The project undertook a systematic study of chlorination of titanium oxycarbide and oxycarbonitride with the aim to develop further understanding of kinetics and mechanisms of the chlorination reactions. The project studied titania, ilmenite ores, and synthetic rutile reduced by carbon in argon and nitrogen and chlorinated at different temperatures, gas flow rates and compositions. Chlorination of titanium suboxides, iron and impurities in ilmenite was also examined. Chlorination of titanium oxycarbide Ti(O,C) or oxycarbonitride Ti(O,C,N) can be implemented at 200 to 400 deg.C, while the commercial chlorination process in the production of titanium metal or titania pigment requires 800 to 1100 deg.C. This makes chlorination of Ti(O,C) or Ti(O,C,N) an attractive technology in processing of titanium minerals. Chlorination reaction is strongly exothermal, which increased the sample temperature up to 200 deg.C above the furnace temperature. The chlorination of Ti(O,C) or Ti(O,C,N) was ignited at 150 deg.C to 200 deg.C depending on the sample composition. Their chlorination at 235 deg.C to 400 deg.C was close to completion in less than 30 min. The chlorination rate of titanium oxycarbide or oxycarbonitride increased with increasing gas flow rate. Sample composition had a significant effect on the extent of chlorination. The optimum results were obtained for titanium oxycarbide or oxycarbonitride produced with carbon to titania molar ratio of 2.5; these samples contained no detectable excess of carbon or unreduced titanium suboxides. In chlorination of reduced ilmenite ores and synthetic rutile, Ti(O,C) or Ti(O,C,N), metallic iron and Ti2O3 were chlorinated. The rate and extent of chlorination of titanium increased with increasing carbon to TiO2 ratio. Chlorination of Ti2O3 was slow relative to Ti(O,C) or Ti(O,C,N) and iron; chlorination of impurity oxides such as MgO, SiO2 and Al2O3 was not observed. The project also examined chlorination of Ti(O,C) or Ti(O,C,N) in ilmenite ore and synthetic rutile after removal of iron, which was achieved by aerated leaching of reduced samples in heated flask containing 0.37 M of ammonium chloride solution. Iron removal from the ilmenite ore or synthetic rutile resulted in higher rate and extent of chlorination of titanium oxycarbide or oxycarbonitride.

The project undertook a systematic study of chlorination of titanium oxycarbide and oxycarbonitride with the aim to develop further understanding of kinetics and mechanisms of the chlorination reactions. The project studied titania, ilmenite ores, and synthetic rutile reduced by carbon in argon and nitrogen and chlorinated at different temperatures, gas flow rates and compositions. Chlorination of titanium suboxides, iron and impurities in ilmenite was also examined. Chlorination of titanium oxycarbide Ti(O,C) or oxycarbonitride Ti(O,C,N) can be implemented at 200 to 400 deg.C, while the commercial chlorination process in the production of titanium metal or titania pigment requires 800 to 1100 deg.C. This makes chlorination of Ti(O,C) or Ti(O,C,N) an attractive technology in processing of titanium minerals. Chlorination reaction is strongly exothermal, which increased the sample temperature up to 200 deg.C above the furnace temperature. The chlorination of Ti(O,C) or Ti(O,C,N) was ignited at 150 deg.C to 200 deg.C depending on the sample composition. Their chlorination at 235 deg.C to 400 deg.C was close to completion in less than 30 min. The chlorination rate of titanium oxycarbide or oxycarbonitride increased with increasing gas flow rate. Sample composition had a significant effect on the extent of chlorination. The optimum results were obtained for titanium oxycarbide or oxycarbonitride produced with carbon to titania molar ratio of 2.5; these samples contained no detectable excess of carbon or unreduced titanium suboxides. In chlorination of reduced ilmenite ores and synthetic rutile, Ti(O,C) or Ti(O,C,N), metallic iron and Ti2O3 were chlorinated. The rate and extent of chlorination of titanium increased with increasing carbon to TiO2 ratio. Chlorination of Ti2O3 was slow relative to Ti(O,C) or Ti(O,C,N) and iron; chlorination of impurity oxides such as MgO, SiO2 and Al2O3 was not observed. The project also examined chlorination of Ti(O,C) or Ti(O,C,N) in ilmenite ore and synthetic rutile after removal of iron, which was achieved by aerated leaching of reduced samples in heated flask containing 0.37 M of ammonium chloride solution. Iron removal from the ilmenite ore or synthetic rutile resulted in higher rate and extent of chlorination of titanium oxycarbide or oxycarbonitride.

Les gisements uranifères nigériens sont localisés dans les formations carbonifères et jurassiques du bassin de Tim Mersoï. AREVA est actionnaire de 3 sites miniers de cette région: la SOMAÏR et la COMINAK dans le district d'Arlit, en exploitation depuis 50ans, et IMOURAREN, 80km plus au Sud, dont l'exploitation est programmée pour 2015. La minéralisation du gisement d'Imouraren est comprise dans la formation fluviatile du Tchirézrine 2 (Jurassique), formée de chenaux et de plaines d'inondation. Les faciès de remplissage de chenaux vont des grès grossiers aux grès très fins (cortège détritique : quartz et feldspaths), tandis que les faciès de débordement sont constitués d'analcimolites. La minéralogie secondaire est acquise lors de 2 évènements : 1- la diagenèse, avec formation de minéraux argileux, d'analcime, de quartz et d'albite secondaires, et 2- un épisode de circulations de fluides, qui induit une altération des minéraux détritiques et diagénétiques, la formation de nouvelles phases et le dépôt de l'uranium. Cette altération dessine une zonation minéralogique à l'échelle du gisement.L'hétérogénéité du Tchirézrine 2, tant au niveau des faciès que de la minéralogie, se perçoit lors du traitement du minerai, puisqu'il réagit différemment selon sa provenance, avec parfois des problèmes de récupération de l'U. Des essais de traitement de minerais, ont montré que analcimes et chlorites étaient les deux pénalisants, pour 3 raisons : 1- les piégeages des phases U au sein des analcimes, 2- la dissolution de ces 2 minéraux a tendance à faire sortir des conditions de solubilisation de l'U (pH et Eh) et à former de nombreux sulfates, 3- problèmes de percolation. Une méthode de détection des minerais riches en analcimes, basée sur la spectroscopie infrarouge, a été développée afin d'optimiser les mélanges de minerais et ainsi de réduire les effets néfastes des pénalisants lors du traitement. / Nigerian uraniferous deposits are located in carboniferous and jurassic formations of Tim Mersoï basin. AREVA is shareholder of 3 mine sites in this area: SOMAÏR and COMINAK, both in exploitation since 1960’s and IMOURAREN, 80km further South, whose exploitation is planned for 2015. Mineralization of Imouraren deposit is included in the fluvial formation of Tchirezrine 2 (Jurassic), composed of channels and flood plains. Facies of channel infillings range from coarse sandstones to siltstones, while overflow facies are composed of analcimolites.Secondary mineralogy was acquired during 2 stages: 1- diagenesis, with formation of clay minerals, analcime, secondary quartz and albites, and 2- stage of fluids circulations, which induced alteration of detrital and diagenetic minerals, formation of new phases and uranium deposition. A mineralogical zoning, at the scale of deposit resulted from this alteration. The heterogeneity of Tchirezrine 2, at the level of both facies and mineralogy, is also evidenced during ore treatment, as ore reacts differently depending on its source, with sometimes problems of U recovery. Ore treatment tests showed that analcimes and chlorites were both penalizing minerals, because of 1- the sequestration of U-bearing minerals into analcimes, 2- their dissolution which trends to move away from U solubilization conditions (pH and Eh) and to form numerous sulfates, and 3- problems of percolation. A detection method of analcime-rich ores, based on infrared spectroscopy, was developed in order to optimize ore blending and so to reduce negative effects during ore treatment process.