A unified lumped approach in kinetic modeling of biomass pyrolysis

Thermogravimetry analysis and gas chromatography techniques are used at different heating rates (from 5 to 50 K/min) to map all the products and to develop suitable kinetic models of biomass pyrolysis. A three-independent-parallel-reactions model is used to model kinetic of total devolatilization. This part accounts for the total char yield and devolatilization time. The evolutions of condensable vapors (tar and H₂O) and non-condensable gases (H₂, CH₄, CO and CO₂) are also studied using gas chromatography technique. It is shown that the final total yield of gases increases by increasing the heating rate, whereas those of tar decrease by increasing heating rate. A kinetic model was then proposed and the parameters for that were calculated, which can predict the change of the gases yields at different heating rates. The performance of the kinetic models was evaluated for other experimental works available in the literature or by exposing the biomass to different heating program.     

Kinetic analyses of biomass pyrolysis using the distributed activation energy model

The pyrolysis behaviors of several agricultural residues have been investigated by using thermogravimetric analysis. The evolving rates of the gaseous products during the pyrolysis such as H₂, CH₄, H₂O, CO and CO₂ were also measured by the TG-MS techniques. Without any assumption and mathematical fitting, we could obtain the very proper kinetic parameters (the distribution curve of activation energy, f(E), and the activation energy dependent frequency factor, k₀(E)) of biomass pyrolysis by utilizing the distributed activation energy model (DAEM) proposed by Miura and Maki [Miura K, Maki T. Energ Fuel 1998;12:864]. The peaks of f(E) curve for rice straw, rice husk, corncob and cellulose were found to be 170, 174, 183, and 185 kJ/mol, respectively. The k₀ value increased from an order of 10¹¹ to an order of 10¹⁸ s⁻¹, while E increased from 120 to 250 kJ/mol. The catalytic effects of alkali and alkaline earth metals during the pyrolysis play a major role in the variation of f(E) curve among the different biomass species.     

Prediction of pyrolysis kinetic parameters from biomass constituents based on simplex-lattice mixture design

The aim of this study is to determine the effect of the main chemical components of biomass:cel ulose, hemicel-lulose and lignin, on chemical kinetics of biomass pyrolysis. The experiments were designed based on a simplex-lattice mixture design. The pyrolysis was observed by using a thermogravimetric analyzer. The curves obtained from the employed analytical method fit the experimental data (R2 N 0.9). This indicated that this method has the potential to determine the kinetic parameters such as the activation energy (Ea), frequency factor (A) and re-action order (n) for each point of the experimental design. The results obtained from the simplex-lattice mixture design indicated that cellulose had a significant effect on Ea and A, and the interaction between cellulose and lignin had an important effect on the reaction order, n. The proposed models were then proved to be useful for predicting pyrolysis behavior in real biomass and so could be used as a simple approximation for predicting the overall trend of chemical reaction kinetics.     

Thermogravimetric characteristics and kinetic study of biomass co-pyrolysis with plastics

The pyrolysis of pure biomass, high density polyethylene (HDPE), polypropylene (PP) and polyethylene terephthalate (PET), plastic mixtures [HDPE+PP+PET (1: 1: 1)], and biomass/plastic mixture (9: 1, 3: 1, 1: 1, 1: 3 and 1: 9) were investigated by using a thermogravimetric analyzer under a heating rate at 10 °C/min from room temperature to 800 °C. Paper was selected as the biomass sample. Results obtained from this comprehensive investigation indicated that biomass was decomposed mainly in the temperature range of 290–420 °C, whereas thermal degradation temperature of plastic mixture is 390–550 °C. The percentage weight loss difference (W) between experimental and theoretical ones was calculated, which reached a significantly high value of (−)15 to (−)50% at around 450 °C in various blend materials. These thermogravimetric results indicate the presence of significant interaction and synergistic effect between biomass and plastic mixtures during their co-pyrolysis at the high temperature region. With increase in the amount of plastic mixture in blend material, the char production has diminished at final pyrolysis temperature range. Additionally, a kinetic analysis was performed to fit with TGA data, the entire pyrolysis processes being considered as one or two consecutive first order reactions.     

生物质热解特性研究

以竹材、稻壳、木屑为原料,通过常规热解结合快速热解研究生物质热解特性。结果表明,生物质常规热解的液体得率较低,相比而言竹材最高,稻壳最低,且热解温度是影响竹材和木屑热解的主要因素,其液体得率随温度的升高呈先增后减的变化规律;快速热解方面,利用居里点裂解仪和GC—MS在线分析竹材热解的液相组成,其组成以糠醛和酚类物质为主,它们分别来源于纤维素、半纤维素和木质素的热解。     

Kinetic study of Chinese biomass slow pyrolysis: Comparison of different kinetic models

The slow pyrolysis of six Chinese biomasses was studied by thermogravimetric experiments. Non-linear square fitting method is used to calculate DTG data. The analysis results show that it is not possible to exactly represent the biomass pyrolysis by a one-step model with different mechanisms. Thus, three-pseudocomponent models were used to simulate the biomass pyrolysis. It was found that the three-pseudocomponent model with n-order kinetics (model II) is more accurate than the model with first-order kinetics (model I). Activation energies of three-pseudocomponents in model II are bigger than the values in model I. It is shown that model II yields the best simulation results, especially with respect to describe accurately the pyrolysis of the first pseudocomponent (hemicellulose) and the last one (lignin). Nevertheless, with regard to a practical utilization, the three-pseudocomponent model with a reaction order of one could be used, because the accuracy to represent biomass pyrolysis is high enough. Unrealistic high values of the reaction order are avoided, and thus this model is more realistic with respect to the chemical interpretation of the reaction order.     

Effect of cellulose, lignin, alkali and alkaline earth metallic species on biomass pyrolysis and gasification

Fundamental pyrolysis/gasification characteristics of natural biomass and acid-washed biomass without alkali and alkaline earth metals (AAEM) were investigated by a thermogravimetric analyzer (TGA) and a fixed-bed reactor. In these experiments, six types of biomass were used and the contents of cellulose, lignin and AAEM species in the biomass were measured. It was observed that the characteristic of biomass pyrolysis and gasification was dependent on its components and AAEM species on the basis of TGA experiments. During biomass pyrolysis, the tar and gas yields increased with the growth of cellulose content, but the char yield decreased. There were two reactions indicating two major decomposition mechanisms. The first stage of decomposition showed rapid mass decrease due to the volatilization of cellulose, while the second stage became slow attributed to the lignin decomposition. The higher the cellulose content, the faster the pyrolysis rate. In contrast, the pyrolysis rate of biomass with higher lignin content became slower. In addition, the rises of cellulose content elevated the peak temperature of gasification and prolonged the gasification time. Meanwhile, the effect of AAEM species on gasification behavior was studied by comparing unwashed and acid-washed biomass. AAEM species increased the peak gasification value, whereas decreased initial gasification temperature. It revealed that the activity of biomass gasification was attributed to the interaction between AAEM-cellulose/lignin.     

A novel test method for catalysts in the treatment of biomass pyrolysis oil

A novel microscale test method was developed for testing catalysts. A pyrolyser connected to a gas chromatograph was used for pyrolysing the biomass sample and for leading the pyrolysis vapours through the catalyst for instant analysis. The injection port of the gas chromatograph was used as a fixed-bed catalyst reactor. Detection of reaction products was carried out with an atomic emission detector to quantify the various elements or with a mass selective detector to identify the compounds.

The test method was applied to treating pyrolysis vapours of Scots pine sawdust with ZnO, MgO, dolomite and limestone. Mass balances for carbon and hydrogen were determined with and without the catalyst. The carbon yields in liquid fraction decreased with all the catalysts studied. The highest yields were obtained with ZnO. Product distribution in pyrolysis vapours was rather similar with ZnO or without any catalyst. With MgO, dolomite and limestone, the compounds of pyrolysis vapours comprised mainly gases, water and degradation products of polysaccharides as well as some aromatic hydrocarbons.     

A study on the pyrolysis of asphalt

The pyrolysis of asphalt has been studied using thermogravimetric analysis at atmospheric pressure and with nitrogen as the ambient gas. The heating rates ranged from 50 or 80 °C min⁻¹ to a final temperature of 650 °C. A two-stage first-order model is established to describe the pyrolysis of asphalt. In the model, the activation energy, E, is different for each stage, but is independent of the type of asphalt and its heating rate. The frequency factor depends on the heating rate and is independent of the asphalt. The final yield of volatiles depends on the type of asphalt. The modeled results agree with the experimental measurements, so the model is reasonable.     

Study of the kinetic behaviour of biomass and coal during oxyfuel co-combustion

In this study, the thermogravimetric analysis(TGA) method has been used to evaluate the kinetic behavior of biomass, coal and its blends during oxyfuel co-combustion. The thermogravimetric results have been evaluated by the Coats–Redfern method and validated by Criado's method. TG and DTG curves indicate that as the oxygen concentration increases the ignition and burn out temperatures approach a lower temperature region. The combustion characteristic index shows that biomass to coal blends of 28% and 40% respectively can achieve enhanced combustion up to 60% oxygen enrichment. In the devolatilization region, the activation energies for coal and blends reduce while in the char oxidation region, they increase with rise in oxygen concentration. Biomass, however, indicates slightly different combustion characteristic of being degraded in a single step and its activation energies increase with rise in oxygen concentration. It is demonstrated in this work that oxygen enrichment has more positive combustion effect on coal than biomass. At 20% oxygen enrichment, 28% and 40% blends indicate activation energy of 132.8 and 125.5 kJ·mol~(-1) respectively which are lower than coal at 148.1 kJ·mol~(-1) but higher than biomass at 81.5 kJ·mol~(-1) demonstrating synergistic effect of fuel blending. Also, at char combustion step, an increase in activation energy for 28% blend is found to be 0.36 kJ·mol~(-1) per rise in oxygen concentration which is higher than in 40% blend at 0.28 kJ·mol~(-1).     

Catalytic pyrolysis of biomass for biofuels production

Fast pyrolysis bio-oils currently produced in demonstration and semi-commercial plants have potential as a fuel for stationary power production using boilers or turbines but they require significant modification to become an acceptable transportation fuel. Catalytic upgrading of pyrolysis vapors using zeolites is a potentially promising method for removing oxygen from organic compounds and converting them to hydrocarbons. This work evaluated a set of commercial and laboratory-synthesized catalysts for their hydrocarbon production performance via the pyrolysis/catalytic cracking route. Three types of biomass feedstocks; cellulose, lignin, and wood were pyrolyzed (batch experiments) in quartz boats in physical contact with the catalysts at temperature ranging from 400 °C to 600 °C and catalyst-to-biomass ratios of 5-10 by weight. Molecular-beam mass spectrometry (MBMS) was used to analyze the product vapor and gas composition. The highest yield of hydrocarbons (approximately 16 wt.%, including 3.5 wt.% of toluene) was achieved using nickel, cobalt, iron, and gallium-substituted ZSM-5. Tests performed using a semi-continuous flow reactor allowed us to observe the change in the composition of the volatiles produced by the pyrolysis/catalytic vapor cracking reactions as a function of the catalyst time-on-stream. The deoxygenation activity decreased with time because of coke deposits formed on the catalyst.     

Modeling the combined impact of moisture and char shrinkage on the pyrolysis of a biomass particle

A detailed computational model of pyrolysis of a moist, shrinking biomass particle is presented. This model is used to examine the effect of varying the moisture content for a single shrinking biomass particle subjected to a constant external temperature. Particle half-thicknesses ranging from 5 μm to 2 cm, temperatures from 800 to 2000 K, moisture contents from 0 to 30% (dry basis), and shrinkage factors from 1.0 to 0.4 are examined. The impact of moisture content and shrinkage was found to be a function of pyrolysis regime. In general, coupling between moisture content and shrinkage was found to result in longer pyrolysis times than if they were considered separately. Additionally, coupling between moisture content and shrinkage increased tar yield and decreased light hydrocarbon yield compared to considering moisture and shrinkage separately.     

Comparison of the thermal reactivities of isolated lignin and holocellulose during pyrolysis

Woody shells of Turkish hazelnuts which are rich in lignin content offer an important potential as a renewable energy source. Hence, this study focuses on the investigation of the thermal reactivities of the real macromolecular ingredients of this biomass species. Hazelnut shells were treated with chemicals to isolate its holocellulose (hemicelluloses + cellulose) and lignin. Scanning Electron Microscopy (SEM) images revealed the significant differences between the physical features of the untreated biomass and its isolated ingredients. Thermal properties of the biomass and these ingredients were examined by Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) techniques under non-isothermal pyrolysis conditions from ambient to 900 °C. It was found that unlike holocellulose, lignin slowly decomposes in a wider temperature range, and its decomposition is associated with exothermic heat flow. It was also concluded that the hemicellulosics in holocellulose have very important effects with respect to the char yield and the exothermicity of the process. Besides, inorganics in biomass play a catalytic role during pyrolysis. The activation energies calculated according to Borchardt-Daniels' kinetic model were 64.8 and 51.8 kJ/mol for the pyrolysis of holocellulose and lignin, respectively, and each of them is higher than that for the untreated biomass.     

Pyrolysis kinetics of atmospheric residue and its SARA fractions

Thermal analysis of atmospheric residue from heavy crude oil and its SARA fractions was carried out and the tendency of each fraction toward coke formation was determined. The coke yield was 16.3 wt.% for atmospheric residue, 43.1 wt.% for asphaltenes, 4.6 wt.% for resins, 3.8 wt.% for aromatics, and 0.3 wt.% for saturates. Pyrolysis kinetics of residue and its fractions, i.e., asphaltenes, resins and aromatics was also investigated. The TG experiments were conducted at three different heating rates of 8, 12, and 16 °C/min from room temperature up to 800 °C under nitrogen atmosphere to verify the weight variation with reaction temperature. Isoconversional analysis to fit data assuming first order kinetics was employed. Asphaltenes was the fraction that produces coke in higher amount having a range of activation energy of 41.0–58.6 kcal mol⁻¹ whereas activation energy for atmospheric residue ranged from 11.5 to 30.0 kcal mol⁻¹.     

Modelling intra-particle phenomena of biomass pyrolysis

The characteristic times of the main intra particle phenomena of wood pyrolysis are discussed to develop a new model of biomass pyrolysis. The model accounts for a simplified multi-step chemical decomposition with the formation of tars at liquid phase inside the particle. The tars at liquid phase are then competitively converted into a secondary char and gases and evaporated following a Clausius–Clapeyron law. To our knowledge, a tar evaporation law had so far never been coupled with cellulose pyrolysis kinetics. The convective mass transport of all the volatile species through the porous particle is modelled by a Darcy's law. This model offers a first approach to simulate the tar (at liquid phase) life time and its intra-particle conversion. The Clausius–Clapeyron evaporation parameters are reviewed and modified if levoglucosan or cellobiosan are supposed as the main tar compounds at liquid phase. The effects of these parameters on cellulose pyrolysis mass loss rate are modelled and discussed. Mass transfer limitations can lead to a high intra-particle over-pressure and can control the life time of tar at liquid phase and the subsequent “secondary” char formation from the liquid tar conversion.     

Kinetics of pyrolysis,combustion and gasification of three biomass fuels

The paper compares the microstructural properties and the intrinsic reactivity of pine seed shells, olive husk and wood chips upon pyrolysis, combustion and gasification (with CO₂ and H₂O). Such biomasses, all of interest in energy production, are quite different from one another in terms of O/C and H/C content, of porosimetric structure and of ash content.     

Kinetic study on the thermal degradation of a biomass and its compost: Composting effect on hydrogen production

Compost from vegetable residues is usually used as an organic amendment to soil; however, their thermal degradation characteristics show that it could be used as raw material in air gasification facilities. According to the obtained data, hydrogen production is positively affected by composting, increasing hydrogen concentration in the raw gas from 15.2 to 22.6 vol%. This effect is related with physicochemical changes that occur during thermophilic stage of composting. After this step it does not observes any progress on hydrogen production.On the other hand, in order to compare thermal degradation of a biomass (Leucaena leucocephala) and two composts with different maturation levels, non-isothermal thermogravimetric analysis (TGA) has been used. Under inert atmosphere, data have been adequately simulated assuming three fractions (hemicellulose, cellulose and lignin) in both biomass and composts. However, under air atmosphere we have used a simplified model that assume two components in biomass (holocellulose and lignin) and three in composts (including humic substances). Using nth-order kinetic equations to describe component degradations, we have calculated a set of kinetic parameters which do not differ of the reported for other lignocellulosic materials. This procedure allows obtaining an approximate composition of samples.     

Effects of particle size on the fast pyrolysis of oil mallee woody biomass

This study aims to investigate the effects of biomass particle size (0.18-5.6 mm) on the yield and composition of bio-oil from the pyrolysis of Australian oil mallee woody biomass in a fluidised-bed reactor at 500 °C. The yield of bio-oil decreased as the average biomass particle size was increased from 0.3 to about 1.5 mm. Further increases in biomass particle size did not result in any further decreases in the bio-oil yield. These results are mainly due to the impact of particle size in the production of lignin-derived compounds. Possible inter-particle interactions between bio-oil vapour and char particles or homogeneous reactions in vapour phases were not responsible for the decreases in the bio-oil yield. The bio-oil samples were characterised with thermogravimetric analysis, UV-fluorescence spectroscopy, Karl-Fischer titration as well as precipitation in cold water. It was found that the yields of light bio-oil fractions increased and those of heavy bio-oil fractions decreased with increasing biomass particle size. The formation of pyrolytic water at low temperatures (<500 °C) is not greatly affected by temperature or particle size. It is believed that decreased heating rates experienced by large particles are a major factor responsible for the lower bio-oil yields from large particles and for the changes in the overall composition of resulting oils. Changes in biomass cell structure during grinding may also influence the yield and composition of bio-oil.     

Structural evolution of chars from biomass components pyrolysis in a xenon lamp radiation reactor

The structural evolution of the chars from pyrolysis of biomass components(cellulose, hemicellulose and lignin)in a xenon lamp radiation reactor was investigated. The elemental composition analysis showed that the C content increased at the expense of H and O contents during the chars formation. The values of ΔH/C/ΔO/Cfor the formation of cellulose and hemicellulose chars were close to 2, indicating that dehydration was the dominant reaction. Meanwhile, the value was more than 3 for lignin char formation, suggesting that the occurrence of demethoxylation was prevalent. FTIR and XRD analyses further disclosed that the cellulose pyrolysis needed to break down the stable crystal structure prior to the severe depolymerization. As for hemicellulose and lignin pyrolysis, the weak branches and linkages decomposed firstly, followed by the major decomposition. After the devolatilization at the main pyrolysis stage, the three components encountered a slow carbonization process to form condensed aromatic chars. The SEM results showed that the three components underwent different devolatilization behaviors, which induced various surface morphologies of the chars.     

The effect of lignin and inorganic species in biomass on pyrolysis oil yields, quality and stability

This paper investigates four reference fuels and three low lignin Lolium Festuca grasses which were subjected to pyrolysis to produce pyrolysis oils. The oils were analysed to determine their quality and stability, enabling the identification of feedstock traits which affect oil stability. Two washed feedstocks were also subjected to pyrolysis to investigate whether washing can enhance pyrolysis oil quality. It was found that the mineral matter had the dominate effect on pyrolysis in compared to lignin content, in terms of pyrolysis yields for organics, char and gases. However the higher molecular weight compounds present in the pyrolysis oil are due to the lignin derived compounds as determined by results of GPC and liquid-GC/MS. The light organic fraction also increased in yield, but reduced in water content as metals increased at the expense of the lignin content. It was found that the fresh oil and aged oil had different compound intensities/concentrations, which is due to a large number of reactions occurring when the oil is aged day by day. These findings agree with previous reports which suggest that a large amount of re-polymerisation occurs as levoglucosan yields increase during the aging progress, while hydroxyacetaldehyde decrease. In summary the paper reports a window for producing a more stable pyrolysis oil by the use of energy crops, and also show that washing of biomass can improve oil quality and stability for high ash feedstocks, but less so for the energy crops.