CO2 gasification of woody biomass chars: The influence of K and Si on char reactivity

Although the influence of metallic and alkaline elements on biomass char reactivity is well known, a quantitative assessment of this catalytic effect is hard to obtain because of the chemical and textural complexity of biomass. The effect of K and Si on the CO₂ gasification reactivity of a biomass char was studied using thermogravimetric analysis. A beech sample was pyrolyzed at 800 °C and then impregnated with known amounts of silicon or potassium allowing to obtain a wide range of K/Si ratios. The reactivity of the impregnated samples was studied under a CO₂ (20% vol.) atmosphere. The results show that at low conversion ratios, the char reactivity depends on its textural properties, with strong diffusional limitations. When conversion reaches 60%, the presence of a catalyst (K) and an inhibitor (Si) becomes the major parameter influencing reactivity. From these experiments, a general trend was obtained between K/Si ratio and reactivity as a function of conversion.     

Changes in commercial wood charcoals by thermal treatments

As a continuation of a recent study of commercial wood charcoals as far as their potential production of carbon adsorbents is concerned, we have studied the influence of the final heating temperature (T) as carbonization variable in the range 250–1000 °C on the yield and on the characteristics of granular chars prepared from two very different charcoals: a holm-oak charcoal manufactured by partial combustion in a charcoal kiln and an eucalyptus charcoal industrially manufactured in a continuous furnace. Our study also includes the changes produced in both charcoals heated at 250 °C in air for 24 h, and their influences on the adsorption of water vapour at 25 °C. The samples were characterized by thermogravimetry, chemical analyses, Fourier transform infrared spectroscopy, densimetric measurements and mercury porosimetry. T affects the char yield, the chemical composition and the porosity of each char series differently. In particular, the total open pore volumes (to helium) of the starting charcoals, 0.475 and 1.044 cm³ g⁻¹, increase to 0.872 and 1.293 cm³ g⁻¹ heating up to 1000 and 500 °C, respectively. The changes by carbonization are mainly due to devolatilization; moreover, a moderate structural shrinkage occurs heating the eucalyptus charcoal at T > 500 °C. Concerning the air treatments, the yields do not present a significant difference; carbonyl groups are formed and the resulting pore structures depend on the starting charcoals. Water adsorption is larger for the eucalyptus carbons (approximately type V isotherms) than for the holm-oak carbons (type II isotherms).     

Modelling of transport processes in a developing char

A mathematical model, simulation results and laboratory experiments are reported to describe the degradation of fire retardant polymeric materials.The model describes the heat and mass balances of a polymer layer with finite thickness. The degradation is initiated by a constant heat flux at the top of the layer. It is assumed that the polymer degrades to a fixed mass of char and volatile gas in an instantaneous step, at the moment when the temperature reaches a critical value. The most important heat transport mechanism is conduction, which dominates the temperature profile. The mass transport of gas is described by Darcy's law, with a simplifying condition that the overall solid volume is constant during degradation. The transport processes have been modelled in one spatial dimension.Calculations and experiments have been carried out to establish the effects of critical parameters such as layer thickness, heat flux and material properties.     

Effect of nitrogen additives on flame retardant action of tributyl phosphate: Phosphorus-nitrogen synergism

The effects of three nitrogen additives (urea, guanidine carbonate, and melamine formaldehyde) on the flame retardant action of cotton cellulose treated with tributyl phosphate (TBP) were investigated in this research. The limiting oxygen index (LOI) of treated cotton cellulose clearly revealed the synergistic interactions of TBP and nitrogen compounds. The Kissinger method was used to evaluate the kinetics of thermal decomposition on treated cellulose. The results show that adding nitrogen additives increases the activation energy at a higher degree of degradation, thus indicating better thermal stability at higher temperatures. Scanning electron microscope pictures of chars formed after a LOI test show the formation of protective polymeric coatings on char surfaces. Evaluating char surfaces using attenuated total reflectance-Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggests that these coatings are composed of species containing phosphorus-nitrogen-oxygen. Possible chemical interactions of phosphorus and nitrogen compounds during the burning process and the formation of a protective coating could be the reason for the observed synergism. Potential reaction pathways contributing to the formation of this protective polymeric coating have also been proposed.     

Synergistic effects of novolac-based char former with magnesium hydroxide in flame retardant polyamide-6

In this paper, a novel synergistic flame retardant system containing magnesium hydroxide (MH) and methyl-blocked novolac (MBN) synthesized by Williamson ether route, were used for the flame retardance of polyamide-6 (PA6). The investigations showed that the thermal oxidative stability of MBN was obviously enhanced in the presence of MH compared with virgin novolac due to the decrease of phenol hydroxide groups subjected to be oxidized. It proved that MBN plays double roles: on the one hand, it remarkably promotes char formation and effectively eliminates the melt drips of PA6, therefore endows the materials with good flame retardancy; on the other hand, it also serves as an efficient lubricant and compatibilizer between MH and PA6, leading to the great improvement of the processability, as well as finer dispersion of MH in matrix, thus the flame retardant PA6 with good comprehensive performance can be obtained.     

Effect of chemical modifications caused by heat treatment on mechanical properties of Grevillea robusta wood

Grevillea robusta, a Kenyan wood species of low durability was heat treated under inert atmosphere in laboratory conditions at temperatures between 220 and 250 °C. Modulus of rupture (MOR) and modulus of elasticity (MOE) were determined for different heat treatment conditions. MOR and MOE reduced with increase in heat treatment weight loss. MOE reduced insignificantly for weight loss less than 16% while reduction of MOR was more significant. For a fixed heat treatment temperature by varying the treatment duration, sugar content was analysed by HPLC after acidic hydrolysis and Klason lignin was determined. The amount of sugars other than glucose decreased with treatment time and was near zero after 7 h, while lignin quantity increased gradually. Wood acidity determined by titration decreased after heat treatment indicating degradation of uronic acids present in hemicelluloses. Chemical modifications of wood components were determined by CP/MAS ¹³C NMR analysis. Spectra indicated significant degradation of hemicelluloses. Increase of treatment duration resulted in the appearance of new signals, particularly obvious on spectra of samples treated for 15 h, attributed to carbonaceous materials involved in char formation.     

Flame retardation and char formation mechanism of intumescent flame retarded polypropylene composites containing melamine phosphate and pentaerythritol phosphate

The flame retardation of polypropylene (PP) composites containing melamine phosphate (MP) and pentaerythritol phosphate (PEPA) was characterized by cone calorimeter. The formation mechanism of the char obtained from the combustion of the composites after cone calorimeter testing was studied by scanning electron microscopy (SEM), Fourier transform infrared spectra (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Raman diffusion. Results demonstrated that the PP composite containing MP and PEPA showed good flame retardancy. It had been found that the intumescent char could be principally divided into three parts, i.e. outer, middle and inner char layer, according to their different structures and components.     

煤粉燃烧颗粒粒子云辐射特性的研究

分析了在560nm的测量波长处煤粉炉中炭粒和飞灰粒子云的辐射特性。利用Mie理论,分别计算了燃烧器出口和炉膛的上部颗粒粒子云的辐射特性,发现在燃烧器出口区,炭粒对颗粒总体辐射减弱系数的影响较大,占90%以上;而在炉膛的上部,飞灰的影响较大。从数值计算结果中可以看出,飞灰粒子云的散射率高达91.6%,其对辐射的散射作用比吸收更强,而炭粒子的散射率仅为50%。     

Volatile–char interactions: Roles of in situ volatiles with distinctly-different chemistry in determining char structure and reactivity

This study reports the roles of volatiles with distinctly-different chemistry in determining char reactivity and char structure during in situ volatile–char interactions under non-catalytic conditions. Volatiles were generated in situ from polyethylene (PE), double-acid washed biosolid (DAWB), polyethylene glycol (PEG) or cellulose and interacted with char prepared from DAWB that is free of catalytically-active inorganic species in a two-stage reactor at 1000 °C. The experimental results show that both H- and O-containing reactive species play different roles during in situ volatile–char interactions. It has been found that char reactivity decreases substantially after in situ volatile–char interactions. Results from Raman analysis of the char after in situ interactions with the PE volatiles show H-containing reactive species substantially enhance the condensation of the aromatic ring systems within the char, thus slightly decreasing the H content in char and also making char carbon structure considerably less reactive. It has also been found that the reactivity of char after in situ volatile–char interactions increases with increasing O/H molar ratio of volatiles. The results indicate that O-containing reactive species in volatiles can react with char to form CO complex oxides that mitigate the carbon structure from condensing into large aromatic ring systems, thus increasing O and H contents in char and enhancing char reactivity.     

A semi-detailed kinetic model of char combustion with consideration of thermal annealing

The present paper presents a semi-detailed kinetic model of coal char combustion which embodies consideration of thermal annealing as a mechanism leading to the loss of char combustion reactivity along burn off. The distinctive feature of this model is that deactivation induced by thermal annealing is followed along with combustion. Thermodeactivation is modelled according to the power-law equation proposed by Senneca and Salatino [1]. A semi-detailed combustion mechanism was taken after Hurt and Calo [2] and includes three steps: formation of carbon–oxygen complexes (chemisorption), switch-over of surface oxides and desorption of oxygen complexes to yield combustion products. Computation results allow to discuss the impact of thermal annealing on char combustion under conditions of practical interest.