CN115947602B - ZrB (ZrB) 2 Metal ceramic-based inert anode and preparation method and application thereof - Google Patents
ZrB (ZrB) 2 Metal ceramic-based inert anode and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 27
- 239000003792 electrolyte Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000011195 cermet Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000002457 bidirectional effect Effects 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 29
- 150000003839 salts Chemical class 0.000 abstract description 15
- 239000010953 base metal Substances 0.000 abstract description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 11
- 229910018054 Ni-Cu Inorganic materials 0.000 description 6
- 229910018481 Ni—Cu Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a ZrB 2 A base metal ceramic inert anode, a preparation method and application thereof; the method utilizes ceramic component ZrB with better conductivity 2 (conductivity 1X 10) 4 S/cm‑1.2×10 5 S/cm) is a ceramic phase, cu (Ni) with better toughness is used as a metal phase to prepare the metal ceramic inert anode, the good conductivity of the metal ceramic inert anode is maintained, the molten salt corrosion resistance of the inert anode is improved, and the cathode raw aluminum also has higher purity.
Description
Technical Field
The invention relates to a ZrB 2 A base high-conductivity high-temperature-resistant molten salt corrosion-resistant metal ceramic inert anode and a preparation method and application thereof belong to the technical field of aluminum electrolysis.
Background
ZrB 2 Due to its good conductivity (conductivity 1X 10 4 S/cm-1.2×10 5 S/cm) and resistance to corrosion by high temperature molten salts are now of increasing interest. Inert metal ceramicIn order to achieve the balance of compactness, mechanical property, conductivity and high-temperature molten salt corrosion resistance, ceramic components are often added into the anode to withstand high-temperature molten salt corrosion, and then high-content metal components are added to improve the conductivity of the metal ceramic, so that the metal ceramic inert anode is preferentially corroded in the electrolysis process, a large number of micropores are formed in the surface of the metal ceramic inert anode, a permeation channel is provided for high-temperature molten salt electrolyte, and the corrosion of the metal ceramic inert anode is serious. Although coating the surface of the metal phase with a certain amount of spinel oxide powder may be used to avoid preferential corrosion of the metal phase in the high temperature molten salt compared to the ceramic phase (201110146867.4); or controlling certain electrolytic corrosion conditions to ensure that the metal ceramic inert anode reaches dynamic corrosion balance (201210066342.4) of the surface compact spinel type oxide ceramic corrosion and the continuous formation of a new compact spinel type oxide ceramic layer inside the metal ceramic inert anode, but has little effect on large-scale aluminum electrolysis.
Disclosure of Invention
Aiming at the defects of the prior aluminum electrolysis inert anode, the invention aims to provide a ZrB 2 A base metal ceramic inert anode, a preparation method and application thereof.
Due to ZrB 2 The conductivity of the ceramic is 1 multiplied by 10 4 S/cm-1.2×10 5 S/cm, compared with common aluminum electrolysis inert anode NiFe 2 O 4 The electrical conductivity of NiO-Cu/Ni is 10-100S/cm, which is improved by three orders of magnitude; zrB 2 The high conductivity of the ceramic can greatly reduce the Cu/Ni metal content in the cermet, and a large number of holes are not generated on the surface of the anode due to preferential corrosion of a large number of Cu/Ni metals in the aluminum electrolysis process, so that the electrolyte can be quickly permeated to cause premature failure of the anode. And ZrB 2 The ceramic can also resist high temperature molten salt corrosion, thus ZrB 2 The metal ceramic can reach the balance of the conductivity and the high-temperature molten salt corrosion resistance of the metal ceramic inert anode.
In order to achieve the technical purpose, the invention aims at being realized by the following technical means.
ZrB (ZrB) 2 Base metal ceramicCeramic inert anode: comprises ZrB 2 A major ceramic component, and a Cu and/or Ni metal phase with better toughness.
Further, the ZrB 2 An inert anode of metal ceramic, wherein the proportion of each component comprises ZrB 2 90-95% of metal phase and 5-10% of metal phase.
ZrB according to the invention 2 The preparation method of the metal ceramic-based inert anode comprises the following steps: firstly weighing ZrB 2 Ball-milling and mixing Cu and/or Ni powder in a ball-milling medium containing a dispersing agent and a binder, and (3) drying the mixed powder, pressing and forming the mixed powder into a green body, and finally sintering the green body in a protective atmosphere to obtain the finished product.
Further, the dispersing agent is at least one of water, ethanol and methanol; the binder is at least one of polyvinyl alcohol and polyethylene glycol.
Further: the grinding ball material comprises: steel balls or zirconium balls; the diameter is 1-5cm; ball material ratio is 1:1-1:2, ball milling and mixing are carried out for 120-150min.
Further, the mixed powder is dried and then is formed by bidirectional compression molding under the pressure of 100-300MPaIs a green body of (c).
Further, the sintering temperature is 1150-1400 ℃ and the sintering time is 2-6h.
The invention also provides the ZrB 2 The application method of the metal ceramic-based inert anode is used for aluminum electrolysis or rare earth electrolysis.
Further, the electrolyte comprises the following components in percentage by mass during electrolysis: na (Na) 3 AlF 6 And/or K 3 AlF 6 60～80％，AlF 3 5～30％，CaF 2 ≤10％，Al 2 O 3 3～5％。
Further, the condition parameters at the time of electrolysis range: (1) depth of immersion of anode into electrolyte: 1-4cm; (2) cathode aluminum: the height is 1.5-3.5cm; (3) anode bottom current density: 0.8-1.1A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the (4) pole pitch: 2-4cm; (5) electrolyte level: 5-9cm; (6) electrolysis temperature:800-960 ℃. The electrolysis time is not less than 10 hours.
ZrB of the invention 2 The base high-conductivity high-temperature-resistant molten salt corrosion-resistant metal ceramic inert anode is ZrB with better conductivity 2 The ceramic component takes Cu (Ni) with better toughness as a metal phase, improves the conductivity of the metal ceramic inert anode and improves the molten salt corrosion resistance of the inert anode.
The technical principle of the invention has the beneficial technical effects compared with the prior art:
principle of: a large number of researches show that the ZrB with good conductivity is prepared at the temperature and the current density of the invention 2 The ceramic is a metal ceramic inert anode prepared by ceramic phase, and then is put into proper electrolyte for electrolytic corrosion, and because the metal components in the metal ceramic inert anode are less, zrB is simultaneously carried out 2 The ceramic has good conductivity, and ZrB is used in the aluminium electrolysis process 2 The metal-based cermet inert anode will be compared with NiFe 2 O 4 The NiO metal ceramic inert anode has improved conductivity and molten salt corrosion resistance, can effectively slow down the anode corrosion speed, and meanwhile, has fewer anode components dissolved in electrolyte and less amount of elemental metal generated in cathode discharge, thereby keeping the original cathode aluminum of the anode to have higher purity.
If it is less than 90% ZrB 2 The anode has poor conductivity, high cell voltage and high energy consumption in the electrolysis process.
If more kinds of metals are doped, the effect is not improved, and the impurities in the original aluminum are more, which is unfavorable for the purity of the original aluminum.
The beneficial effects are that: (1) The technical proposal of the invention can simultaneously improve the conductivity and corrosion resistance of the metal ceramic inert anode for aluminum electrolysis and the purity of the original aluminum, and solves the problems of NiFe at present 2 O 4 The problems of reduced conductivity, improved resistance to molten salt corrosion of the anode, and the like caused by preferential corrosion of metal due to excessive Cu (Ni) metal content of the NiO-Cu (Ni) cermet inert anode in the aluminum electrolysis process. (2) The technical scheme of the invention has simple and convenient process and is easy to popularize and apply.
Detailed Description
The following examples are presented to further illustrate the invention and are not intended to limit the scope of the invention as claimed.
Example 1
Firstly weighing ZrB according to a proportion 2 And Cu or/and Ni powder, ball milling and mixing for 120min in a ball milling medium containing dispersant absolute ethyl alcohol and binder polyethylene glycol, wherein the diameter range is 1-3cm; ball-material ratio 1:1, and the mixed powder is formed by bidirectional compression molding under 200MPa pressure after being driedFinally, the green body is placed in an electric furnace, and the green body is placed in N 2 Sintering for 3h at 1400 ℃ according to a certain heating system in the atmosphere to obtain a ceramic inert anode sample 5 (20 Ni-Cu)/95 ZrB with a regular shape 2 。
5(20Ni-Cu)/95ZrB 2 (20% Ni and 80% Cu constitute the metallic phase, 5% metallic phase and 95% ZrB) 2 Constituting a ceramic inert anode) and 5 (20 Ni-Cu)/95 (NiFe 2 O 4 -10 NiO) (20% Ni and 80% Cu constitute the metallic phase, 90% NiFe 2 O 4 And 10% NiO constitute the ceramic phase, 5% of the metal phase and 95% of the ceramic phase constitute the ceramic inert anode) and 5 (20 Ni-Cu)/95 (NiFe) 2 O 4 -10NiO-10ZrB 2 ) (20% Ni and 80% Cu constitute the metallic phase, 80% NiFe) 2 O 4 And 10% NiO and 10% ZrB 2 Constitute a ceramic phase, 5% of the metal phase and 95% of the ceramic phase constitute a ceramic inert anode) the ceramic inert anode, the conductivity at 960 ℃ being 168.2S/cm, 52.5S/cm and 75.6S/c, respectively; at electrolyte 78.07% Na 3 AlF 6 -9.5％AlF 3 -5.0％CaF 2 -7.43％Al 2 O 3 Medium (primary crystal temperature 947 ℃, superheat degree 13 ℃) and current density of 0.98A/cm 2 ) Electrolysis for 120h (electrolysis temperature 960 ℃); depth of anode immersed in electrolyte: 2cm, cathode aluminum: height 2.5cm, pole pitch: 3cm, electrolyte level: after 5cm, it was found that 5 (20 Ni-Cu)/95 ZrB 2 The anode corrosion rate was 0.64 cm/year -1 ，5(20Ni-Cu)/95(NiFe 2 O 4 -10 NiO) with a corrosion rate of 1.23 cm-year -1 ，5(20Ni-Cu)/95(NiFe 2 O 4 -10NiO-10ZrB 2 ) The corrosion rate is 0.96 cm-year -1 . The purity of the raw aluminum is 99.5wt%, 98.8wt% and 99.1wt%, respectively. Description ZrB 2 The metal ceramic can improve the high-temperature conductivity and high-temperature molten salt corrosion resistance of the metal ceramic inert anode. W (W) loss ＝(W b ×C b +W a ×C a )×10 -6 ×365×24/(s Anode ×ρ Anode ×t)(1)
W in (1) loss Defined as the annual rate of corrosion of the anode (cm. Year) -1 )，W b C is the total electrolyte (g) b W for impurity concentration (ppm) into electrolyte a C is the total amount (g) of cathode aluminum a To enter the concentration (ppm) of impurities in the cathode aluminum liquid, the sAnode is the surface area (cm) of the anode immersed during electrolysis 2 ) ρanode is the volume density (g/cm) of the anode 3 ) T is the electrolysis time (h).
Example 2:
10(20Ni-Cu)/90ZrB 2 the preparation method is the same as in example 1
10(20Ni-Cu)/90ZrB 2 And 10 (20 Ni-Cu)/90 (NiFe) 2 O 4 -10 NiO) cermet inert anode having conductivities at 183.7S/cm and 69.2S/cm, respectively, at 910 ℃; at low temperature electrolyte 23.4K 3 AlF 6 -54.6Na 3 AlF 6 -22.5％AlF 3 -5.0％Al 2 O 3 Middle (primary crystal temperature 890 ℃, superheat 20 ℃ and current density 1.0A/cm) 2 ) Electrolysis for 120h (electrolysis temperature 910 ℃); depth of anode immersed in electrolyte: 2cm, cathode aluminum: height 2.5cm, pole pitch: 3cm, electrolyte level: after 5cm, it was found that 10 (20 Ni-Cu)/90 ZrB 2 The anode corrosion rate was 0.71 cm/year -1 ，10(20Ni-Cu)/90(NiFe 2 O 4 -10 NiO) with a corrosion rate of 1.48 cm-year -1 . The purity of the raw aluminum was 99.3wt% and 98.7wt%, respectively. Description ZrB 2 The metal ceramic can improve the high-temperature conductivity and high-temperature molten salt corrosion resistance of the metal ceramic inert anode.
Claims (9)
1. ZrB (ZrB) 2 The metal ceramic-based inert anode is characterized in that: comprises ZrB 2 A ceramic component mainly, and a Cu and/or Ni metal phase with better toughness; the ratio of each component comprises ZrB 2 90% -95% of metal phase and 5% -10% of metal phase.
2. ZrB according to claim 1 2 The preparation method of the metal ceramic-based inert anode is characterized by comprising the following steps of: the method comprises the following steps: firstly weighing ZrB 2 Ball-milling and mixing Cu and/or Ni powder in a ball-milling medium containing a dispersing agent and a binder, and (3) drying the mixed powder, pressing and forming the mixed powder into a green body, and finally sintering the green body in a protective atmosphere to obtain the finished product.
3. The preparation method according to claim 2, characterized in that: the dispersing agent is at least one of water, ethanol and methanol; the binder is at least one of polyvinyl alcohol and polyethylene glycol.
4. The preparation method according to claim 2, characterized in that: the grinding ball material comprises: steel balls or zirconium balls; the diameter is 1-5cm; ball material ratio is 1:1-1:2, ball milling and mixing are carried out for 120-150min.
5. The preparation method according to claim 2, characterized in that: and drying the mixed powder, and performing bidirectional compression molding under the pressure of 100-300MPa to obtain a green body with phi 20mm multiplied by 40 mm.
6. The preparation method according to claim 2, characterized in that: the sintering temperature is 1150-1400 ℃ and the sintering time is 2-6h.
7. ZrB according to claim 1 2 An inert anode based on cermet or ZrB prepared by the method of any one of claims 2-6 2 The application method of the metal ceramic-based inert anode is characterized by comprising the following steps of: is used for aluminum electrolysis or rare earth electrolysis.
8. The application method according to claim 7, wherein the electrolyte comprises the following components in percentage by mass during electrolysis: na (Na) 3 AlF 6 And/or K 3 AlF 6 60~80%，AlF 3 5~30%，CaF 2 ≤10%，Al 2 O 3 3~5%。
9. The method of claim 7, wherein the range of parameters of the electrolysis conditions is: (1) depth of immersion of anode into electrolyte: 1-4cm; (2) cathode aluminum; (3) anode bottom current density: 0.8-1.1A/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the (4) pole pitch: 2-4cm; (5) electrolyte level: 5-9cm; (6) electrolysis temperature: 800-960 ℃.
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| Preparation of ZrB2-based nanocomposites with limited grain growth by means of low-temperature hot-pressing using Cu additive;Rujie He et al.;International Journal of Materials Research;第104卷(第10期);第1034-1035页 * |
| Processing and properties of ZrB2-Cu composites sintered by Hot-pressing sintering;Wei Shang et al.;Key Engineering Materials;447-450 * |
| 化学镀铜制备ZrB2-Cu复合粉末的工艺研究;朱时珍 等;稀有金属材料与工程;第42卷;614-617 * |
| 硼化物陶瓷及其复合材料的研究进展;贾成科;张鑫;彭浩然;谢旭霞;任先京;;热喷涂技术(第01期);全文 * |
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