CN117051444A - Anode device, electrolysis device and method for refining titanium - Google Patents
Anode device, electrolysis device and method for refining titanium Download PDFInfo
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- CN117051444A CN117051444A CN202311221218.5A CN202311221218A CN117051444A CN 117051444 A CN117051444 A CN 117051444A CN 202311221218 A CN202311221218 A CN 202311221218A CN 117051444 A CN117051444 A CN 117051444A
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- anode
- inner cylinder
- titanium
- outer cylinder
- molten salt
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- 239000010936 titanium Substances 0.000 title claims abstract description 87
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 65
- 238000007670 refining Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000004020 conductor Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011810 insulating material Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation 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
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
- C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
-
- 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
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
- C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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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 discloses an anode device, an electrolysis device and a method, wherein the anode device comprises an anode rod and a charging basket; the charging basket comprises an inner cylinder and an outer cylinder, and the inner cylinder is sleeved in the outer cylinder at intervals; the bottom ends of the inner cylinder and the outer cylinder are fixed on the bottom plate, and the top ends of the inner cylinder and the outer cylinder are fixed on the top plate; the inner cylinder, the outer cylinder, the top plate and the bottom plate form a charging cavity, and through holes are formed in the walls of the inner cylinder and the outer cylinder; the middle part of the anode rod is fixed on the top plate, the bottom end of the anode rod passes through the top plate and extends into the inner cylinder, and the anode rod positioned in the inner cylinder is not contacted with the inner cylinder; raw material coarse titanium is arranged in the charging cavity. The anode device adopts the inert anode rod made of the conductive material as an anode electrode, and the titanium raw material is indirectly dissolved out, so that the problem that partial near-potential impurities and titanium are dissolved out together and deposited due to the fact that the titanium raw material is directly adopted as an anode is solved, and the refining coefficient of the impurities is improved.
Description
Technical Field
The invention relates to the technical field of rare metal refining, in particular to an anode device, an electrolysis device and a method for refining titanium.
Background
Crude titanium or titanium-containing materials contain some amount of impurity elements, and it is common to remove these impurities by electrorefining to obtain titanium of higher purity. The molten salt electrolytic refining titanium takes crude titanium and titanium-containing materials as an anode directly, a certain amount of alkali metal or alkaline earth metal halide mixture with low valence ions is added as electrolyte, and metal materials are taken as a cathode to form an electrolytic cell. Under the action of direct current, the titanium in the anode dissolves out into electrolyte in a divalent or trivalent ion state, and migrates to the cathode under the action of electric field force or concentration gradient, and pure titanium is obtained on the surface of the cathode through electrochemical reduction.
The specific electrolytic refining principle is as follows: impurity elements having a potential more positive than titanium are not eluted at the anode and remain in the residual anode; the impurity element with the electrode potential being more negative than the titanium enters the electrolyte along with the dissolution of the titanium, but the impurity element diffused to the cathode is preferentially separated out and remains in the electrolyte due to the deposition potential being more negative than the titanium, thereby achieving the purpose of removing the impurities by electrolytic refining.
However, some of the impurity elements in the crude titanium or titanium-containing material are close to the titanium potential, they are dissolved out into the electrolyte together with titanium during electrolysis and are electrochemically deposited together with titanium on the cathode surface, and the refining effect is not substantially achieved or is poor. As shown in table 1, elements that are difficult to refine during the electrolytic refining of titanium.
Table 1 shows typical elements which are difficult to refine and their potentials
Therefore, the prior art method for obtaining high purity titanium by electrorefining a titanium raw material has a problem that part of impurities are difficult to refine.
Disclosure of Invention
The invention aims to provide an anode device, which adopts an inert anode rod made of a conductive material as an anode electrode, and indirectly dissolves out titanium raw materials, so that the problems that partial near-potential impurities and titanium are jointly dissolved out and deposited due to the fact that the titanium raw materials are directly adopted as the anode are solved, and the refining coefficient of the impurities is improved.
In order to achieve the above object, the present invention provides an anode apparatus comprising an anode rod and a charging basket; wherein,
the charging basket comprises an inner cylinder and an outer cylinder, and the inner cylinder is sleeved in the outer cylinder at intervals; the bottom ends of the inner cylinder and the outer cylinder are fixed on the bottom plate, and the top ends of the inner cylinder and the outer cylinder are fixed on the top plate; the inner cylinder, the outer cylinder, the top plate and the bottom plate form a charging cavity, and through holes are formed in the cylinder walls of the inner cylinder and the outer cylinder;
the middle part of the anode rod is fixed on the top plate, the bottom end of the anode rod passes through the top plate and extends into the inner cylinder, and the anode rod in the inner cylinder is not in contact with the inner cylinder;
raw material coarse titanium is arranged in the charging cavity.
The anode device is characterized in that the charging basket is an annular basket formed by a hollow inner cylinder, an outer cylinder and a bottom plate, wherein the outer cylinder surrounds the outer part of the inner cylinder, the outer cylinder and the inner cylinder have size difference, a certain space is formed, the inner cylinder and the outer cylinder are fixed on the bottom plate, and through holes are formed in the side walls of the inner cylinder and the outer cylinder.
In the anode device of the present invention, the charging cavity is filled with raw material coarse titanium, including but not limited to one or more of titanium sponge, waste titanium material, titanium powder, etc. Preferably, the raw titanium is loosely packed in the charge cavity so as to be permeable to the electrolyte.
In the electrolysis process, ti in molten salt electrolyte 2+ Ti generation on the anode rod surface 2+ Oxidation to Ti 3+ Is a reaction of the produced Ti 3+ Into the charging cavity of the charging basket, and reacts with titanium in raw titanium placed in the charging cavity to generate Ti 2+ Namely, raw material crude titanium is chemically dissolved out and enters molten salt electrolyte to generate Ti 2+ And (3) carrying out electrochemical reduction on the cathode to obtain pure titanium.
According to an anode arrangement of the present invention, preferably the anode rod is graphite.
According to the anode device of the present invention, preferably, the materials of the inner cylinder, the outer cylinder and the bottom plate are insulating materials.
According to an anode device of the present invention, preferably, the insulating material is boron nitride.
According to the anode device of the invention, preferably, the opening ratio of the inner cylinder and the outer cylinder is 50% -70%.
According to an anode arrangement of the present invention, the anode rod is preferably circular, square or rectangular in cross section.
According to an anode device of the present invention, preferably, the charging cavity is provided with one or more of titanium sponge, waste titanium material, titanium powder, and the like.
The invention also provides an electrolysis device for electrolytically refining titanium, which comprises the anode device, wherein the anode device is arranged in a molten salt container for containing molten salt electrolyte, and the anode device and a cathode made of conductive materials form the electrolysis device. Preferably, the molten salt electrolyte is a chloride molten salt electrolyte containing 1wt% or more of Ti 2+ . Preferably, the chloride molten salt electrolyte is NaCl-KCl-TiCl 2 Comprising 1wt% or more of Ti 2+ 。
In addition, the invention also provides a method for refining titanium by using the anode device, which comprises the following steps:
placing the anode device in a molten salt container for containing molten salt electrolyte, forming an electrolytic cell with a cathode made of conductive materials, switching on a power supply for electrolysis, and collecting high-purity titanium at the cathode.
According to the method of the present invention, preferably, the electrolysis temperature ranges from 800 to 1000 ℃.
According to the method of the present invention, preferably, the molten salt electrolyte is a chloride molten salt electrolyte containing 1wt% or more of Ti 2+ 。
The method for electrolytically refining titanium comprises the following steps:
ti in molten salt electrolyte 2+ First, generating electrochemical oxidation reaction on the surface of anode rod to generate Ti 3+ As shown in formula (1).
Ti 2+ -e ＝ Ti 3+ (1)
Ti 3+ The Ti is diffused into the raw material coarse titanium through the through holes to react with Ti in the formula (2).
2Ti 3+ +Ti ＝ 3Ti 2+ (2)
Generated Ti 2+ Diffusion to the cathode through the through-holes is electrochemical reduced to pure Ti.
At the same time, the impurity element in the raw material coarse titanium can also be mixed with Ti generated on the surface of the anode rod 3+ The following chemical reactions occur:
V + 2TiCl 3 ＝ VCl 2 + 2TiCl 2 (3)
Cr + 2TiCl 3 ＝ CrCl 2 + 2TiCl 2 (4)
Fe + 2TiCl 3 ＝ FeCl 2 + 2TiCl 2 (5)
Zr + 2TiCl 3 ＝ ZrCl 2 + 2TiCl 2 (6)
reactions gibbs free energy calculations were performed on reactions (3) - (6) above using HSC6.0 software, the results are shown in figure 4. The calculation results show that none of the above reactions (3) - (6) can proceed spontaneously at a temperature ranging from 800 to 1000 ℃, thus indicating Ti generated on the surface of the anode rod 3+ The chemical dissolution of the impurity elements in the crude titanium is not caused, and the impurity elements remain in the anode scrap, thereby improving the refining effect of the impurity elements compared with the conventional technique.
The beneficial effects of the invention are as follows:
the anode device adopts the inert anode rod made of the conductive material as an anode electrode, and the titanium raw material is indirectly dissolved, so that the problem that partial near-potential impurities and titanium are dissolved together and deposited due to the fact that the titanium raw material is directly adopted as an anode is solved, and the refining coefficient of the impurities is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are necessary for the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention and that other embodiments may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural view of an anode device according to the present invention.
Fig. 2 is a cross-sectional view of an anode assembly AA of the present invention.
FIG. 3 is a schematic view of an electrolytic device according to the present invention.
FIG. 4 is a graph showing the free energy of Gibbs and temperature of each component of an electrolyzer of the present invention in electrorefining titanium.
Wherein, 10-anode rod, 20-charging basket, 21-outer cylinder, 22-inner cylinder, 23-outer cylinder through hole, 24-inner cylinder through hole, 25-bottom plate, 26-charging cavity, 30-top plate, 40-cathode, 50-molten salt container.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
It should be noted that, in the embodiments of the present invention, all the expressions "first" and "second" are used to distinguish two entities with the same name but different entities or different parameters, and it is noted that the "first" and "second" are merely used for convenience of expression, and should not be construed as limiting the embodiments of the present invention, and the following embodiments are not described one by one.
Example 1
As shown in fig. 1 to 2, an anode assembly of the present embodiment includes an anode rod 10 and a charging basket 20; the specific structure is as follows:
the charging basket 20 comprises an inner cylinder 22 and an outer cylinder 21 which are made of boron nitride, and the inner cylinder 22 is sleeved in the outer cylinder 21 at intervals; the bottom ends of the inner cylinder 22 and the outer cylinder 21 are fixed on a bottom plate 25 made of boron nitride, and the top ends of the inner cylinder 22 and the outer cylinder 21 are fixed on a top plate 30; the inner cylinder 22, the outer cylinder 21, the top plate 30 and the bottom plate 25 form a charging cavity 26, the cylinder walls of the inner cylinder 22 and the outer cylinder 21 are provided with an inner cylinder through hole 24 and an outer cylinder through hole 23, and the opening rates of the inner cylinder and the outer cylinder are 60 percent;
the anode rod 10 is made of graphite, the cross section of the anode rod is circular, and the middle part of the anode rod 10 is fixed on the top plate 30; the bottom end of the anode rod 10 extends into the inner cylinder 22 through the top plate 30, and the anode rod 10 located in the inner cylinder 22 is not in contact with the inner cylinder 22;
raw material coarse titanium is arranged in the charging cavity 26, and is one or more of titanium sponge, waste titanium material, titanium powder and the like; the raw titanium is loosely packed in the charge cavity 26 so as to be permeable to electrolyte.
Example 2
As shown in fig. 3, an apparatus for electrorefining titanium of the present embodiment includes the above-mentioned anode apparatus, which is placed in a molten salt container 50 containing molten salt electrolyte, and constitutes an electrolysis apparatus with a cathode 40 made of a conductive material; the molten salt electrolyte is NaCl-KCl-TiCl 2 A chloride molten salt electrolyte comprising 1wt% or more of Ti 2+ 。
The method for electrolytically refining titanium by the anode assembly of this example 1 comprises the steps of:
the anode device is placed in a fused salt container 50 for containing a chloride fused salt electrolyte, wherein the chloride fused salt electrolyte is NaCl-KCl-TiCl 2 Comprising 1wt% or more of Ti 2+ The method comprises the steps of carrying out a first treatment on the surface of the The anode device and the cathode 40 made of conductive materials form an electrolytic cell, the electrolytic principle is shown in figure 3, the power is turned on to electrolyze at 900 ℃, and high-purity titanium is collected at the cathode 40.
Compared with the prior art, ti 3+ The method does not react with V, cr, zr, fe and other impurity elements in raw material crude titanium in a temperature range controlled by the method, so that the quantity of the impurities entering an electrolyte can be effectively reduced, and the refining coefficient of the corresponding impurities is improved to more than 95%; in addition, based on the above characteristics, crude titanium having a high impurity content such as V, cr, zr, fe can be used as a raw material to obtain high purity titanium having a purity of 5N or more.
It should be noted that, each component or step in each embodiment may be intersected, replaced, added, and deleted, and therefore, the combination formed by these reasonable permutation and combination transformations shall also belong to the protection scope of the present invention, and shall not limit the protection scope of the present invention to the embodiments.
The foregoing is an exemplary embodiment of the present disclosure, and the order in which the embodiments of the present disclosure are disclosed is merely for the purpose of description and does not represent the advantages or disadvantages of the embodiments. It should be noted that the above discussion of any of the embodiments is merely exemplary and is not intended to suggest that the scope of the disclosure of embodiments of the invention (including the claims) is limited to these examples and that various changes and modifications may be made without departing from the scope of the invention as defined in the claims. The functions, steps and/or actions of the method claims in accordance with the disclosed embodiments described herein need not be performed in any particular order. Furthermore, although elements of the disclosed embodiments may be described or claimed in the singular, the plural is contemplated unless limitation to the singular is explicitly stated.
Those of ordinary skill in the art will appreciate that: the above discussion of any embodiment is merely exemplary and is not intended to imply that the scope of the disclosure of embodiments of the invention, including the claims, is limited to such examples; combinations of features of the above embodiments or in different embodiments are also possible within the idea of an embodiment of the invention, and there are many other variations of the different aspects of the embodiments of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, equivalent substitutions, improvements, and the like, which are made within the spirit and principles of the embodiments of the invention, are included within the scope of the embodiments of the invention.
Claims (10)
1. An anode assembly comprising an anode stem and a charging basket; wherein,
the charging basket comprises an inner cylinder and an outer cylinder, and the inner cylinder is sleeved in the outer cylinder at intervals; the bottom ends of the inner cylinder and the outer cylinder are fixed on the bottom plate, and the top ends of the inner cylinder and the outer cylinder are fixed on the top plate; the inner cylinder, the outer cylinder, the top plate and the bottom plate form a charging cavity, and through holes are formed in the cylinder walls of the inner cylinder and the outer cylinder;
the middle part of the anode rod is fixed on the top plate, the bottom end of the anode rod passes through the top plate and extends into the inner cylinder, and the anode rod in the inner cylinder is not in contact with the inner cylinder;
raw material coarse titanium is arranged in the charging cavity.
2. An anode assembly according to claim 1, wherein the anode stem is graphite.
3. An anode assembly according to claim 1 wherein the materials of the inner and outer cylinders and the base plate are insulating materials.
4. An anode assembly according to claim 3, wherein said insulating material is boron nitride.
5. An anode assembly according to claim 1, wherein the opening ratio of the inner and outer cylinders is 50-70%.
6. An anode assembly according to claim 1, wherein the charging cavity is provided with one or more of titanium sponge, waste titanium material, titanium powder, etc.
7. An electrolysis apparatus for refining titanium according to any one of claims 1 to 6, wherein the anode apparatus is placed in a molten salt container containing molten salt electrolyte and is formed into an electrolysis apparatus with a cathode made of conductive material; the molten salt electrolyte is a chloride molten salt electrolyte and contains more than 1wt% of Ti 2+ 。
8. A method of refining titanium using an anode assembly of claim 1, comprising the steps of:
placing the anode device in a molten salt container for containing molten salt electrolyte, forming an electrolytic cell with a cathode made of conductive materials, switching on a power supply for electrolysis, and collecting high-purity titanium at the cathode.
9. The method of claim 8, wherein the electrolysis temperature ranges from 800 to 1000 ℃.
10. The method of claim 8 wherein the molten salt electrolyte is a chloride molten salt electrolyte comprising greater than 1wt% Ti 2+ 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311221218.5A CN117051444A (en) | 2023-09-20 | 2023-09-20 | Anode device, electrolysis device and method for refining titanium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311221218.5A CN117051444A (en) | 2023-09-20 | 2023-09-20 | Anode device, electrolysis device and method for refining titanium |
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| Publication Number | Publication Date |
|---|---|
| CN117051444A true CN117051444A (en) | 2023-11-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311221218.5A Pending CN117051444A (en) | 2023-09-20 | 2023-09-20 | Anode device, electrolysis device and method for refining titanium |
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| Country | Link |
|---|---|
| CN (1) | CN117051444A (en) |
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2023
- 2023-09-20 CN CN202311221218.5A patent/CN117051444A/en active Pending
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