CN101935853A - Alloy oxygen evolution anode for aluminum electrolysis - Google Patents
Alloy oxygen evolution anode for aluminum electrolysis Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 92
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 85
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 70
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 20
- 239000001301 oxygen Substances 0.000 title claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 15
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- -1 or Hf Inorganic materials 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 230000035939 shock Effects 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001610 cryolite Inorganic materials 0.000 abstract description 2
- 230000003628 erosive effect Effects 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 229910016569 AlF 3 Inorganic materials 0.000 description 7
- 229910004261 CaF 2 Inorganic materials 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000004663 powder metallurgy Methods 0.000 description 4
- 239000011195 cermet Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017060 Fe Cr Inorganic materials 0.000 description 2
- 229910002544 Fe-Cr Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
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Abstract
一种铝电解用合金析氧阳极材料，涉及有色金属冶金熔盐电解技术领域。本发明的新型析氧阳极为高Cr含量的M-Cr-R合金材料，其中，M是Fe、或Ni、或Co金属或由它们组成的合金；R是Al、或Zr、或Y、或Hf、或稀土金属、或它们的氧化物。合金阳极材料的组成范围：Cr为25～90wt％，R为0.001～1wt％，余量为M。在电解过程中，M-Cr-R合金析氧阳极表面生成了连续、致密、具有自我修复能力的Cr2O3膜或富Cr的复合氧化膜，使M-Cr-R合金阳极具有良好的抗氧化性和抵御冰晶石熔盐侵蚀的性能，具有较长的使用寿命，获得电解铝产品中的杂质含量可低于0.3wt％。M-Cr-R合金阳极材料还具有强度高、导电性好、抗热震性好、易于加工、易于导电杆连接等特点。因此，本发明的M-Cr-R合金析氧阳极在铝电解工业中具有广泛的应用前景。An alloy oxygen-evolving anode material for aluminum electrolysis relates to the technical field of non-ferrous metal metallurgy molten salt electrolysis. The novel oxygen-evolving anode of the present invention is M-Cr-R alloy material with high Cr content, wherein, M is Fe, or Ni, or Co metal or an alloy composed of them; R is Al, or Zr, or Y, or Hf, or rare earth metals, or their oxides. The composition range of the alloy anode material: Cr is 25-90wt%, R is 0.001-1wt%, and the balance is M. During the electrolysis process, a continuous, dense, self-healing Cr 2 O 3 film or a Cr-rich composite oxide film is formed on the surface of the M-Cr-R alloy oxygen evolution anode, which makes the M-Cr-R alloy anode have good The performance of resisting oxidation and cryolite molten salt erosion has a long service life, and the impurity content in the obtained electrolytic aluminum product can be lower than 0.3wt%. The M-Cr-R alloy anode material also has the characteristics of high strength, good electrical conductivity, good thermal shock resistance, easy processing, and easy connection of conductive rods. Therefore, the M-Cr-R alloy oxygen evolution anode of the present invention has broad application prospects in the aluminum electrolysis industry.
Description
技术领域technical field
本发明涉及有色金属冶金熔盐电解技术领域，主要涉及一种用于铝电解工业的新型合金析氧阳极。The invention relates to the technical field of molten salt electrolysis of non-ferrous metal metallurgy, and mainly relates to a novel alloy oxygen evolution anode used in the aluminum electrolysis industry.
背景技术Background technique
Hall-Héroult炼铝法作为现今唯一的工业炼铝法主要是利用冰晶石-氧化铝熔盐体系电解生产铝。以炭素材料分别作为阴阳极，通入直流电在930℃～960℃进行电解，炭阳极发生电化学反应析出CO2，阴极沉积得到金属铝。炭素阳极属于消耗型阳极，实际生产中，每生产一吨铝则需要消耗400～415kg的炭阳极。炭素阳极材料的费用大约占了整个铝生产成本的12～15％。在电解过程中释放大量温室气体CO2、CO、CF4和C2F4等氟碳化合物，严重污染大气。The Hall-Héroult aluminum smelting method, as the only industrial aluminum smelting method today, mainly uses the cryolite-alumina molten salt system to produce aluminum by electrolysis. The carbon material is used as the anode and cathode respectively, and direct current is passed through to carry out electrolysis at 930°C to 960°C. The carbon anode undergoes an electrochemical reaction to precipitate CO 2 , and the cathode deposits to obtain metal aluminum. Carbon anodes are consumable anodes. In actual production, 400-415kg of carbon anodes are required to produce one ton of aluminum. The cost of carbon anode materials accounts for about 12-15% of the entire aluminum production cost. During the electrolysis process, a large amount of fluorocarbons such as CO 2 , CO, CF 4 and C 2 F 4 are released, seriously polluting the atmosphere.
一百多年来，人们一直在研究取代消耗型炭素阳极的析氧阳极。析氧阳极的主反应是O2的析出，电极消耗很慢。可以彻底消除CO2、CO以及CF4、C2F4等氟碳化合物的排放，有利于保护环境。析氧阳极材料主要包括三种类型，陶瓷材料、金属陶瓷材料和合金材料。陶瓷材料具有优异的抗熔盐腐蚀性能，但较差的导电性以及抗热震性能限制了它的应用。金属陶瓷材料兼顾了陶瓷的抗腐蚀性和金属的导电性，但材料的抗热震性、与导电杆的连接等问题，阻碍了其工业化应用。相比于陶瓷、金属陶瓷材料，合金材料具有强度高、导电性好、机械加工性能好等优点，是最近几年阳极材料的研究重点。合金作为阳极材料的关键是在电极与熔盐电解质界面上形成致密、连续、粘附性好且具有良好导电性能的氧化物保护层。电解过程中，电解质中的氧离子在合金氧化膜的表面放电，析出氧气，同时伴随少量氧化物的溶解。For more than 100 years, people have been studying oxygen evolution anodes to replace consumable carbon anodes. The main reaction of the oxygen evolution anode is the evolution of O 2 , and the electrode consumption is very slow. It can completely eliminate the emission of CO 2 , CO and fluorocarbons such as CF 4 and C 2 F 4 , which is beneficial to protect the environment. Oxygen evolution anode materials mainly include three types, ceramic materials, cermet materials and alloy materials. Ceramic materials have excellent resistance to molten salt corrosion, but poor electrical conductivity and thermal shock resistance limit its application. Cermet materials take into account the corrosion resistance of ceramics and the electrical conductivity of metals, but the thermal shock resistance of materials and the connection with conductive rods hinder their industrial application. Compared with ceramics and cermet materials, alloy materials have the advantages of high strength, good electrical conductivity, and good machinability, and are the focus of research on anode materials in recent years. The key to alloys as anode materials is to form a dense, continuous, well-adhesive and conductive oxide protective layer on the interface between the electrode and the molten salt electrolyte. During the electrolysis process, the oxygen ions in the electrolyte are discharged on the surface of the alloy oxide film, and oxygen is precipitated, accompanied by the dissolution of a small amount of oxide.
中国专利“金属基铝电解惰性阳极及其制备方法”(专利公开号：1443877A)描述了各种组成合金阳极材料。该专利中描述的合金材料包括了先前研究中已证明不具有惰性性能的材料，如Fe、Ni、Cu材料等。同时，也包括了某些根本不可能实现的阳极材料，如Al-Zn合金等；该合金的熔点低于660℃，而实际铝电解生产的工作温度都要高于800℃，因此该合金材料在实际应用中根本无法实现。该专利中所提供的合金中Cr的含量均小于22wt.％，没有给出高Cr含量合金阳极的任何可以具体实施的信息。The Chinese patent "Metal-Based Aluminum Electrolytic Inert Anode and Its Preparation Method" (Patent Publication No.: 1443877A) describes various alloy anode materials. The alloy materials described in this patent include materials that have been proven not to have inert properties in previous studies, such as Fe, Ni, Cu materials, etc. At the same time, it also includes some anode materials that are impossible to realize, such as Al-Zn alloy; It is simply impossible to achieve in practical applications. The content of Cr in the alloys provided in this patent is all less than 22wt.%, without giving any practical information on alloy anodes with high Cr content.
发明内容Contents of the invention
本发明提出一种新型的铝电解用合金析氧阳极材料。The invention proposes a novel alloy oxygen-evolving anode material for aluminum electrolysis.
本发明的新型合金析氧阳极为高Cr含量的M-Cr-R合金材料，其中，M是Fe、或Ni、或Co金属或由它们组成的合金；R是Zr、或Y、或Hf、或镧系稀土金属、或它们的氧化物；合金阳极材料的组成范围：Cr为25～90wt％，R为0.001～1wt％，余量为M。The novel alloy oxygen evolution anode of the present invention is M-Cr-R alloy material with high Cr content, wherein, M is Fe, or Ni, or Co metal or an alloy composed of them; R is Zr, or Y, or Hf, Or lanthanide rare earth metals, or their oxides; the composition range of the alloy anode material: Cr is 25-90wt%, R is 0.001-1wt%, and the balance is M.
该合金材料在电解的条件下，通过合金元素的氧化，在阳极的表面生成完整、均匀、致密的Cr2O3膜或富Cr的复合氧化膜。以Fe-Cr合金为例，在电解过程中，合金阳极中的Fe，Cr元素同时向合金表面扩散，形成了FeCr2O4尖晶石结构的氧化膜；在Fe-Cr合金中，再添加Ni或Co金属元素可以抑制Fe元素的往合金表面扩散，促进合金中Cr元素发生选择性氧化，在合金表面形成单一的Cr2O3膜。在Ni-Cr合金体系中，由于合金中Ni元素在合金中的扩散速度较慢，使Cr元素发生选择性氧化，合金表面生成的氧化膜为Cr2O3膜。The alloy material forms a complete, uniform and dense Cr 2 O 3 film or a Cr-rich composite oxide film on the surface of the anode through the oxidation of alloy elements under electrolysis conditions. Taking Fe-Cr alloy as an example, during the electrolysis process, the Fe and Cr elements in the alloy anode diffuse to the alloy surface at the same time, forming an oxide film with a FeCr 2 O 4 spinel structure; in the Fe-Cr alloy, adding Ni or Co metal elements can inhibit the diffusion of Fe elements to the alloy surface, promote the selective oxidation of Cr elements in the alloy, and form a single Cr 2 O 3 film on the alloy surface. In the Ni-Cr alloy system, due to the slow diffusion rate of the Ni element in the alloy, the Cr element is selectively oxidized, and the oxide film formed on the surface of the alloy is Cr 2 O 3 film.
本发明的高Cr含量的M-Cr-R合金析氧阳极，在冰晶石-氧化铝熔盐体系中电解过程中，电极表面可以保持完整、均匀、致密的Cr2O3膜或富Cr的复合氧化膜。该氧化膜在冰晶石-氧化铝熔盐体系中的溶解度较小，例如，在1000℃，含Al2O35wt％的冰晶石-氧化铝熔盐体系中电解，熔盐中溶解的各种物质的含量为：Cr2O30.05wt％，NiO0.18wt％，Co3O40.14wt％，Fe2O30.003wt％。铝电解时，氧化膜发生不断的溶解，合金中高含量的成膜元素Cr可以扩散到合金表面形成新的Cr2O3膜或富Cr的复合氧化膜。这保证了Cr2O3膜或富Cr的复合氧化膜具有良好抵御冰晶石电解质侵蚀的性能。因此，本发明提出的高Cr含量的M-Cr-R合金析氧阳极表面形成的Cr2O3膜或富Cr的复合氧化膜在电解过程中具有“自我修复”能力。同时，Cr2O3膜是一种p型半导体材料，在电解过程中具有良好的电导性能。在本发明中，通过往合金中添加少量的Y、或Zr、或Hf、或镧系稀土金属、或它们的氧化物来产生活性元素效应，促进合金中Cr元素的选择性氧化，细化氧化膜的晶粒，提高氧化膜与合金基体的结合力。合金析氧阳极材料属于金属材料，其机械加工性能以及导电性良好，使得阳极的外形加工以及导电杆的连接变的相对的简单。同时，合金阳极材料可以采用工艺简单的合金熔炼法和粉末冶金法制备，生产成本大大减低，使其在铝电解工业中具有广泛的应用前景。The M-Cr-R alloy oxygen-evolving anode with high Cr content of the present invention can maintain a complete, uniform and dense Cr2O3 film or Cr-rich film on the surface of the electrode during the electrolysis process in the cryolite-alumina molten salt system. Composite oxide film. The solubility of the oxide film in the cryolite-alumina molten salt system is small. For example, at 1000°C, electrolysis in the cryolite-alumina molten salt system containing 5wt% Al 2 O 3 The contents of substances are: Cr 2 O 3 0.05wt%, NiO 0.18wt%, Co 3 O 4 0.14wt%, Fe 2 O 3 0.003wt%. During aluminum electrolysis, the oxide film is continuously dissolved, and the high-content film-forming element Cr in the alloy can diffuse to the surface of the alloy to form a new Cr 2 O 3 film or a Cr-rich composite oxide film. This ensures that the Cr 2 O 3 film or the Cr-rich composite oxide film has good performance against cryolite electrolyte erosion. Therefore, the Cr 2 O 3 film or Cr-rich composite oxide film formed on the surface of the M-Cr-R alloy oxygen evolution anode with high Cr content proposed by the present invention has the ability of "self-repair" during the electrolysis process. At the same time, the Cr 2 O 3 film is a p-type semiconductor material, which has good electrical conductivity in the electrolysis process. In the present invention, the active element effect is produced by adding a small amount of Y, or Zr, or Hf, or lanthanide rare earth metals, or their oxides to the alloy, which promotes the selective oxidation of the Cr element in the alloy, and refines the oxidation. The crystal grains of the film improve the bonding force between the oxide film and the alloy matrix. The alloy oxygen evolution anode material is a metal material, and its machinability and electrical conductivity are good, which makes the shape processing of the anode and the connection of the conductive rod relatively simple. At the same time, the alloy anode material can be prepared by simple alloy melting method and powder metallurgy method, and the production cost is greatly reduced, so that it has a wide application prospect in the aluminum electrolysis industry.
具体实施方式Detailed ways
以下，将通过具体实施例对本发明做进一步描述。Hereinafter, the present invention will be further described through specific examples.
实施例1Example 1
Fe-50Cr-1Ce合金采用粉末冶金法制备。The Fe-50Cr-1Ce alloy is prepared by powder metallurgy.
电解用合金阳极的尺寸规格为40mm×25mm×10mm，在25mm×10mm面上端开Φ4mm×8mm的螺孔，合金阳极通过不锈钢导杆与直流电源连接。电解前，合金阳极在950℃的电解温度下氧化预处理2h。电解实验在阳极电流密度0.8A/cm2条件下进行100h，电解温度为950℃。电解试验的熔盐电解质采用NaF-AlF3体系，分子比为2.2，其余组成为CaF25wt％，Al2O35wt％。石墨为阴极。电解后收集到的铝产品测得纯度为99.15％。The size specification of the alloy anode for electrolysis is 40mm×25mm×10mm, and a screw hole of Φ4mm×8mm is opened on the surface of 25mm×10mm. The alloy anode is connected to the DC power supply through a stainless steel guide rod. Before electrolysis, the alloy anode was oxidized and pretreated at an electrolysis temperature of 950 °C for 2 h. The electrolysis experiment was carried out for 100h under the condition of anodic current density of 0.8A/cm 2 , and the electrolysis temperature was 950℃. The molten salt electrolyte used in the electrolysis test adopts the NaF-AlF 3 system, the molecular ratio is 2.2, and the rest composition is CaF 2 5wt%, Al 2 O 3 5wt%. Graphite is the cathode. The aluminum product collected after electrolysis has a measured purity of 99.15%.
实施例2Example 2
Ni-40Cr-0.5Ce合金采用真空熔炼法制备。Ni-40Cr-0.5Ce alloy is prepared by vacuum melting method.
电解用合金阳极的尺寸规格为40mm×25mm×10mm，在25mm×10mm面上端开Φ4mm×8mm的螺孔，合金阳极通过不锈钢导杆与直流电源连接。电解前，合金阳极在960℃的电解温度下氧化预处理2h。电解实验在阳极电流密度0.5A/cm2条件下进行200h，电解温度为960℃。电解试验的熔盐电解质采用NaF-AlF3体系，分子比为2.3，其余组成为CaF25wt％，Al2O35wt％。，石墨为阴极。电解后收集到的铝产品测得纯度为99.78％。The size specification of the alloy anode for electrolysis is 40mm×25mm×10mm, and a screw hole of Φ4mm×8mm is opened on the surface of 25mm×10mm. The alloy anode is connected to the DC power supply through a stainless steel guide rod. Before electrolysis, the alloy anode was oxidized and pretreated at an electrolysis temperature of 960 °C for 2 h. The electrolysis experiment was carried out for 200h under the condition of anodic current density of 0.5A/cm 2 , and the electrolysis temperature was 960℃. The molten salt electrolyte used in the electrolysis test uses the NaF-AlF 3 system, the molecular ratio is 2.3, and the rest composition is CaF 2 5wt%, Al 2 O 3 5wt%. , graphite as the cathode. The aluminum product collected after electrolysis has a measured purity of 99.78%.
实施例3Example 3
Co-30Cr-0.1CeO2合金采用真空熔炼法制备。Co-30Cr-0.1CeO 2 alloy was prepared by vacuum melting method.
电解用合金阳极的尺寸规格为40mm×25mm×10mm，在25mm×10mm面上端开Φ4mm×8mm的螺孔，合金阳极通过不锈钢导杆与直流电源连接。电解前，合金阳极在950℃的电解温度下氧化预处理2h。电解实验在阳极电流密度0.8A/cm2条件下进行100h，电解温度为950℃。电解试验的熔盐电解质采用NaF-AlF3体系，分子比为2.3，其余组成为CaF25wt％，Al2O35wt％。，石墨为阴极。电解后收集到的铝产品测得纯度为98.92％。The size specification of the alloy anode for electrolysis is 40mm×25mm×10mm, and a screw hole of Φ4mm×8mm is opened on the surface of 25mm×10mm. The alloy anode is connected to the DC power supply through a stainless steel guide rod. Before electrolysis, the alloy anode was oxidized and pretreated at an electrolysis temperature of 950 °C for 2 h. The electrolysis experiment was carried out for 100h under the condition of anodic current density of 0.8A/cm 2 , and the electrolysis temperature was 950℃. The molten salt electrolyte used in the electrolysis test uses the NaF-AlF 3 system, the molecular ratio is 2.3, and the rest composition is CaF 2 5wt%, Al 2 O 3 5wt%. , graphite as the cathode. The aluminum product collected after electrolysis has a measured purity of 98.92%.
实施例4Example 4
Fe-30Ni-35Cr-0.01Ce合金采用真空熔炼法制备。Fe-30Ni-35Cr-0.01Ce alloy is prepared by vacuum melting method.
电解用合金阳极的尺寸规格为40mm×25mm×10mm，在25mm×10mm面上端开Φ4mm×8mm的螺孔，合金阳极通过不锈钢导杆与直流电源连接。电解前，合金阳极在950℃的电解温度下氧化预处理2h。电解实验在阳极电流密度0.5A/cm2条件下进行200h，电解温度为950℃。电解试验的熔盐电解质采用NaF-AlF3体系，分子比为2.2，其余组成为CaF25wt％，Al2O35wt％。，石墨为阴极。电解后收集到的铝产品测得纯度为99.28％。The size specification of the alloy anode for electrolysis is 40mm×25mm×10mm, and a screw hole of Φ4mm×8mm is opened on the surface of 25mm×10mm. The alloy anode is connected to the DC power supply through a stainless steel guide rod. Before electrolysis, the alloy anode was oxidized and pretreated at an electrolysis temperature of 950 °C for 2 h. The electrolysis experiment was carried out for 200h under the condition of anodic current density of 0.5A/cm 2 , and the electrolysis temperature was 950℃. The molten salt electrolyte used in the electrolysis test adopts the NaF-AlF 3 system, the molecular ratio is 2.2, and the rest composition is CaF 2 5wt%, Al 2 O 3 5wt%. , graphite as the cathode. The aluminum product collected after electrolysis has a measured purity of 99.28%.
实施例5Example 5
Fe-25Co-35Cr-0.02Y2O3合金采用热等静压烧结技术制备。Fe-25Co-35Cr-0.02Y 2 O 3 alloy was prepared by hot isostatic pressing sintering technology.
电解用合金阳极的尺寸规格为40mm×25mm×10mm，在25mm×10mm面上端开Φ4mm×8mm的螺孔，合金阳极通过不锈钢导杆与直流电源连接。电解前，合金阳极在960℃的电解温度下氧化预处理2h。电解实验在阳极电流密度0.5A/cm2条件下进行100h，电解温度为960℃。电解试验的熔盐电解质采用NaF-AlF3体系，分子比为2.3，其余组成为CaF25wt％，Al2O35wt％。，石墨为阴极。电解后收集到的铝产品测得纯度为98.82％。The size specification of the alloy anode for electrolysis is 40mm×25mm×10mm, and a screw hole of Φ4mm×8mm is opened on the surface of 25mm×10mm. The alloy anode is connected to the DC power supply through a stainless steel guide rod. Before electrolysis, the alloy anode was oxidized and pretreated at an electrolysis temperature of 960 °C for 2 h. The electrolysis experiment was carried out for 100h under the condition of anodic current density of 0.5A/cm 2 , and the electrolysis temperature was 960℃. The molten salt electrolyte used in the electrolysis test uses the NaF-AlF 3 system, the molecular ratio is 2.3, and the rest composition is CaF 2 5wt%, Al 2 O 3 5wt%. , graphite as the cathode. The aluminum product collected after electrolysis has a measured purity of 98.82%.
实施例6Example 6
Ni-30Co-40Cr-0.005Ce合金采用粉末冶金法制备。Ni-30Co-40Cr-0.005Ce alloy is prepared by powder metallurgy.
电解用合金阳极的尺寸规格为40mm×25mm×10mm，在25mm×10mm面上端开Φ4mm×8mm的螺孔，合金阳极通过不锈钢导杆与直流电源连接。电解前，合金阳极在960℃的电解温度下氧化预处理2h。电解实验在阳极电流密度0.8A/cm2条件下进行200h，电解温度为960℃。电解试验的熔盐电解质采用NaF-AlF3体系，分子比为2.3，其余组成为CaF25wt％，Al2O35wt％。，石墨为阴极。电解后收集到的铝产品测得纯度为99.65％。The size specification of the alloy anode for electrolysis is 40mm×25mm×10mm, and a screw hole of Φ4mm×8mm is opened on the surface of 25mm×10mm. The alloy anode is connected to the DC power supply through a stainless steel guide rod. Before electrolysis, the alloy anode was oxidized and pretreated at an electrolysis temperature of 960 °C for 2 h. The electrolysis experiment was carried out for 200h under the condition of anodic current density of 0.8A/cm 2 , and the electrolysis temperature was 960℃. The molten salt electrolyte used in the electrolysis test uses the NaF-AlF 3 system, the molecular ratio is 2.3, and the rest composition is CaF 2 5wt%, Al 2 O 3 5wt%. , graphite as the cathode. The aluminum product collected after electrolysis has a measured purity of 99.65%.
实施例7Example 7
Fe-30Ni-15Co-40Cr-0.01Ce合金采用粉末冶金法制备。The Fe-30Ni-15Co-40Cr-0.01Ce alloy is prepared by powder metallurgy.
电解用合金阳极的尺寸规格为40mm×25mm×10mm，在25mm×10mm面上端开Φ4mm×8mm的螺孔，合金阳极通过不锈钢导杆与直流电源连接。电解前，合金阳极在960℃的电解温度下氧化预处理2h。电解实验在阳极电流密度0.8A/cm2条件下进行200h，电解温度为960℃。电解试验的熔盐电解质采用NaF-AlF3体系，分子比为2.3，其余组成为CaF25wt％，Al2O35wt％。，石墨为阴极。电解后收集到的铝产品测得纯度为99.44％。The size specification of the alloy anode for electrolysis is 40mm×25mm×10mm, and a screw hole of Φ4mm×8mm is opened on the surface of 25mm×10mm. The alloy anode is connected to the DC power supply through a stainless steel guide rod. Before electrolysis, the alloy anode was oxidized and pretreated at an electrolysis temperature of 960 °C for 2 h. The electrolysis experiment was carried out for 200h under the condition of anodic current density of 0.8A/cm 2 , and the electrolysis temperature was 960℃. The molten salt electrolyte used in the electrolysis test uses the NaF-AlF 3 system, the molecular ratio is 2.3, and the rest composition is CaF 2 5wt%, Al 2 O 3 5wt%. , graphite as the cathode. The aluminum product collected after electrolysis has a measured purity of 99.44%.
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| CN115323435A (en) * | 2022-09-02 | 2022-11-11 | 昆明理工大学 | An electrochemical metallurgical method for extracting metals and sulfur from metal sulfides |
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| CN1443877A (en) * | 2003-04-18 | 2003-09-24 | 石忠宁 | Metal base aluminium electrolytic inert anode and its preparation method |
| CN101736368A (en) * | 2010-01-13 | 2010-06-16 | 北京科技大学 | Noble metal ceramic composite coating inert anode for aluminum electrolysis and preparation method thereof |
| CN101824631A (en) * | 2009-03-02 | 2010-09-08 | 北京有色金属研究总院 | Composite alloy inert anode for aluminum electrolysis and aluminum electrolysis method utilizing same |
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| CN1443877A (en) * | 2003-04-18 | 2003-09-24 | 石忠宁 | Metal base aluminium electrolytic inert anode and its preparation method |
| CN101824631A (en) * | 2009-03-02 | 2010-09-08 | 北京有色金属研究总院 | Composite alloy inert anode for aluminum electrolysis and aluminum electrolysis method utilizing same |
| CN101736368A (en) * | 2010-01-13 | 2010-06-16 | 北京科技大学 | Noble metal ceramic composite coating inert anode for aluminum electrolysis and preparation method thereof |
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| CN113897639A (en) * | 2021-11-19 | 2022-01-07 | 河南世源铝业科技有限公司 | Aluminum-separating oxygen-evolution electrode for electrolytic aluminum and preparation method thereof |
| CN113897639B (en) * | 2021-11-19 | 2024-06-07 | 河南世源铝业科技有限公司 | Aluminum-oxygen-separating electrode for electrolytic aluminum and preparation method thereof |
| CN115323435A (en) * | 2022-09-02 | 2022-11-11 | 昆明理工大学 | An electrochemical metallurgical method for extracting metals and sulfur from metal sulfides |
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