화학공학소재연구정보센터
Energy & Fuels, Vol.21, No.2, 778-792, 2007
Stable oxides on chars and impact of reactor materials at high temperatures
This paper reports our first study on the deactivation of young chars in flame conditions. The quantity and strength of surface oxides on young chars are monitored in situ by temperature-programmed desorption (TPD) up to 1700 degrees C. Young chars contain more abundant surface oxides than old chars over a wide range of temperature. Lignite chars possess more oxides than chars derived from a bituminous coal. Chars oxidized at 629 degrees C show desoprtion products at three distinct temperatures: 725, 1430, and 1700 degrees C. The TPD peaks around 725 degrees C correspond to activation energies in the range of 107-170 kJ/mol and have been well-documented in the literature. CO desorbed at around 1430 degrees C corresponds to activation energies over 300 kJ/mol, signifying the possible roles of strongly bound oxides on the basal planes of carbon. Search of the oxygen source for the huge amount of CO production at 1700 degrees C reveals that commonly adopted alumina tubes and support materials decompose to Al2O(g) and emit a notable amount of O-2 at temperatures above 1300 degrees C. Moreover, alumina tube and support materials react with CO and form CO2; they also react with carbon and form CO and aluminum oxycarbides. SiC tube, on the other hand, is oxidized by O-2, CO2, and H2O and forms SiO(g), SiO2(s), Si(OH)(4(g)), and CO above 650 degrees C. Moreover, Si can also form through a secondary reaction of SiC and SiO2. Thus, alumina appears suitable for the oxidation part of the experiments, where up to 120 ppm of O-2 emission is acceptable at a temperature of 1700 degrees C. SiC appears acceptable for TPD, though a small amount of SiC may be oxidized by the TPD product, CO2, at temperatures above 900 degrees C. Oxidation of SiC prior to TPD should be avoided.