Towards the large-scale synthesis of carbon nanotubes in fluidised beds

Carbon nanotubes (CNTs) are a form of crystalline carbon with extraordinary properties, making them valuable in a broad range of applications. However, the lack of suitable large-scale manufacturing techniques, which we define as being of the order 10000 tonnes per annum, continues to inhibit their widespread use. Of the three established synthesis methods for CNTs: (i) chemical vapour deposition (CVD), (ii) laser ablation, and (iii) arc discharge, CVD techniques show the greatest promise for economically viable, large-scale synthesis. In particular, the fluidised bed CVD (FBCVD) technique, where the CVD reaction occurs within a fluidised bed of catalyst particles, has the potential to produce high quality CNTs, inexpensively, in large quantities. In this work we report on the development of a catalytic chemical vapour deposition process, using batch fluidised bed reactors, for the synthesis of straight and spiral carbon nanotubes at pilot scale (up to 1 kg/hr). We believe this to be the first report of the synthesis of spiral carbon nanotubes using fluidised bed CCVD. Iron, nickel and cobalt transition metal catalysts supported on non-porous alumina substrates were fluidised in a mixture of nitrogen, hydrogen and ethylene at temperatures between 550 and 800 degrees C for between 15 and 90 minutes. Nanotube yield was inferred from thermogravimetric analysis and the quality and size of the CNTs from transmission electron microscopy. Conflicting information in the literature about the influence of synthesis parameters on CNT properties suggests that further investigation is necessary to understand the synthesis process at a fundamental level, i.e., independent of reactor design and operation.