition amount of the auxiliary agent is too small and the local concentration of the reducing agent is too high, the inhibition capability of the auxiliary agent on the reduction reaction is poor, so that the local reduction reaction is too severe; too much adjuvant addition, too low local concentration of the reducing agent, can result in too slow a reduction reaction, thereby affecting the purity of the tantalum-niobium alloy.
Optionally, the mass ratio of the leaching slag to the reducing agent is 100: (15-30).
The addition amount of the reducing agent is small, so that insufficient reduction can be caused, and the purity of the tantalum-niobium alloy is affected; excessive addition of the reducing agent causes an increase in the residual amount of the reducing agent, thereby affecting the purity of the tantalum-niobium alloy.
Optionally, the temperature of the sodium modification roasting is 800-1000 ℃.
Too low roasting temperature and too slow reaction; the temperature is too high, tungsten element can be converted into a tungsten simple substance, the melting point of the tungsten simple substance is high, and the residual quantity of tungsten is increased, so that the purity of the tantalum-niobium alloy is affected.
Optionally, a sodium-containing reducing agent is added in the sodium roasting process.
Optionally, the mass ratio of the sodium-containing reducing agent to the tantalum-niobium scrap is (20-40): 100.
adding a sodium-containing reducing agent in the sodium roasting process, wherein the sodium-containing reducing agent can primarily reduce tantalum element and niobium element; the sodium-containing reducing agent is converted into a strong alkaline substance, and the strong alkaline substance converts tungsten element and silicon element into soluble salts, so that the tungsten element and the silicon element are removed.
The second aspect of the application also provides a tantalum-niobium alloy which is obtained by smelting through the smelting method.
The third aspect of the application also provides application of the tantalum-niobium alloy in the aerospace industry, the preparation of tantalum capacitors and/or the preparation of communication equipment.
Detailed Description
The following detailed description discloses embodiments of the tantalum-niobium alloy, methods of smelting and applications thereof. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the following description is provided for a thorough understanding of the present application by those skilled in the art, and is not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
Specifically, as follows, the first aspect of the embodiment of the present application provides a method for smelting tantalum-niobium alloy, which includes the following steps:
sodium roasting the tantalum-niobium waste material, and washing with water to obtain leaching residues;
mixing leaching slag, a reducing agent and an auxiliary agent, then carrying out pyrometallurgy, and casting after smelting to obtain tantalum-niobium alloy;
the reducing agent comprises at least one of active metal and carbon simple substance;
the auxiliary agent comprises at least one of a sodium source and a calcium source;
the temperature of the pyrometallurgy is 2800-3500 ℃.
In the application, the tantalum-niobium scrap contains tantalum element and niobium element; also contains tungsten element, silicon element, etc. In order to prepare the high-purity tantalum-niobium alloy, firstly, sodium roasting is carried out on tantalum-niobium scraps to convert silicon element into sodium silicate and tungsten element into sodium tungstate; removing tungsten element and silicon element in the tantalum-niobium scraps by water washing by utilizing the water solubility of sodium silicate and sodium tungstate; and the tantalum element and the niobium element are primarily reduced, so that the tungsten element, the silicon element and other water-soluble impurities are removed by washing after sodium roasting.
The leaching slag, the reducing agent and the auxiliary agent are mixed and then subjected to pyrometallurgy to prepare the high-purity tantalum-niobium alloy; under the action of a reducing agent, the tantalum oxide is converted into metal tantalum, and the niobium oxide is converted into metal niobium; at the pyrometallurgical temperatures of the present application, the niobium metal will be converted to a liquid; and forming a tantalum-niobium alloy with the metallic tantalum; the active metal is in a gaseous state at the temperature of the application, so that the residual quantity in the formed tantalum-niobium alloy is low; meanwhile, as the reactivity of the active metal is high, the concentration of the active metal needs to be reduced by an auxiliary agent to prevent the reaction from being too severe; while the carbon element reduces the metal oxide (tantalum oxide and niobium oxide) to metal, and then part of the metal oxide is converted into gaseous carbon oxide (such as CO or CO 2 ) Also, the alloy does not remain in a large amount in the tantalum-niobium alloy, namely the alloy is smelted by a fire method at the temperature and alsoThe raw material and the auxiliary agent are matched in a synergistic way, so that the tantalum-niobium alloy with high purity is prepared.
The tantalum-niobium alloy prepared by the scheme can be further applied to the preparation of tantalum metal, and the tantalum metal has excellent physical properties and chemical properties (excellent corrosion resistance, excellent high temperature resistance and high strength) and has wide application fields; the tantalum-niobium alloy prepared by the scheme has wide application prospect in the aerospace industry, capacitors and communication equipment (5G and above).
In some embodiments, the active metal comprises at least one of elemental sodium, a sodium alloy, elemental calcium, and a calcium alloy.
The sodium simple substance, the sodium alloy, the calcium simple substance and the calcium alloy have low boiling points and high activity, and can fully reduce tantalum oxide and niobium oxide.
In some embodiments, the sodium source comprises at least one of sodium hydroxide and sodium carbonate.
By adding sodium hydroxide or sodium carbonate as an auxiliary agent, the contact area between materials can be reduced, and local reaction is prevented from being too severe.
In some embodiments, the calcium source comprises at least one of calcium hydroxide, calcium oxide, and calcium carbonate.
By adding calcium hydroxide, calcium oxide or calcium carbonate as auxiliary agent, the contact area between materials can be reduced, and local reaction is prevented from being too severe.
In some embodiments, the pyrometallurgy is for a period of 1h to 3h.
The pyrometallurgy time is too short, and the reaction is insufficient, so that the purity of the tantalum-niobium alloy is affected; and the smelting time is too long and the energy consumption is too high.
In some embodiments, the leach residue and the adjunct are present in a mass ratio of 100: (15-25).
If the addition amount of the auxiliary agent is too small and the local concentration of the reducing agent is too high, the inhibition capability of the auxiliary agent on the reduction reaction is poor, so that the local reduction reaction is too severe; too much adjuvant addition, too low local concentration of the reducing agent, can result in too slow a reduction reaction, thereby affecting the purity of the tantalum-niobium alloy.
In some embodiments, the mass ratio of the leaching residue to the reducing agent is 100: (15-30).
The addition amount of the reducing agent is small, so that insufficient reduction can be caused, and the purity of the tantalum-niobium alloy is affected; excessive addition of the reducing agent causes an increase in the residual amount of the reducing agent, thereby affecting the purity of the tantalum-niobium alloy.
In some embodiments, the elemental carbon is graphite.
In some embodiments, the reducing agent consists of an active metal and elemental carbon.
In some embodiments, the mass ratio of the active metal to the elemental carbon is 1: (2-3).
The consumption of the active metal is excessive, and the production cost is high; the use of too little active metal results in reduced reducibility of the pyrometallurgy system, thereby affecting the purity of the tantalum-niobium alloy.
In some embodiments, the reducing agent consists of elemental sodium, elemental calcium, and elemental carbon.
The boiling point of the sodium simple substance is 883 ℃, the boiling point of the calcium simple substance is 1484 ℃, and the sodium simple substance and the calcium simple substance are gasified to form a reducing atmosphere in the pyrometallurgy process; in the heating process of pyrometallurgy, sodium elementary substance is gasified first to form a reducing atmosphere; in the gasification process of the sodium simple substance, the sodium simple substance is primarily reduced with solid niobium oxide and tantalum pentoxide; the calcium simple substance is gasified and contacted with molten niobium pentoxide (the melting point is 1460 ℃), so that high-efficiency reduction is realized; finally, tantalum pentoxide (melting point is 1800 ℃) is melted and fully contacted with carbon simple substance in the system for further reduction; in the application, the reduction efficiency is further improved by further selecting the reducing agent; thereby further improving the purity of the tantalum-niobium alloy.
In some embodiments, the mass ratio of elemental sodium, elemental calcium, and elemental carbon in the reducing agent is 1: (2-3): (6-12).
In some embodiments, the mass ratio of elemental sodium, elemental calcium, and elemental carbon in the reducing agent is 1: (2-3): (6-10).
In some embodiments, the mass ratio of elemental sodium, elemental calcium, and elemental carbon in the reducing agent is 1: (2-3): (6-9).
In some embodiments, the pyrometallurgical heating process consists of the following heating stages:
heating in the first section: heating to 1000-1200 deg.c at 20-30 deg.c; the temperature rise time is 0.5 h-1 h;
the first section keeps warm: preserving heat for 0.5-1 h at 1000-1200 ℃;
and (3) heating in the second stage: heating to 1800-1900 ℃ at 1000-1200 ℃; the temperature rise time is 0.5 h-1 h;
and (3) heat preservation in the second section: preserving heat for 0.4 to 0.6 hours at 1800 to 1900 ℃;
and (3) heating in the third stage: heating to 2800-3500 ℃ at 1800-1900 ℃; the temperature rise time is 1 h-1.5 h.
In some embodiments, the pyrometallurgical temperature is 2800 ℃ to 3000 ℃.
In some embodiments, the third stage elevated temperature has a final temperature of 2800 ℃ to 3000 ℃.
In some embodiments, the sodium salt calcination temperature is 800 ℃ to 1000 ℃.
Too low roasting temperature and too slow reaction; the temperature is too high, tungsten element can be converted into a tungsten simple substance, the melting point of the tungsten simple substance is high, and the residual quantity of tungsten is increased, so that the purity of the tantalum-niobium alloy is affected.
In some embodiments, a sodium-containing reducing agent is added during the sodium roasting process.
Adding a sodium-containing reducing agent in the sodium roasting process, wherein the sodium-containing reducing agent can primarily reduce tantalum element and niobium element; the sodium-containing reducing agent is converted into a strong alkaline substance, and the strong alkaline substance converts tungsten element and silicon element into soluble salts, so that the tungsten element and the silicon element are removed.
In some embodiments, the mass ratio of the sodium-containing reducing agent to the tantalum-niobium scrap is (20-40): 100.
in some embodiments, the sodium-containing reducing agent comprises at least one of elemental sodium and a sodium alloy.
In some embodiments, the sodium salt calcination time is 1h to 2h.
In some embodiments, the temperature of the water used for water washing is 20 ℃ to 30 ℃.
In some embodiments, the water wash time is from 0.5h to 1h.
In some embodiments, the tantalum pentoxide in the tantalum niobium scrap is above 1.5% by mass.
In some embodiments, the mass fraction of niobium pentoxide in the tantalum niobium scrap is above 1.5%.
In some embodiments, the mass fraction of tungsten oxide in the tantalum niobium scrap is above 1.5%.
In some embodiments, the mass fraction of silicon oxide in the tantalum niobium scrap is above 20%.
By controlling smelting conditions, the method realizes recovery of tantalum-niobium metal from tantalum-niobium scraps with high silicon content, low tantalum content and low niobium content, and greatly reduces production cost.
The second aspect of the embodiment of the application also provides a tantalum-niobium alloy which is obtained by smelting through the smelting method.
The third aspect of the embodiment of the application also provides application of the tantalum-niobium alloy in the aerospace industry, preparation of tantalum capacitors and/or preparation of communication equipment.
The mass content of each element (in terms of oxide) in the tantalum-niobium scrap used in the present example and comparative example is as follows:
tantalum pentoxide 2.67%, niobium pentoxide 1.89%, tungsten trioxide 1.53%, silicon dioxide 36.3% and the balance other impurities.
Example 1
The embodiment is a smelting method of tantalum-niobium alloy, which comprises the following steps:
s1, mixing tantalum-niobium scraps and sodium simple substances, performing sodium roasting (the roasting temperature is 900 ℃ for 1.5 h), and washing (the water temperature for washing is 25 ℃ for 1 h) to obtain leaching residues;
the mass ratio of the sodium simple substance to the tantalum-niobium scrap is 1:4, a step of;
s2, mixing leaching residues, a reducing agent and an auxiliary agent, and then heating and pyrometallurgy (the pyrometallurgy temperature is 3000 ℃ C., and the time is 2 h); casting after smelting is completed to prepare tantalum-niobium alloy;
the mass ratio of the leaching slag to the auxiliary agent in the step is 100:18;
the mass ratio of the leaching residue to the reducing agent is 100:22;
the reducing agent comprises the following preparation raw materials in parts by mass:
1 part of sodium simple substance, 2.4 parts of calcium simple substance and 10 parts of graphite;
the auxiliary agent consists of a sodium source (sodium hydroxide) and a calcium source (calcium oxide and calcium carbonate, wherein the mass ratio of the calcium oxide to the calcium carbonate is 1:3); the mass ratio of the sodium source to the calcium source is 1:2;
the heating process before pyrometallurgy consists of the following heating stages:
heating in the first section: heating to 1200 ℃ at 25 ℃; the temperature rise time is 0.8h;
the first section keeps warm: preserving heat for 0.6h at 1200 ℃;
and (3) heating in the second stage: raising the temperature to 1850 ℃ at 1200 ℃; the temperature rise time is 0.6h;
and (3) heat preservation in the second section: preserving heat for 0.5h at 1850 ℃;
and (3) heating in the third stage: 1850 ℃ to 3000 ℃; the temperature rise time was 1.2h.
Example 2
The embodiment is a smelting method of tantalum-niobium alloy, which comprises the following steps:
s1, mixing tantalum-niobium scraps and sodium simple substances, performing sodium roasting (the roasting temperature is 1000 ℃ for 1.5 h), and washing (the water temperature for washing is 25 ℃ for 1 h) to obtain leaching residues;
the mass ratio of the sodium simple substance to the tantalum-niobium scrap is 1:5, a step of;
s2, mixing leaching residues, a reducing agent and an auxiliary agent, and then heating and pyrometallurgy (the pyrometallurgy temperature is 2900 ℃ C., and the time is 2 h); casting after smelting is completed to prepare tantalum-niobium alloy;
the mass ratio of the leaching slag to the auxiliary agent in the step is 100:20, a step of;
the mass ratio of the leaching residue to the reducing agent is 100:20, a step of;
the reducing agent comprises the following preparation raw materials in parts by mass:
1 part of sodium simple substance, 2 parts of calcium simple substance and 8 parts of graphite;
the auxiliary agent consists of a sodium source (sodium carbonate) and a calcium source (calcium oxide and calcium carbonate, wherein the mass ratio of the calcium oxide to the calcium carbonate is 1:3); the mass ratio of the sodium source to the calcium source is 1:2;
the heating process before pyrometallurgy consists of the following heating stages:
heating in the first section: heating to 1100 ℃ at 25 ℃; the temperature rise time is 0.5h;
the first section keeps warm: preserving heat for 1h at 1100 ℃;
and (3) heating in the second stage: heating to 1100 ℃ to 1800 ℃; the temperature rise time is 1h;
and (3) heat preservation in the second section: preserving heat for 0.6h at 1800 ℃;
and (3) heating in the third stage: heating to 2900 ℃ at 1800 ℃; the temperature rise time was 1h.
Example 3
The embodiment is a smelting method of tantalum-niobium alloy, which comprises the following steps:
s1, mixing tantalum-niobium scraps and sodium simple substances, performing sodium roasting (the roasting temperature is 920 ℃ and the time is 1.5 h), and washing (the washing temperature is 25 ℃ and the time is 0.5 h) to obtain leaching residues;
the mass ratio of the sodium simple substance to the tantalum-niobium scrap is 1:4, a step of;
s2, mixing leaching residues, a reducing agent and an auxiliary agent, and then heating and pyrometallurgy (the pyrometallurgy temperature is 2800 ℃ and the time is 2 h); casting after smelting is completed to prepare tantalum-niobium alloy;
the mass ratio of the leaching slag to the auxiliary agent in the step is 100:20, a step of;
the mass ratio of the leaching residue to the reducing agent is 100:30;
the reducing agent comprises the following preparation raw materials in parts by mass:
1 part of sodium simple substance, 3 parts of calcium simple substance and 10 parts of graphite;
the auxiliary agent consists of a sodium source (sodium carbonate) and a calcium source (calcium oxide and calcium carbonate, wherein the mass ratio of the calcium oxide to the calcium carbonate is 1:3); the mass ratio of the sodium source to the calcium source is 1:2;
the heating process before pyrometallurgy consists of the following heating stages:
heating in the first section: heating to 1120 ℃ at 25 ℃; the temperature rise time is 0.6h;
the first section keeps warm: preserving heat for 1h at 1120 ℃;
and (3) heating in the second stage: heating to 1880 ℃ at 1120 ℃; the temperature rise time is 1h;
and (3) heat preservation in the second section: preserving heat for 0.5h at 1880 ℃;
and (3) heating in the third stage: heating to 2800 ℃ at 1880 ℃; the temperature rise time was 1h.
Example 4
The embodiment is a smelting method of tantalum-niobium alloy, which comprises the following steps:
s1, mixing tantalum-niobium scraps and sodium simple substances, performing sodium roasting (the roasting temperature is 950 ℃ for 1.5 h), and washing (the water temperature for washing is 25 ℃ for 1 h) to obtain leaching residues;
the mass ratio of the sodium simple substance to the tantalum-niobium scrap is 1:5, a step of;
s2, mixing leaching residues, a reducing agent and an auxiliary agent, and then heating and pyrometallurgy (the pyrometallurgy temperature is 3100 ℃ and the time is 2 h); casting after smelting is completed to prepare tantalum-niobium alloy;
the mass ratio of the leaching slag to the auxiliary agent in the step is 100:18;
the mass ratio of the leaching residue to the reducing agent is 100:25, a step of selecting a specific type of material;
the reducing agent comprises the following preparation raw materials in parts by mass:
1 part of sodium simple substance, 2.8 parts of calcium simple substance and 11 parts of graphite;
the auxiliary agent consists of a sodium source (sodium hydroxide) and a calcium source (calcium oxide and calcium carbonate, wherein the mass ratio of the calcium oxide to the calcium carbonate is 1:3); the mass ratio of the sodium source to the calcium source is 1:2;
the heating process before pyrometallurgy consists of the following heating stages:
heating in the first section: heating to 1150 ℃ at 25 ℃; the temperature rise time is 1h;
the first section keeps warm: preserving heat for 0.8h at 1150 ℃;
and (3) heating in the second stage: heating to 1150 ℃ to 1810 ℃; the temperature rise time is 0.6h;
and (3) heat preservation in the second section: preserving heat for 0.6h at 1810 ℃;
and (3) heating in the third stage: heating to 3100 ℃ at 1810 ℃; the temperature rise time was 1.5h.
Example 5
The embodiment is a smelting method of tantalum-niobium alloy, which comprises the following steps:
s1, mixing tantalum-niobium scraps and sodium simple substances, performing sodium roasting (the roasting temperature is 860 ℃ for 1.5 h), and washing (the water temperature for washing is 25 ℃ for 1 h) to obtain leaching residues;
the mass ratio of the sodium simple substance to the tantalum-niobium scrap is 1:4, a step of;
s2, mixing leaching residues, a reducing agent and an auxiliary agent, and then heating and pyrometallurgy (the pyrometallurgy temperature is 3200 ℃ and the pyrometallurgy time is 2 h); casting after smelting is completed to prepare tantalum-niobium alloy;
the mass ratio of the leaching slag to the auxiliary agent in the step is 100:17;
the mass ratio of the leaching residue to the reducing agent is 100:26;
the reducing agent comprises the following preparation raw materials in parts by mass:
1 part of sodium simple substance, 2.2 parts of calcium simple substance and 9 parts of graphite;
the auxiliary agent consists of a sodium source (sodium carbonate) and a calcium source (calcium oxide and calcium carbonate, wherein the mass ratio of the calcium oxide to the calcium carbonate is 1:3); the mass ratio of the sodium source to the calcium source is 1:2;
the heating process before pyrometallurgy consists of the following heating stages:
heating in the first section: raising the temperature to 1160 ℃ at 25 ℃; the temperature rise time is 0.5h;
the first section keeps warm: preserving heat for 0.5h at 1160 ℃;
and (3) heating in the second stage: heating to 1160 deg.C to 1900 deg.C; the temperature rise time is 1h;
and (3) heat preservation in the second section: preserving heat for 0.5h at 1900 ℃;
and (3) heating in the third stage: heating to 3200 ℃ at 1900 ℃; the temperature rise time was 1.5h.
Example 6
This example is a method for smelting tantalum-niobium alloy, and differs from example 5 only in that:
the reducing agent is replaced with graphite.
Example 7
This example is a method for smelting tantalum-niobium alloy, and differs from example 5 only in that:
the reducing agent is replaced by sodium simple substance.
Example 8
This example is a method for smelting tantalum-niobium alloy, and differs from example 5 only in that:
the reducing agent is replaced by a simple substance of calcium.
Example 9
This example is a method for smelting tantalum-niobium alloy, and differs from example 5 only in that:
the temperature raising process in example 5 was replaced with the following temperature raising process:
the temperature rising process consists of the following temperature rising stages:
heating in the first section: raising the temperature to 1160 ℃ at 25 ℃; the temperature rise time is 0.5h;
the first section keeps warm: preserving heat for 0.5h at 1160 ℃;
and (3) heating in the second stage: heating to 1160 deg.C to 3200 deg.C; the temperature rise time was 2.5h.
Example 10
This example is a method for smelting tantalum-niobium alloy, and differs from example 5 only in that:
the temperature raising process in example 5 was replaced with the following temperature raising process:
the temperature rising process consists of the following temperature rising stages:
heating to 3200 ℃ at 25 ℃; the temperature rise time was 3h.
The purity and yield test methods of the tantalum-niobium alloys prepared in examples 1 to 10 were as follows:
the content of tantalum and niobium in the tantalum-niobium alloy is carried out according to GB/T-15076.2; the purity and yield of the tantalum-niobium alloy are calculated by testing the contents of tantalum and niobium in the tantalum-niobium alloy; the test results are shown in Table 1.
Table 1 results of purity and yield tests of tantalum-niobium alloys prepared in examples 1 to 10
| - | Purity (%) | Yield (%) |
| Example 1 | 56.6 | 95.3 |
| Example 2 | 55.9 | 95.1 |
| Example 3 | 55.4 | 94.6 |
| Example 4 | 54.7 | 94.2 |
| Example 5 | 54.9 | 93.4 |
| Example 6 | 50.1 | 90.5 |
| Example 7 | 48.3 | 86.6 |
| Example 8 | 48.9 | 87.4 |
| Example 9 | 52.3 | 91.8 |
| Example 10 | 51.7 | 90.3 |
From a comparison of example 5 and examples 6 to 8, it is known that: the reduction effect of the composite reducing agent is better than that of a single reducing agent; the reason is that: the composite reducing agent can be used for carrying out multistage reduction on the oxide, so that the reduction effect is improved, and the purity and the yield of the tantalum-niobium alloy are further improved.
From a comparison of example 5 and examples 9 to 10, it is known that: the three-stage heating process is adopted, so that the reduction effect of the tantalum-niobium scrap is further improved; the reason is that: and in the three-stage heating process, the reducing agents which are different in heat preservation sections and play a main reducing effect are different, so that the reducing effect of the reducing agents is further improved, and the tantalum-niobium alloy with higher purity is prepared.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (10)
1. The smelting method of the tantalum-niobium alloy is characterized by comprising the following steps of:
sodium roasting the tantalum-niobium waste material, and washing with water to obtain leaching residues;
mixing leaching slag, a reducing agent and an auxiliary agent, then carrying out pyrometallurgy, and casting after smelting to obtain tantalum-niobium alloy;
the reducing agent comprises at least one of active metal and carbon simple substance;
the auxiliary agent comprises at least one of a sodium source and a calcium source;
the temperature of the pyrometallurgy is 2800-3500 ℃.
2. The method for smelting tantalum-niobium alloy according to claim 1, wherein said active metal comprises at least one of sodium simple substance, sodium alloy, calcium simple substance and calcium alloy.
3. The method of claim 1, wherein the sodium source comprises at least one of sodium hydroxide and sodium carbonate.
4. The method of claim 1, wherein the calcium source comprises at least one of calcium oxide and calcium carbonate.
5. The method of claim 1, wherein the pyrometallurgical time is 1h to 3h.
6. The method for smelting tantalum-niobium alloy according to claim 1, wherein the mass ratio of said leaching residue to said auxiliary agent is 100: (15-25).
7. The method for smelting a tantalum-niobium alloy according to claim 1, wherein the mass ratio of said leaching slag to said reducing agent is 100: (15-30).
8. The method for smelting a tantalum-niobium alloy according to claim 1, wherein the sodium-modified firing temperature is 800 ℃ to 1000 ℃;
and/or adding a sodium-containing reducing agent in the sodium roasting process;
and/or the mass ratio of the sodium-containing reducing agent to the tantalum-niobium scrap is (20-40): 100.
9. a tantalum-niobium alloy, characterized by being smelted by the smelting method according to any one of claims 1 to 8.
10. Use of a tantalum-niobium alloy according to claim 9 in the aerospace industry, in the manufacture of tantalum capacitors and/or in the manufacture of communication devices.
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