Crane, JH; (2014) Separation of VOCl3 from TiCl4 using soya oil. Doctoral thesis , UCL (University College London).

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Abstract

This thesis investigated the reactivity of the metal chlorides TiCl4, VOCl3 and VCl4 with different organic ligands. The chosen ligands were based around the chemical structure of soya oil due to its relevance to the industrial chlorine process used to manufacture TiO2. This thesis primarily used nuclear magnetic resonance (NMR)spectroscopy to characterise the reactions of the metal chlorides with soya oil and component parts, namely the glycerol and the alkene. This thesis goes on to investigate the coordination chemistry of the metal chlorides with ligands including diester groups. The chemical properties of the metal chlorides are known to be similar and hence hard to separate, the reactions studied provide a mechanism for their separation using diesters. It will be shown that TiCl4 coordinates with the ligands without the loss of any chlorine atoms and without disrupting the ligand. The VOCl3 reacted with the ligands, releasing a chlorine atom to produce a VOCl2 adduct. The difference in reactivity provides a removal mechanism. In the industrial process TiCl4 is present in very high concentrations and the coordination of TiCl4 can be seen as reversible and in equilibrium. Whereas, the VOCl3 converts VOCl3 into VOCl2, VOCl2 has a higher boiling point and can therefore be removed by distillation. 4

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