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Sea water pollution resisting oxide anode and its prepn

An oxide and seawater-resistant technology, applied in the field of electrochemistry, can solve the problems of complex seawater composition, electrocatalytic deactivation, high oxygen content, save material loss and human resources, good oxygen corrosion resistance, and low precious metal content. Effect

Inactive Publication Date: 2007-01-03
725TH RES INST OF CHINA SHIPBUILDING INDAL CORP
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  • Summary
  • Abstract
  • Description
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Problems solved by technology

For example, the lower concentration of chloride ions in seawater will lead to a decrease in current efficiency and a higher oxygen content in the precipitated gas; the composition of seawater is complex, and harmful ions, especially Mn 2+ It will deposit on the surface of the anode and cause problems such as electrocatalytic "deactivation"
In addition, the abrasion of solid suspended matter in seawater and the scouring effect of fast seawater flow may cause mechanical damage to the oxide anode, etc.
Due to the above reasons, the oxide anodes currently used in the chlor-alkali industry cannot meet the requirements of marine use
U.S. Patent USP.4,479,864 has reported a kind of titanium base Pt-Ir-Ru oxide anode that is used in seawater environment, and the weight ratio of its composition is Pt: Ir: Ru=(15~85):(5~35):( 10-50), this oxide anode can maintain high current efficiency in low temperature seawater; however, the oxide anode is made of noble metals, and the production cost is high, and the author did not use this oxide anode in Long-term electrolytic performance in seawater was studied

Method used

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  • Sea water pollution resisting oxide anode and its prepn

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] The pretreated titanium matrix is ​​made into a 30mm × 60mm sheet sample, then weigh 1.00 grams of chloroiridic acid, 1.58 grams of ruthenium chloride, measure 25.52 milliliters of dibutyltin dilaurate, and dissolve it in 70 ml of n-butanol Stir evenly in the middle, as an oxide anode coating solution, at this time Ru:Ir:Sn=10:6:84 (wt.%). Brush the prepared coating solution evenly on the surface of the titanium substrate, dry at 60°C for 10 minutes, and then sinter at 470°C for 10 minutes. Repeat the above process until the loading reaches 10g / m 2 , and finally sintered at 470 ° C for 1 h to make an oxide anode. The oxide anode prepared according to the above method has an initial current efficiency of 92%, and after 720 hours of continuous electrolysis in Qingdao seashore natural seawater, the chlorine evolution current efficiency is 77.2%, while adding 20ppm Mn 2+ The current efficiency of chlorine evolution is 74.7% after continuous electrolysis in natural seawate...

Embodiment 2

[0021] Make the pretreated titanium matrix into a 30mm×60mm sheet sample, then weigh 1.00g of chloroiridic acid, 0.85g of ruthenium chloride, measure 0.20ml of dibutyltin dilaurate, and dissolve it in 10ml of n-butanol Stir evenly in the middle, as an oxide anode coating solution, at this time Ru:Ir:Sn=45:50:5 (wt.%). Brush the prepared coating solution evenly on the surface of the titanium substrate, dry at 80°C for 10 minutes, and then sinter at 420°C for 10 minutes. Repeat the above process until the loading reaches 10g / m 2 , and finally sintered at 420 ° C for 1 h to make an oxide anode. The initial current efficiency of the oxide anode prepared according to the above method is 97%, and the chlorine evolution current efficiency is 70.2% after continuous electrolysis in the natural seawater of Qingdao seashore for 720 hours, while adding 20ppm Mn 2+ After 10 days of continuous electrolysis in natural seawater, the current efficiency of chlorine evolution is 68.5%.

Embodiment 3

[0023] The pretreated titanium matrix is ​​made into a 30mm × 60mm sheet sample, then weigh 1.00 grams of chloroiridic acid, 0.79 grams of ruthenium chloride, measure 3.05 milliliters of dibutyltin dilaurate, and dissolve it in 20 ml of n-butanol Stir evenly in the middle, as an oxide anode coating solution, at this time Ru:Ir:Sn=25:30:45 (wt.%). Brush the prepared coating solution evenly on the surface of the titanium substrate, dry at 100°C for 10 minutes, and then sinter at 400°C for 10 minutes. Repeat the above process until the loading reaches 10g / m 2 , and finally sintered at 400 ° C for 1 h to make an oxide anode. The initial current efficiency of the oxide anode prepared according to the above method is 97%, and the chlorine evolution current efficiency is 75.8% after 720 hours of continuous electrolysis in Qingdao coastal natural seawater, while adding 20ppm Mn 2+The current efficiency of chlorine evolution is 76.5% after continuous electrolysis in natural seawater ...

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Abstract

The sea water pollution resisting oxide anode includes titanium or titanium alloy base and oxide coating on the base, and features that the oxide coating contains RuO2, IrO2, SnO2, PtO2 and Ta2O5 in the amount of Ru 10-45 wt%, (Ir+Pt) 6-50 wt%, and (Ta+Sn) 5-84 wt%. The oxide anode is prepared through dissolving chloroiridic acid, rhthenium chloride, chloroplatinic acid, tantalum choride and dibutyl tin dilaurate based on the said composition in n-butyl alcohol to form the coating fluid; coating the coating fluid to treated titanium base; drying at 60-120 deg.c for 10 min; sintering at 350-520 deg.c for 10 min; repeating the forgoing steps until reaching oxide coating of 6-15 g / sq m; and final sintering at 400-520 deg.c for 1hr. The oxide anode of the present invention may be used widely in electrolyzing water for treating sea water, salty water, swimming pool water, etc.

Description

technical field [0001] The invention belongs to the field of electrochemistry, and relates to an oxide anode suitable for producing chlorine by seawater electrolysis and a preparation method thereof. Background technique [0002] At present, the electrolysis method has been used on a large scale in the chlor-alkali industry. It mainly electrolyzes alkali metal chloride aqueous solution to produce chlorine gas, alkali metal hydroxide, alkali metal hypochlorite and alkali metal chlorate. The electrolytic cell in the chlor-alkali industry is generally a diaphragm electrolytic cell with alternating cathodes and anodes. The diaphragm is a hydraulically permeable porous diaphragm or a substantially hydraulically impermeable ion exchange membrane, which is located between the anode and the cathode. The anode material is "DSA" - dimensionally stable anode, the most widely used at present is to coat the mixed oxide of ruthenium and titanium on the industrial pure titanium substrate ...

Claims

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Application Information

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IPC IPC(8): C25B11/06
Inventor 王均涛韩严许立坤
Owner 725TH RES INST OF CHINA SHIPBUILDING INDAL CORP
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