Dominant design variables in pyrolysis of biomass particles of different geometries in thermally thick regime

In this study, a simultaneous chemical kinetics and heat transfer model is used to predict the effects of the most important physical and thermal properties (thermal conductivity, heat transfer coefficient, emissivity, reactor temperature and heat of reaction number) of the feedstock on the convective-radiant pyrolysis of biomass fuels for different geometries such as slab, cylinder and sphere. The pyrolysis rate is simulated by a kinetic scheme involving two parallel primary reactions and a third secondary reaction between volatile and gaseous products and the char. Finite difference pure implicit scheme utilizing the Tri-Diagonal Matrix Algorithm (TDMA) is employed for solving heat transfer model equation. Runge-Kutta fourth order method is used for solving the chemical kinetics model equations. Simulations are carried out for different geometries considering the equivalent radius ranging from to , and the temperature ranging from to .For conversion in the thermally thick regime (intra-particle heat transfer control), it is found that variations in the properties mainly affect the activity of primary reactions. The highest sensitivity is associated with reactor temperature and emissivity. Applications of these findings in reactor design and operation are discussed. The results obtained using the model used in the present study are in excellent agreement with many reported experimental studies, much better than the agreement with earlier models reported in the literature.     

Pyrolysis of single large biomass particle: Simulation and experiments

Pyrolysis and heat transfer characteristics of single large biomass particle were investigated using three-dimensional unsteady heat transfer model coupled with chemical reactions. The consumption of biomass and the production of products were simulated. Some experiments were designed to provide model parameters for simulation calculations. The simulation was verified by pyrolysis experiments of large biomass particle in a vertical tube furnace. The simulation results show the internal heat and mass transfer law during the pyrolysis of large biomass particle. When the biomass particle diameter is between 10 and 30 mm, for every 5 mm increase in particle diameter, the time required for complete pyrolysis will increase on average by about 50 s. When the pyrolysis temperature is between 673 K and 873 K, a slight decrease in the pyrolysis temperature will cause the time required for the biomass to fully pyrolyze to rise significantly. And the phenomenon is more obvious in the low temperature range. The results indicate that the numerical simulation agrees well with the experimental results.     

A phenomenological model of the mechanisms of lignocellulosic biomass pyrolysis processes

A comprehensive particle scale model for pyrolysis of biomass has been developed by coupling the reaction mechanisms and transport phenomena. The model, which also accounts for the combined effect of various parameters such as particle shrinkage and drying, was validated using available experimental data from the literature. The validated model was then used to study the effect of operating temperature and biomass particle size, both of which strongly influenced the rate of biomass conversion. For example, for particle sizes less than 1 mm, a uniform temperature throughout the particle was predicted, thus leading to higher conversion rates in comparison to those in the larger particles. On the other hand, any increase in moisture content led to considerable decrease in the rate of biomass conversion. For the operating conditions considered in this study, the volumetric particle shrinkage also increased the decomposition of biomass to end products.     

Birch wood particle shrinkage during rapid pyrolysis

A study of the shrinkage of cubic (∼5 mm) birch wood particles during pyrolysis is presented. The particles were rapidly injected into a preheated furnace with a constant temperature in the range 350-900°C. The size of the particles in longitudinal, tangential and radial directions was measured until no further mass loss occurs. The volume shrinkage was found to be 45-70% and the shrinkage in the different directions 5-25, 25-40 and 15-40% for longitudinal, tangential and radial directions, respectively. Longitudinal shrinkage commenced after about 60% mass loss and is not strongly dependent on heating rate or on cellulose chain scission. A maximum shrinkage was found for tangential and radial directions at 400 and 500-700°C, respectively, and above these temperatures the shrinkage decreases. The char yield decreases and the char structure becomes more deranged with increasing temperature. Empirical models of shrinkage as a function of conversion are presented.     

Analysis and modelling of wood pyrolysis

In many industrial processes wood is treated as big fragments or pellets. In such conditions kinetics and yields are different with respect to the case of particles with few mg weight. However most of published kinetic models were based on experimental data obtained with very small samples. In this work pyrolysis of wood pellets was investigated by using a special experimental device which allowed to determine kinetics of total weight loss, gas and tar production. Two different heating rates, 0.05 and 1 K/s, were employed to determine kinetic parameters. Dynamic and isothermal pyrolysis tests were carried out on beech and pine wood previously dried in an oven. A simple but realistic kinetic scheme was proposed able to take into account the phenomena that happen in big wood particles. The numerical parameters were determined from the results of experimentation on beech wood. The proposed kinetic model takes into account the presence of two different stages during pyrolysis: a first one involving only unreacted wood and a second one where the products not yet escaped from the solid matrix react further. This kinetic model allowed to fit the experimental data quite well. The model was successfully validated with tests performed at an elevated heating rate (approximately 60–100 K/s) of the external surface of the pellets. In these conditions, the pellets showed a marked gradient of temperature inside, which was suitably considered.     

Heat of wood pyrolysis

The heat of pyrolysis of beech and spruce wood was investigated by means of a differential scanning calorimeter. Wide variations were found for the heat of the primary pyrolysis process, depending on the initial sample weight and on the conditions used in the measurements. However, reporting the heat of the primary pyrolysis process versus the final char yield resulted in a linear correlation. This strong dependency of the heat of wood pyrolysis on the final char yield, that is in turn highly sensitive to the experimental conditions, can explain the uncertainty of the data for the heat of wood pyrolysis reported in the literature. A possible explanation for the variability of the heat of wood pyrolysis depending on the final char yield seems to be an exothermic primary char formation process competing with an endothermic volatile formation process.     

窑街油页岩热解动力学研究

利用差热分析仪对窑街油页岩进行不同恒速升温速率的热解实验,考察升温速率对热解的影响,随着升温速率加快,失重曲线和最大热解速率向高温区。建立Friedman动力学模型对热解数据进行了数学处理,得到了活化能的变化范围为120～190kJ·mol^-1,而且活化能E与频率因子A的对数呈良好的线性关系,对认识油页岩干酪根的热解机理和化学结构提供重要信息。     

Study of pyrolysis kinetics of oil shale

The pyrolysis experiments on oil shale samples from Fushun, Maoming, Huangxian, China, and Colorado, USA, were carried out with the aid of thermogravimetric analyzer (TGA) at a constant heating rate of 5 °C/min. A kinetic model was developed which assumes several parallel first-order reactions with changed activation energies and frequency factors to describe the oil shale pyrolysis. The kinetic parameters of oil shale pyrolysis were determined on the basis of TGA data. The relationship between the kinetic parameters was further investigated and the correlation equations of x_∞-E and ln A-E were obtained. These equations show that the final fractional conversion of each parallel reaction, x_∞(j), can be expressed as an exponential function of the corresponding activation energy. The plot of ln A-E for different reactions becomes a straight line. These relationship equations can provide important information to understand the pyrolysis mechanism and to investigate the chemical structure of oil shale kerogen.     

石脑油裂解装置建模与仿真技术

裂解装置提供了石化行业大部分基础原料，石脑油是目前国内外重要的裂解原料。对石脑油裂解反应过程、结焦过程和裂解炉辐射段的建模与仿真进行了综述：目前对分子动力学研究较多，用于离线仿真能够获得较好的效果，但在线应用不多；自由基动力学模型则是深入研究石脑油裂解过程本质的必然途径，在实际应用中越来越显示出其优越性。     

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.     

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.     

Mechanisms and kinetics of homogeneous secondary reactions of tar from continuous pyrolysis of wood chips

The change of mass and composition of biomass tar due to homogeneous secondary reactions was experimentally studied by means of a lab reactor system that allows the spatially separated production and conversion of biomass tar. A tarry pyrolysis gas was continuously produced by pyrolysis of wood chips (fir and spruce, 10-40 mm diameter) under fixed-bed biomass gasification conditions. Homogeneous secondary tar reactions without the external supply of oxidising agents were studied in a tubular flow reactor operated at temperatures from 500 to 1000 °C and with space times below 0.2 s. Extensive chemical analysis of wet chemical tar samples provided quantitative data about the mass and composition of biomass tar during homogeneous conversion. These data were used to study the kinetics of the conversion of gravimetric tar and the formation of PAH compounds, like naphthalene.It is shown that, under the reaction conditions chosen for the experiments, homogeneous secondary tar reactions become important at temperatures higher than 650 °C, which is indicated by the increasing concentrations of the gases CO, CH₄, and H₂ in the pyrolysis gas. The gravimetric tar yield decreases with increasing reactor temperatures during homogeneous tar conversion. The highest conversion reached in the experiments was 88% at a reference temperature of 990 °C and isothermal space time of 0.12 s. Hydrogen is a good indicator for reactions that convert the primary tar into aromatics, especially PAH. Soot appears to be a major product from homogeneous secondary tar reactions.     

Validation of a numerical approach to model pyrolysis of biomass and assessment of kinetic data

The objective of this contribution is to introduce a numerical approach that predicts pyrolysis of various biomasses under various boundary conditions such as particle geometry and heating rate. Hence, the approach is applicable to numerical tools that help exploiting further the potential of biomass as an energy resource. Furthermore, it is intended to represent the general trend of state of the art in model developments. The presented model itself is based on one-dimensional and transient differential conservation equations for mass, momentum, species and energy. In order to account for a variety of reaction schemes a formulation based on the Arrhenius equation including intrinsic modelling is chosen. It is believed to represent the majority of kinetic pyrolysis data derived from experiments. Applying this single numerical approach to predict pyrolysis under varying experimental conditions for different materials always revealed good agreement with measurements.     

生物质热解气喷雾冷凝的传热传质特性

生物质热解气的快速冷凝是影响生物油品质和出油率的关键因素之一。喷雾冷凝是实现快速冷凝的有效方法。文中以生物质热解气的关键组分所形成的多组分体系为研究对象,采用多组分体系传热传质经典的膜模型,使用Maxwell-Stefan方程描述其质量传递,结合气液相际传质的特点,进行了喷雾冷凝过程中的传热传质耦合计算。通过计算获得了液滴直径、液滴平均温度以及混合气体平均温度的变化规律,并探讨了初始流速、喷雾液滴直径和气液质量流量比对热解气冷凝过程的影响。     

Heat and mass transfer of single droplet/wet particle drying

A theoretical model, which considers the fully unsteady character of both heat and mass transfer during the drying of single droplet/wet particle, is presented. The model enables prediction of pressure and fraction distributions of air-vapour mixture within the capillary pores of the wet particle crust. The simulations of the drying process of a single silica droplet under different conditions show a permanent rising of pressure within the capillary pores, but the corresponding vapour fraction remains less than unity. The comparison between the drying histories of the silica droplet, predicted by the present model with the data, calculated by the model which assumes a quasi-steady-state mass transfer and linear pressure profile within the capillary pores, shows inconsiderable differences between the droplet/wet particle temperature and mass time-changes. At the same time, the present model predicts pressure build-up and temperature rising within the particle wet core. However, in the studied cases the temperature of the wet core temperature does not exceed the liquid saturation temperature and therefore no boiling of liquid within the particle wet core is observed.     

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.     

Heat transfer characteristics of molten plastics in a vertical falling film reactor

The heat transfer efficiency during the pyrolysis process is a key factor to be considered in the design of pyrolysis reactors. In this study, the average apparent heat transfer characteristics of molten plastic pyrolysis in a vertical falling film reactor were explored by experiments and numerical simulation and the apparent heat transfer coefficients were determined. In addition, the temperature distribution and the thickness of the liquid film in the reactor were predicted and the influences of pyrolysis temperatures on the average apparent heat transfer coefficients were discussed.     

Development of a comprehensive free radical photopolymerization model incorporating heat and mass transfer effects in thick films

A comprehensive kinetic model describing photopolymerization is developed which allows variation of temperature, species concentrations, and light intensity through the thickness of a photopolymerized film. Heat and mass transfer effects are included, as is the generation of heat by both reaction and light absorption. In addition to initiation, propagation, and termination mechanisms, both primary radical termination and inhibition are incorporated into the model. The possible presence and diffusion of an inert solvent are also accounted for. Thus, the model is useful for examining complex polymerization kinetics and behavior in industrially and commercially important thick film photopolymerizations, such as the curing of contact lenses, dental restorative materials, photolithographic resists, and optoelectronic coatings. The comprehensive model is used to predict polymerization rate, temperature, and conversion profiles in a variety of systems. The effects of heat generation and the thermal boundary conditions are explored, with the result that heat generation in thick samples leads to greatly increased conversions approaching 100 percent. Increased temperature in these samples also may lead to the appearance of two rate maxima, with the first due to the temperature increase and the second caused by the autoacceleration process. The magnitude of the temperature increase, along with the resultant effects, is more pronounced in insulated systems.