Composite anode for hydrometallurgy and its preparation method and application

Abstract

The invention discloses a composite anode for hydrometallurgy and its preparation method and application. The structure of the composite anode is metal substrate / non-oxide intermediate layer / selective electrocatalytic oxygen evolution layer, wherein the non-oxide intermediate layer can isolate Oxygen diffuses to the metal substrate to avoid passivation of the metal substrate, and the selective electrocatalytic oxygen evolution layer can selectively catalyze oxygen evolution while inhibiting Mn in the electrolyte 2+ depletion. The composite anode can be used in the electrochemical metallurgical process of non-ferrous metals such as zinc, manganese, copper, etc., and when it is used for the electrodeposition of metal manganese, it can realize the equal current density of the cathode and the anode and the electrodeposition without diaphragm, which greatly reduces the energy of the electrodeposition process. Consumption, inhibition of Mn 2+ Oxidation losses at the anode improve cathodic current efficiency.

Description

technical field

[0001] The invention belongs to the technical field of hydrometallurgy, and in particular relates to a composite anode for nonferrous metal electrodeposition, a preparation method and application thereof. Background technique

[0002] In the smelting of non-ferrous metals, more than 80% of non-ferrous metals in the world are produced by wet process. However, the energy consumption of the electrowinning process in hydrometallurgy is relatively high, accounting for about 80% of the total energy consumption. The main reason for the high energy consumption of the electrowinning process is that the traditional Pb-based alloy anode has been used in the electrolytic system, and its oxygen evolution overpotential is close to 1V, which increases the unnecessary power consumption by nearly 1000kWh / t-Zn, accounting for about 1000kWh / t-Zn of the electrowinning process energy consumption. 30% of. In addition, the traditional Pb-based alloy anode also has the following d...

Examples

Embodiment 1

[0047] When the composite anode for hydrometallurgy of the present invention is used as a zinc electrodeposition anode, the working anode is Al / Sn-Ni-Ag / MnO 2 , the oxygen barrier intermediate layer Sn-Ni-Ag ternary alloy, its thickness is 40μm, the electrocatalytic oxygen evolution layer is MnO 2 layer, the anode structure is a flat plate, and the cathode is an aluminum electrode.

[0048] Its Al / Sn-Ni-Ag / MnO 2 The composite anode preparation method is as follows:

[0049] (1) Cut the Al plate into 10mm×10mm×2mm samples by wire cutting method, and use 1200-mesh metallographic sandpaper to polish the surface, and place it in 10% acetone solution to clean the surface of the Al substrate by ultrasonic vibration Take out the oil stains and impurities, wash them with distilled water and ethanol, and set aside.

[0050] (2) The Sn-Ni-Ag coating was prepared on the surface of the Al substrate by electroless plating.

[0051] The bath system is: SnCl (40%), NiCl (30%), AgCl (30%)...

Embodiment 2

[0060] When the composite anode for hydrometallurgy of the present invention is used as a copper electrodeposition anode, the working anode is Fe / Sn / MnO 2 , the oxygen barrier middle layer Sn, its thickness is 42μm, the electrocatalytic oxygen evolution layer is MnO 2 layer, the anode structure is a flat plate, and the cathode is a stainless steel electrode.

[0061] Its Fe / Sn / MnO 2 The composite anode preparation method is as follows:

[0062] (1) Using the wire cutting method, cut the Fe plate into a sample of 10mm×10mm×2mm, and polish the surface with 1200-mesh metallographic sandpaper, and place it in 10% acetone solution with ultrasonic vibration to remove the surface of the Fe substrate Take out the oil stains and impurities, wash them with distilled water and ethanol, and set aside.

[0063] (2) The Sn coating was prepared on the surface of the Fe substrate by electroless plating.

[0064] The plating solution system is: SnCl (30g / L), sodium hypophosphite (4g / L) as ...

Embodiment 3

[0073] When the composite anode for hydrometallurgy of the present invention is used as a manganese electrodeposition anode, the working anode is Ti / TiB 2 / MnO 2 , the anode structure is grid-shaped, in which the oxygen barrier layer TiB 2 The thickness is 120μm, and the electrocatalytic oxygen evolution layer is MnO 2 layer, and the cathode is a stainless steel electrode.

[0074] Its Ti / TiB 2 / MnO 2 The composite anode preparation method is as follows:

[0075] (1) Using the method of wire cutting, the Ti plate is cut into a sample of 10mm×10mm×2mm, and the surface is polished with 1200 mesh metallographic sandpaper, and the polished Ti substrate is placed in 5% sodium hydroxide Soak in the solution, and then rub the metal substrate with sandpaper, then place the metal substrate in 10% oxalic acid solution, under boiling, etch for 2 hours, take it out and wash it with distilled water and ethanol for later use.

[0076] (2) Prepare TiB on the surface of Ti substrate by ...

technical field

[0001] The invention belongs to the technical field of hydrometallurgy, and in particular relates to a composite anode for nonferrous metal electrodeposition, a preparation method and application thereof. Background technique

[0002] In the smelting of non-ferrous metals, more than 80% of non-ferrous metals in the world are produced by wet process. However, the energy consumption of the electrowinning process in hydrometallurgy is relatively high, accounting for about 80% of the total energy consumption. The main reason for the high energy consumption of the electrowinning process is that the traditional Pb-based alloy anode has been used in the electrolytic system, and its oxygen evolution overpotential is close to 1V, which increases the unnecessary power consumption by nearly 1000kWh / t-Zn, accounting for about 1000kWh / t-Zn of the electrowinning process energy consumption. 30% of. In addition, the traditional Pb-based alloy anode also has the following d...

Examples

Embodiment 1

[0047] When the composite anode for hydrometallurgy of the present invention is used as a zinc electrodeposition anode, the working anode is Al / Sn-Ni-Ag / MnO 2 , the oxygen barrier intermediate layer Sn-Ni-Ag ternary alloy, its thickness is 40μm, the electrocatalytic oxygen evolution layer is MnO 2 layer, the anode structure is a flat plate, and the cathode is an aluminum electrode.

[0048] Its Al / Sn-Ni-Ag / MnO 2 The composite anode preparation method is as follows:

[0049] (1) Cut the Al plate into 10mm×10mm×2mm samples by wire cutting method, and use 1200-mesh metallographic sandpaper to polish the surface, and place it in 10% acetone solution to clean the surface of the Al substrate by ultrasonic vibration Take out the oil stains and impurities, wash them with distilled water and ethanol, and set aside.

[0050] (2) The Sn-Ni-Ag coating was prepared on the surface of the Al substrate by electroless plating.

[0051] The bath system is: SnCl (40%), NiCl (30%), AgCl (30%)...

Embodiment 2

[0060] When the composite anode for hydrometallurgy of the present invention is used as a copper electrodeposition anode, the working anode is Fe / Sn / MnO 2 , the oxygen barrier middle layer Sn, its thickness is 42μm, the electrocatalytic oxygen evolution layer is MnO 2 layer, the anode structure is a flat plate, and the cathode is a stainless steel electrode.

[0061] Its Fe / Sn / MnO 2 The composite anode preparation method is as follows:

[0062] (1) Using the wire cutting method, cut the Fe plate into a sample of 10mm×10mm×2mm, and polish the surface with 1200-mesh metallographic sandpaper, and place it in 10% acetone solution with ultrasonic vibration to remove the surface of the Fe substrate Take out the oil stains and impurities, wash them with distilled water and ethanol, and set aside.

[0063] (2) The Sn coating was prepared on the surface of the Fe substrate by electroless plating.

[0064] The plating solution system is: SnCl (30g / L), sodium hypophosphite (4g / L) as ...

Embodiment 3

[0073] When the composite anode for hydrometallurgy of the present invention is used as a manganese electrodeposition anode, the working anode is Ti / TiB 2 / MnO 2 , the anode structure is grid-shaped, in which the oxygen barrier layer TiB 2 The thickness is 120μm, and the electrocatalytic oxygen evolution layer is MnO 2 layer, and the cathode is a stainless steel electrode.

[0074] Its Ti / TiB 2 / MnO 2 The composite anode preparation method is as follows:

[0075] (1) Using the method of wire cutting, the Ti plate is cut into a sample of 10mm×10mm×2mm, and the surface is polished with 1200 mesh metallographic sandpaper, and the polished Ti substrate is placed in 5% sodium hydroxide Soak in the solution, and then rub the metal substrate with sandpaper, then place the metal substrate in 10% oxalic acid solution, under boiling, etch for 2 hours, take it out and wash it with distilled water and ethanol for later use.

[0076] (2) Prepare TiB on the surface of Ti substrate by ...

Images