The preparation of vanadium tetrachloride from vanadium dichloride oxide and vanadium trichloride and the hydrogen reduction process of vanadium tetrachloride.
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概要
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The reactions of VCl<SUB>2</SUB>O and VCl<SUB>3</SUB> with chlorine, and the reaction of VCl<SUB>3</SUB>O, formed by the chlorination of VCl<SUB>2</SUB>O, with chlorine in the presence of carbon were examined. The products formed by the reaction between gaseous VCl<SUB>4</SUB> and hydrogen at various temperatures, and the behavior of VCl<SUB>3</SUB> and VCl<SUB>2</SUB> on heating in a hydrogen stream were examined. The reaction between VCl<SUB>2</SUB>O and chlorine occurs above <I>ca.</I> 120 °C and proceeds markedly above <I>ca.</I> 170 °C to form VCl<SUB>3</SUB>O. VCl<SUB>4</SUB> can be obtained by passing the gaseous VCl<SUB>3</SUB>O together with chlorine through a carbon bed held at <I>ca.</I> 700 °C. The reaction between VCl<SUB>3</SUB> and chlorine occurs above <I>ca.</I> 80 °C and proceeds markedly above <I>ca.</I> 170 °C to form VCl<SUB>4</SUB>. The hydrogen reduction process of VCl<SUB>4</SUB> in the vapor phase may be represented as follows: The reaction between VCl<SUB>4</SUB> and hydrogen, 2VCl<SUB>4</SUB>(g)+H<SUB>2</SUB>(g)→2VCl<SUB>3</SUB>(s)+2HCl(g), proceeds above <I>ca.</I> 500 °C to form VCl<SUB>3</SUB>. Subsequently, the hydrogen reduction of the VCl<SUB>3</SUB>, 2VCl<SUB>3</SUB>(s)+H<SUB>2</SUB>(g)→2VCl<SUB>2</SUB>(s)+2HCl(g), and the disproportionate of the VCl<SUB>3</SUB>, 2VCl<SUB>3</SUB>(s)→VCl<SUB>2</SUB>(s)+VCl<SUB>4</SUB>(g), proceed to form VCl<SUB>2</SUB>. Above <I>ca.</I> 620 °C, the reaction between the VCl<SUB>2</SUB> and hydrogen, VCl<SUB>2</SUB>(s)+H<SUB>2</SUB>(g)→V(s)+2HCl(g), proceeds to form vanadium.
- 公益社団法人 日本化学会の論文
著者
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Yajima Akimasa
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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Saeki Yuzo
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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Matsuzaki Ryoko
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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