Three kinds of Chinese coal and a biomass were pyrolyzed by N 2 and CO 2 in a bench scale fluidized bed reactor. Fourier transform (FT)-Raman/infrared (IR) spectroscopy was used to identify microstructure and to evaluate the structural evolution of chars generated in N 2 and CO 2 environments, which are the main diluting gases of air and oxy-fuel environments. The Raman spectra were fitted with five Lorentzian bands. The reactivities of the char were measured by a thermogravimetric analyzer from room temperature to 1373 K in air and oxy-fuel conditions with O 2 concentration of 21%. The derived activation energy for different samples was correlated with the Raman structural parameters. Results showed that more disordered char was formed with the pyrolysis in CO 2 than that in N 2 , and new O-containing functional structures would be introduced into the char structure in CO 2 atmosphere. The char structures became less ordered as the sample rank decreased. The reactivity of CO 2 char was higher than that of N 2 char, while the combustion atmospheres rarely affected the char reactivity, indicating CO 2 played a more important role on the devolatization process for coal than for char combustion. The activation energy had a good linear correlation for N 2 char with Raman characterizations, while the data points for CO 2 char were perfectly fitted with exponential functions.
INTRODUCTIONO 2 /CO 2 combustion technology now has become a promising way for enrichment of CO 2 in the flue gas to levels as high as 95% by volume to capture CO 2 from the flue gas; 1 at the same time, it can also effectively reduce pollutants such as SO 2 and NO emissions. This novel combustion method has already received general concern all over the world. It has been reported that this technology has a great potential for retrofitting existing coal-fired power plants and building new power plants with several benefits. 2 As combustion generally comprises the process of devolatilization, followed by the combustion of the residue char, the devolatilization process exerts its influence throughout the life of the solid particles from injection to burnout. Therefore, differences in thermal properties and chemical action between N 2 and CO 2 make char combustion in oxy-fuel conditions quite different from conventional conditions. The presence of CO 2 in high concentrations during the initial pyrolysis stage will significantly change the distribution of alkali and alkaline earth metallic (AAEM) species. Then, these changes in the resulting char will substantially alter the coal reactivity and influence the combustion efficiency. 3 Scala et al. 4 found that, in the process of oxyfiring conditions, CO 2 gasification contributes to a comparative extent for carbon consumption at high temperatures and low oxygen concentrations. In addition to the different gas properties, the influence of CO 2 on the reactivity of coal chars is strongly dependent on the raw coal properties. 3,5 However, previous research has rarely examined the effects of structural var...
The electrochemical upgrading of bio-oil is a potential renewable approach toward generating liquid biofuels or industrial chemicals under mild reaction conditions (≤80 °C and ambient pressure). The aromatic structural evolution in biooil is a key consideration in bio-oil application. In this study, a bio-oil sample produced from the fast pyrolysis of rice husk at 500 °C and its lignin-derived oligomers were electrolyzed in an electrolytic cell with platinum electrodes. The samples at discrete time intervals were extracted and analyzed using ultraviolet fluorescence spectroscopy, gas chromatography−mass spectrometry, and Fourier transform ion cyclotron resonance−mass spectrometry (FT-ICR MS). Results showed that aromatic compounds with one and two benzene rings decreased with a prolonged processing time. The unsaturated aromatic compounds were hydrogenated and converted into saturated compounds. Species with more than two aromatic rings were the main compounds detected by FT-ICR MS. The lignin-derived oligomers contained the most phenolic compounds with more than two aromatic rings of the bio-oil. However, the evolution of these phenolic compounds showed different trends between the electrolysis of bio-oil and the lignin-derived oligomer fraction. This phenomenon was attributed to the presence of the light components derived from cellulose/hemicellulose species in the bio-oil. These species were reactive and able to produce radicals that enhanced the hydrogenation reactions. Accordingly, interactions among bio-oil compounds occurred during electrochemical treatment.
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