Elevated pressure secures the highest fixed-carbon yields of charcoal from corncob. Operating at a pressure of 0.8 MPa, a flash-carbonization reactor realizes fixed-carbon yields that range from 70 to 85% of the theoretical thermochemical equilibrium value from Waimanalo corncob. The fixed-carbon yield is reduced to a range from 68 to 75% of the theoretical value when whole Waimanalo corncobs are carbonized under nitrogen at atmospheric pressure in an electrically heated muffle furnace. The lowest fixed-carbon yields are obtained by the standard proximate analysis procedure for biomass feedstocks; this yield falls in a range from 49 to 54% of the theoretical value. A round-robin study of corncob charcoal and fixed-carbon yields involving three different thermogravimetric analyzers (TGAs) revealed the impact of vapor-phase reactions on the formation of charcoal. Deep crucibles that limit the egress of volatiles from the pyrolyzing solid greatly enhance charcoal and fixed-carbon yields. Likewise, capped crucibles with pinholes increase the charcoal and fixed-carbon yields compared to values obtained from open crucibles. Large corncob particles offer much higher yields than small particles. These findings show that secondary reactions involving vapor-phase species (or nascent vapor-phase species) are at least as influential as primary reactions in the formation of charcoal. Our results offer considerable guidance to industry for its development of efficient biomass carbonization technologies. Size reduction handling of biomass (e.g., tub grinders and chippers), which can be a necessity in the field, significantly reduces the fixed-carbon yield of charcoal. Fluidized-bed and transport reactors, which require small particles and minimize the interaction of pyrolytic volatiles with solid charcoal, cannot realize high yields of charcoal from biomass. When a high yield of corncob charcoal is desired, whole corncobs should be carbonized at elevated pressure. Under these circumstances, carbonization is both efficient and quick.
Biochar properties vary, and characterization of biochars is necessary for assessing their potential to sequester carbon and improve soil functions. This study aimed at assessing key surface properties of agronomic relevance for products from slow pyrolysis at 250-800 °C, hydrothermal carbonization (HTC), and flash carbonization. The study further aimed at relating surface properties to current characterization indicators. The results suggest that biochar chemical composition can be inferred from volatile matter (VM) and is consistent for corncob and miscanthus feedstocks and for the three tested production methods. High surface area was reached within a narrow temperature range around 600 °C, whereas cation exchange capacity (CEC) peaked at lower temperatures. CEC and pH values of HTC chars differed from those of slow pyrolysis biochars. Neither CEC nor surface area correlated well with VM or atomic ratios. These results suggest that VM and atomic ratios H/C and O/C are good indicators of the degree of carbonization but poor predictors of the agronomic properties of biochar.
The prosperity of Silicon Valley is built upon a foundation of wood charcoal that is the preferred reductant for the manufacture of pure silicon from quartz. Because ordinary pyrolysis processes offer low yields of charcoal from wood, the production of silicon makes heavy demands on the forest resource. The goal of this paper is to identify process conditions that improve the yield of charcoal from wood. To realize this goal, we first calculate the theoretical fixed-carbon yield of charcoal by use of the elemental composition of the wood feedstock. Next, we examine the influence of particle size, sample size, and pressure on experimental values of the fixed-carbon yields of the charcoal products and compare these values with the calculated theoretical limiting values. The carbonization by thermogravimetric analysis of small samples of small particles of wood in open crucibles delivers the lowest fixed-carbon yields, closely followed by standard proximate analysis procedures that employ a closed crucible and realize somewhat improved yields. The fixed-carbon yields (as determined by thermogravimetry) improve as the sample size increases and as the particle size increases. Further gains are realized when pyrolysis occurs in a closed crucible that hinders the egress of volatiles. At atmospheric pressure, high fixed-carbon yields are obtained from 30 mm wood cubes heated in a closed retort under nitrogen within a muffle furnace. The highest fixed-carbon yields are realized at elevated pressure by the flash carbonization process. Even at elevated pressure, gains are realized when large particles are carbonized. These findings reveal the key role that secondary reactions, involving the interaction of vapor-phase pyrolysis species with the solid substrate, play in the formation of charcoal. Models of biomass pyrolysis, which do not account for the impacts of sample size, particle size, and pressure on the interactions of volatiles with the solid substrate, cannot predict the yield of charcoal from biomass. These findings also offer important practical guidance to industry. Size reduction of wood feedstocks is not only energy and capital intensive; size reduction also reduces the yield of charcoal and exacerbates demands made on the forest resource.
ABSTRACT. Two different corncob samples from different continents and climates were studied by thermogravimetry at linear and nonlinear heating programs in inert gas flow. A distributed activation energy model (DAEM) with three and four pools of reactants (pseudocomponents) was used due to the complexity of the biomass samples of agricultural origin. The resulting models described well the experimental data. When the evaluation was based on a smaller number of experiments, similar model parameters were obtained which were suitable for predicting experiments at higher heating rates. This test indicates that the available experimental information was sufficient for the determination of the model parameters. The checks on the prediction capabilities were considered to be an essential part of the model verification. In another test the experiments of the two samples were evaluated together, 2 assuming more or less common kinetic parameters for both cobs. This test revealed that the reactivity differences between the two samples are due to the differences in their hemicelluloses and extractives.The kinetic parameter values from a similar earlier work on other biomasses (Várhegyi, G.; Bobály, B.; Jakab, E.; Chen, H. Energy Fuels, 2011, 25, 24-32.) could also been used, indicating the possibilities of a common kinetic model for the pyrolysis of a wide range of agricultural by-products.
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