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Experimental research on the pyrolysis and gasification of randomly packed straw pellets was conducted with an emphasis on the reactive properties of the shrinking porous structure of the pellets. The apparent kinetics of such pyrolysis was approximated by the random pore, grain, and volumetric models. The best approximation results were obtained with the grain and random pore models. The self-organized oscillations of the pellet conversion rate during pyrolysis were observed. Two complementary explanations of the phenomenon are proposed. [ABSTRACT FROM AUTHOR]

Abstract: Pyrolysis enables to recover metals and organic feedstock from waste conglomerates such as: automotive shredder residue (ASR). ASR as well as its pyrolysis solid products, is a morphologically and chemically varied mixture, containing mineral materials, including hazardous heavy metals. The aim of the work is to generate fundamental knowledge on the conversion of the organic residues of the solid products after ASR''s microwave pyrolysis, treated at various temperatures and with two different types of gasifying agent: pure steam or 3% (v/v) of oxygen. The research is conducted using a lab-scale, plug-flow gasifier, with an integrated scale for analysing mass loss changes over time of experiment, serving as macro TG at 950, 850 and 760°C. The reaction rate of char decomposition was investigated, based on carbon conversion during gasification and pyrolysis stage. It was found in both fractions that char conversion rate decreases with the rise of external gas temperature, regardless of the gasifying agent. No significant differences between the reaction rates undergoing with steam and oxygen for char decomposition has been observed. This abnormal char behaviour might have been caused by the inhibiting effects of ash, especially alkali metals on char activity or due to deformation of char structure during microwave heating. [Copyright &y& Elsevier]

We studied the characteristics of waste printing paper and cardboard particles in a reactor pyrolyzed by preheated agents with the aim of simulating a real case in a fixed-bed gasifier. A TGA/DSC was first used to study of the kinetics and enthalpy change of the printing paper and cardboard pyrolysis. Pyrolitic conversion was further carried out in a batch-type reactor with non-electrical heating. Syngas, tar and char were produced and characterized from printing paper and cardboard pyrolysis at 400°C, 500°C and 600°C. Different flow rates of carrier gas were applied to study the effect of residence time on the products distribution. When the flow rate increased, the relative mass change of gas agrees with that of tar. With increase in temperature, the yield of furfural, olefins and other non-aromatic compounds in tar decreased, while phenols and heavier aromatic hydrocarbons increased. The evolution of CO2, CO and other gas species in the syngas was presented. Van Krevelan diagram of chars was also presented in the paper. [ABSTRACT FROM AUTHOR]

Highlights: [•] Kinetics study on levoglucosan primary decomposition in cellulose pyrolysis. [•] Including C–O bond scission, C–C bond scission, and levoglucosan dehydration. [•] Transition state calculation without tunneling correction is suitable method. [•] Arrhenius equation for every elementary reaction and every pathway are obtained. [•] One dehydration pathway is a preferred pathway for levoglucosan decomposition. [ABSTRACT FROM AUTHOR]

Abstract: Levoglucosan (1,6-anhydro-β-d-glucopyranose) decomposition is an important step during cellulose pyrolysis and for secondary tar reactions. The mechanism of levoglucosan thermal decomposition was studied in this paper using density functional theory methods. The decomposition included direct Ceaking, direct Ceaking, and dehydration. In total, 9 different pathways, including 16 elementary reactions, were studied, in which levoglucosan serves as a reactant. The properties of the reactants, transition states, intermediates, and products for every elementary reaction were obtained. It was found that 1-pentene-3,4-dione, acetaldehyde, 2,3-dihydroxypropanal, and propanedialdehyde can be formed from the Ceaking decomposition reactions. 1,2-Dihydroxyethene and hydroxyacetic acid vinyl ester can be formed from the Ceaking decomposition reactions. It was concluded that Ceaking is easier than Ceaking due to a lower activation energy and a higher released energy. During the 6 levoglucosan dehydration pathways, one water molecule which composed of a hydrogen atom from C3 and a hydroxyl group from C2 is the preferred pathway due to a lower activation energy and higher product stability. [Copyright &y& Elsevier]

Abstract: The mechanisms and kinetics studies of the formation of levoglucosan and formaldehyde from anhydroglucose radical have been carried out theoretically in this paper. The geometries and frequencies of all the stationary points are calculated at the B3LYP/6-31+G(D,P) level based on quantum mechanics, Six elementary reactions are found, and three global reactions are involved. The variational transition-state rate constants for the elementary reactions are calculated within 450–1500K. The global rate constants for every pathway are evaluated from the sum of the individual elementary reaction rate constants. The first-order Arrhenius expressions for these six elementary reactions and the three pathways are suggested. By comparing with the experimental data, computational methods without tunneling correction give good description for Path1 (the formation of levoglucosan); while methods with tunneling correction (zero-curvature tunneling and small-curvature tunneling correction) give good results for Path2 (the first possibility for the formation of formaldehyde), all the test methods give similar results for Path3 (the second possibility for the formation of formaldehyde), all the modeling results for Path3 are in good agreement with the experimental data, verifying that it is the most possible way for the formation of formaldehyde during cellulose pyrolysis. [Copyright &y& Elsevier]

Abstract: Steam explosion (SE) pretreatment is served to separate the main components of woody biomass. In general there is a noticeable gap in literature in terms of application of steam explosion process to upgrade biomass fuel for wood pellet production. In order to study the influence of steam explosion pretreatment on biomass fuel, Salix wood chips was used as raw material. Four different SE experiments were performed by varying two key process factors; time and temperature. Elementary quality and ash properties of the pretreated residue were investigated. Moreover, physical and thermochemical properties of the pellet, produced from the residue, were also investigated. Reduction in ash content especially in alkali metals was observed in steam treated residue. Pretreatment of biomass also enhanced carbon content and reduced oxygen amount in the fuel which enhanced the heating value of the fuel. Moreover, pretreatment enhanced pellet density, impact resistance, and abrasive resistance of pellet. However, small degradation in ash fusion characteristics and char reactivity was also observed as the severity of the process increased. [Copyright &y& Elsevier]

Abstract: Coconut and cashew nut shells are two typical biomass wastes abundant in most of the tropical countries. However, despite their enormous potential as energy sources, they are hardly studied and their thermal characteristics are still not well known. In this study, both biomasses are thermally degraded through thermogravimetry and their characteristics such as devolatilisation profiles and kinetics are analyzed, from 250 to 900 °C, in an inert atmosphere, at two different heating rates, and compared with wood pellets. The results show that their pyrolysis profiles are different from that of the commonly studied woody biomass. In fact, they present two different peaks instead of the one overlapping peak, for hemicellulose and cellulose. In addition, they present activation energies ranging from that are slightly above the commonly known maximum for biomass. At 10 and 20 °C/min the activation energy varied from about 130 to 174 and 180 to 216 kJ/mol, for cashew and coconut shells, respectively. [Copyright &y& Elsevier]

Secondary pyrolysis in fluidizedbed fast pyrolysis of biomassis the focus of this work. A novel computational fluid dynamics (CFD)model coupled with a comprehensive chemistry scheme (134 species and4169 reactions, in CHEMKIN format) has been developed to investigatethis complex phenomenon. Previous results from a transient three-dimensionalmodel of primary pyrolysis were used for the source terms of primaryproducts in this model. A parametric study of reaction atmospheres(H2O, N2, H2, CO2, CO)has been performed. For the N2and H2O atmosphere,results of the model compared favorably to experimentally obtainedyields after the temperature was adjusted to a value higher than thatused in experiments. One notable deviation versus experiments is pyrolyticwater yield and yield of higher hydrocarbons. The model suggests anot overly strong impact of the reaction atmosphere. However, bothchemical and physical effects were observed. Most notably, effectscould be seen on the yield of various compounds, temperature profilethroughout the reactor system, residence time, radical concentration,and turbulent intensity. At the investigated temperature (873 K),turbulent intensity appeared to have the strongest influence on liquidyield. With the aid of acceleration techniques, most importantly dimensionreduction, chemistry agglomeration, and in-situ tabulation, a convergedsolution could be obtained within a reasonable time (∼30 h).As such, a new potentially useful method has been suggested for numericalanalysis of fast pyrolysis. [ABSTRACT FROM AUTHOR]

Highlights: [•] Biomasses were devolatilized at high temperatures and high heating rates. [•] Biomass decreases its reactivity after torrefaction. [•] The kinetic parameters of torrefied biomasses were determined. [•] CO and H2 are main released volatiles during devolatilization of torrefied biomass. [ABSTRACT FROM AUTHOR]

Pelletized recovered solid waste fuel is often applied in gasification systems to provide feedstock with a stabilized quality and high heating value and to avoid the bridging behavior caused by high moisture content, low particle density, and irregular particle size. However, the swelling properties and the sticky material generated from pyrolysis of the plastic group components also tend to trigger bridging in the retorting zone. It is well known that the plastic group materials, which occupy a considerable proportion of municipal solid waste, can melt together easily even under low temperature. This study investigates the pyrolysis behaviors of typical recovered solid waste pellets, including the devolatilization rate, heat transfer properties, char properties, and swelling/shrinkage properties, in a small fixed-bed facility over a wide temperature range, from 900°C to 450°C. The results are also compared with those from wheat straw pellets, a typical cellulosic fuel. Moreover, the SEM images and BET analysis of the char structure are further analyzed to provide additional explanation for the mechanisms of swelling/shrinkage phenomena observed during heating. [ABSTRACT FROM AUTHOR]

Abstract: Measurements of temperature in the proximity of wood pellets (8mm diameter) and thin wooden stick slices (5cm diameter and 5mm thickness) were conducted to estimate the effects of mixing between the evolving volatiles and hot steam (T >700°C) flowing around the particles. Measurements of mass loss of the slices were conducted to estimate the apparent kinetic parameters of their pyrolysis. A simple kinetic model of the process (type II by Pyle and Zaror (1984) [20]) was investigated. The experiments showed a plateau-like part in the graphs of temperature measured in the proximity to the samples. The existence of this plateau-like part agrees with the general data of calorimetric measurements of pyrolysis, which show extensive energy consumption in the beginning of an active production of volatiles. A hypothesis regarding feedback on the process due to the micro-expansion and mixing of volatiles in the convective boundary layer is discussed. [Copyright &y& Elsevier]

Abstract: Plasma Gasification Melting (PGM) is a novel gasification technology which offers a promising treatment of low-heating-value fuels like municipal solid waste (MSW), medical waste (MW) and other types of waste. By considering the differences in pyrolysis characteristics between cellulosic fractions and plastics in MSW, a semi-empirical model was developed to predict the performance of the PGM process. The measured results of MSW air and steam gasification in a PGM demo-reactor are demonstrated and compared with the model predicted results. Then, the effects of dimensionless operation parameters (ER, PER, and SAMR) are discussed. It was found that all three numbers have positive effects on system cold gas efficiency (CGE). The reasons can be attributed to promoted tar cracking by enhanced heat supply. The effects of PER and ASME on syngas LHV are also positive. The influence of ER on syngas pyrolysis can be divided into two parts. When 0.04

Abstract: Steam explosion (SE) pretreatment has been implemented for the production of wood pellet. This paper investigated changes in biomass structure due to implication of steam explosion process by its pyrolysis behavior/characteristics. Salix wood chip was treated by SE at different pretreatment conditions, and then pyrolysis characteristic was examined by thermogravimetric analyzer (TGA) at heating rate of 10K/min. Both pyrolysis characteristics and structure of biomass were altered due to SE pretreatment. Hemicellulose decomposition region shifted to low temperature range due to the depolymerization caused by SE pretreatment. The peak intensities of cellulose decreased at mild pretreatment condition while they increased at severe conditions. Lignin reactivity also increased due to SE pretreatment. However, severe pretreatment condition resulted in reduction of lignin reactivity due to condensation and re-polymerization reaction. In summary, higher pretreatment temperature provided more active biomass compared with milder pretreatment conditions. [Copyright &y& Elsevier]