Experimental and numerical investigation on the pyrolysis of single coarse lignite particles

This paper reports on the mathematical modeling of the pyrolysis of single coarse lignite particles using a kinetics model coupled with a heat transfer model. The parallel reaction kinetics model of the lignite pyrolysis makes no assumptions about the activation energy distribution and the conversion of sub-reactions. The pyrolysis kinetics parameters were obtained on the basis of experimental data from thermogravimetric analysis (TGA) tests. The heat transfer model includes diffusive, convective and radiative heat transfer modes. The experimental investigations were carried out for single lignite particles in an electrically heated reactor. Measurements of the temperature and mass loss were performed during the pyrolysis in a nitrogen atmosphere. The model predictions for the temperature and mass loss histories agree well with the experimental data, verifying that the mathematical model accurately evaluates the pyrolysis of lignite particles. The effects of temperature and particle size on the pyrolysis time and final residual mass fraction were evaluated using the numerical model.     

Pyrolysis of scrap tire rubbers: Relationships of process variables with pyrolysis time

The functional relationships of industrially interesting variables such as pyrolysis temperature, heating rate, and sample size with pyrolysis time were explored to provide basic information on designing energy efficient processes. Pyrolysis kinetics of scrap tire rubbers tested in this study were investigated to formulate the functional relationships of pyrolysis temperature and heating rate. The pyrolysis time decreases exponentially with increasing pyrolysis temperature and heating rate, indicating high activation energies of pyrolysis reaction of the scrap tire rubbers tested in this study. The effect of heat transfer on the pyrolysis kinetics was evaluated by seeking the functional relationship between the sample size and pyrolysis time.The pyrolysis time increases linearly with increasing sample diameter. The slope of the straight line is proportional to the specific heat of the sample.     

热分析在煤燃烧和热解及气化动力学研究中的应用

论述了煤的燃烧、热解、气化反应动力学的常用的单一升温速率法、多重扫描速率法、动力学补偿效应以及分布活化能动力学模型等热分析研究方法，分析了现用热分析动力学方法的局限性；并对反应控制热分析、微热分析技术、微波热分析以及热分析技术与其他分析技术的联用，热分析技术间的联用等热分析新技术在煤的燃烧、热解、气化反应动力学研究上的应用进行了展望．     

Integrated kinetics and heat flow modelling to optimise waste tyre pyrolysis at different heating rates

Pyrolysis is a promising technology to tackle the waste tyre disposal problem via converting the waste tyres into hydrocarbon fuels. This paper uses the experimental data of tyre pyrolysis (TGA/DTG and DTA) to examine both the kinetics and the heat flow at various heating rates for large tyre particles. An integrated model that considers the mass loss kinetics, exothermic kinetics, and heat flow together was developed. With the aid of the model, a multi-stage pyrolysis operation strategy is proposed. The strategy firstly starts with a heating stage to initialise the exothermic reactions in the pyrolysis. Then it changes to an adiabatic stage, where the exothermic heat is captured to facilitate the endothermic reactions afterwards. The multi-stage operation strategy achieves a significant energy saving comparing with the conventional operation strategy.     

Thermal decomposition behavior of silica‐phenolic composite exposed to one‐sided radiant heating

When polymer‐matrix composite reaches sufficiently high temperature, pyrolysis reactions of the polymer matrix occur. The thermal decomposition behavior of silica‐phenolic composite was investigated using solar radiant heating experiment with one‐sided heat flux. Thermogravimetric studies and combined thermal analysis techniques were performed to characterize the thermal decomposition kinetics of phenolic resin. Simultaneously a thermal response model was used to calculate the through‐thickness temperature distribution. The calculated time‐dependent temperature profile at different material depths were compared with the experimental results measured at the same location. The silica‐phenolic composite exhibited an excellent thermal insulation during thermal exposure. The postheating specimen was sectioned in millimeter segments to determine the density profile. On the basis of the density profile, the transition from char layer to pyrolysis zone to virgin material was estimated. Finally, the material morphology was analyzed for silica‐phenolic composite after thermal exposure. POLYM. COMPOS., 36:1557–1564, 2015. © 2014 Society of Plastics Engineers     

Modelling of the pyrolysis of biomass particles. Studies on kinetics,thermal and heat transfer effects

The present work provides a rationally-based model to describe the pyrolysis of a single solid particle of biomass. As the phenomena governing the pyrolysis of a biomass particle are both chemical (primary and secondary reactions) and physical (mainly heat transfer phenomena), the presented model couples heat transport with chemical kinetics. The thermal properties included in the model are considered to be linear functions of temperature and conversion, and have been estimated from literature data or by fitting the model with experimental data. The heat of reaction has been found to be represented by two values: one endothermic, which prevails at low conversions and the other exothermic, which prevails at high conversions. Pyrolysis phenomena have been simulated by a scheme consisting of two parallel reactions and a third reaction for the secondary interactions between charcoal and volatiles. The model predictions are in agreement with experimental data regarding temperature and mass-loss histories of biomass particles over a wide range of pyrolysis conditions.     

热载气体直接加热石油烃裂解研究进展?I. 裂解装置和技术

概述了以气体为热载体的石油烃直接加热裂解技术及其应用;介绍了热载气体直接加热石油烃裂解的装置组成、运行条件、产物产率、技术改进及发展状况,分析了裂解反应机理和反应动力学;指出热载气体直接加热裂解具有原料适用性广、产物分布灵活、热效率较高和受结焦影响小等优点,但同时也有裂解装置结构较复杂、缺乏系统性研究数据等不足. 最后对热载气体直接加热石油烃裂解的研究进行了展望,指出以氢氧燃烧产生的过热水蒸汽作为热载气体的直接加热裂解技术,在提高换热效率、降低碳排放、扩大原料范围和耦合制取合成气等方面有很大优势,发展前景广阔.     

Lumped reaction kinetic models for pyrolysis of heavy oil in the presence of supercritical water

The reaction kinetics of the pyrolysis of heavy oil in the presence of supercritical water (SCW) and high pressure N₂ were measured. At any reaction temperature applied, the pyrolysis under SCW environments is faster than that under N₂ environments. Meanwhile, at lower temperatures the pyrolysis under both environments is accelerated by the introduction of coke into the feedstock. On the basis of a first‐order four‐lump reaction network consisting of the sequential condensation of maltenes and asphaltenes, the pyrolysis in whichever medium can be preferably described either by the lumped reaction kinetic model modified with autocatalysis and pseudoequilibrium or by the model modified solely with pseudoequilibrium. Benefited from the reduced limitation of diffusion to reaction kinetics, the pyrolysis in the SCW phase is more sensitive to the increase in reaction temperature than that in the oil phase, disengaging readily from the dependence on autocatalysis at a lower temperature. © 2015 American Institute of Chemical Engineers AIChE J, 62: 207–216, 2016     

A particle scale model for municipal solid waste and refuse-derived fuels pyrolysis

The solid phase decomposition during pyrolysis of municipal solid waste (MSW) and refuse-derived fuels (RDF) is modelled on particle scale accounting for heat and mass transfer. Waste pyrolysis is expressed as a linear combination of pyrolysis of its components. The novel characterization method used expresses waste composition in terms of three reference species. The selected species are a mixture of cellulose and hemicellulose, a mixture of polystyrene and polyethylene terephthalate, and a mixture of polyethylene and polypropylene. The pyrolysis kinetics models for these components are taken from the literature. The fractions of the components in the mixtures are optimized to fit the model to non-isothermal mass loss curves from selected experimental reports. The particle scale model has been evaluated against experimental transient temperature profiles at the centre of a large waste pellet during pyrolysis. The model is able to predict the main trend, but shows a more fluctuating temperature curve.     

固体热载体热解高挥发分烟煤产物分布及性质

以三种高挥发分烟煤为原料,对固体热载体煤热解获得的气、油、焦产物产率、组成和性质进行了考察.结果表明,提高煤与热载体的混合热解温度可使煤气和焦油产率有所增加.热解焦油产率可达干煤重量的9%～11%,热解焦油可用于提取具有较高附加值的BTX,PCX,萘及脂肪族烃类等产品.热天平燃烧实验结果显示,热解半焦仍具有很好的着火和燃烧特性,随着热解反应温度的提高,燃烧区间向高温区移动,确定了半焦燃烧的反应动力学及其参数.     

竹材热解动力学特性分析

采用热重分析法研究了氮气气氛下竹材的热解行为及其动力学特性,分析了升温速率和粒径对竹材热解过程及动力学参数的影响. 结果表明,竹材热解分为干燥、预热解、热解和缓慢热解４个阶段;升温速率对竹材的热失重特性有显著影响,当升温速率从40℃/min增加到100℃/min时,竹材热解出现了滞后现象,热解活化能从130.87 kJ/mol下降到73.85 kJ/mol,频率因子及反应级数单调减小;不同升温速率下计算的活化能和频率因子之间存在良好的补偿效应;当粒径大于380 mm时,竹材的热解不仅受动力学控制,受颗粒传热、传质影响也较大.     

Evaluating effects of applying different kinetic models to pyrolysis modeling of fiberglass‐reinforced polymer composites

This research evaluates the effects of applying different kinetic models (KMs), developed based on thermal analysis using thermogravimetric analysis data, when used in typical 1D pyrolysis models of fiberglass‐reinforced polymer (FRP) composites. The effect of different KMs is isolated from the FRP heating by conducting pyrolysis modeling based on measured temperature gradients. Mass loss rate simulations from this pyrolysis modeling with various KMs show changes in the simulations due to applying different KM approaches are minimal in general. Pyrolysis simulations with the most complex KM are conducted at several heat flux levels. Mass loss rate comparison shows there is good overlap between simulations and the experimental data at low incident heat fluxes. Comparison shows there is poor overlap at high incident heat fluxes. These results indicate that increasing complexity of KMs to be used in pyrolysis modeling is unnecessary for these FRP samples and that the basic assumption of considering thermal decomposition of each computational cell in comprehensive pyrolysis modeling as equivalent to that in a thermogravimetric analysis experiment becomes inapplicable at depth and higher heating rates. Copyright © 2014 John Wiley & Sons, Ltd.     

Fast pyrolysis of glucose‐based carbohydrates with added NaCl part 2: Validation and evaluation of the mechanistic model

A mechanistic model considering the significant catalytic effects of Na⁺ on fast pyrolysis of glucose‐based carbohydrates was developed in Part 1 of this study. A computational framework based on continuous distribution kinetics and mass action kinetics was constructed to solve the mechanistic model. Agreement between model yields of various pyrolysis products with experimental data from fast pyrolysis of glucose‐based carbohydrates dosed with NaCl ranging from 0–0.34 mmol/g at 500 °C validated the model and demonstrated the robustness and extendibility of the mechanistic model. The model was able to capture the yields of major and minor products as well as their trends across NaCl concentrations. Modeling results showed that Na⁺ accelerated the rate of decomposition and reduced the time for complete thermoconversion of carbohydrates. The sharp reduction in the yield of levoglucosan (LVG) from fast pyrolysis of cellulose in the presence of NaCl was mainly caused by reduced decomposition of cellulose chains via end‐chain initiation and depropagation due to Na⁺ favoring competing dehydration reactions. Analysis of the contributions of reaction pathways showed that the decomposition of LVG made a minor contribution to its yield reduction and contributed less than 0.5% to the final yield of glycolaldehyde from fast pyrolysis of glucose‐based carbohydrates in the presence of NaCl. © 2015 American Institute of Chemical Engineers AIChE J, 62: 778–791, 2016     

Experimental studies on the thickness of upward flame over poly(methyl methacrylate) slabs

Experiments were performed to investigate the flame thickness of the upward flame on the poly(methyl methacrylate) slabs with width of 100‐400 mm. The results indicated that the flame thickness exhibited an increase first and then decrease trend in the upright orientation, and the maximum thickness location was approximately equal to the pyrolysis front location. The thickness of the flame along the lateral side of slab was less than that of the interior flame. The flame maximum thickness as a function of pyrolysis height and width was obtained, which showed the maximum thickness provided a power law increase with the pyrolysis height and width. Furthermore, the maximum thickness exhibited a power law increase with the total heat release rate as well. Based on the obtained flame thickness, the radiation heat flux at the pyrolysis height was estimated by using a simplified model. Comparison with the calculated convective heat flux revealed approximated pyrolysis heights for upward flame transition from convective heat flux controlled to radiation heat flux controlled.     

A model of devolatilization behavior in lignite pyrolysis with solid heat carriers

To elucidate the influence of the process conditions on pyrolytic products, the interactions between transport phenomena and pyrolysis kinetics are quantitatively analyzed at the level of a single coal particle. A comprehensive mathematical model is formulated to predict intraparticle multiphysics and devolatilization behaviors; the model contains two correlative one-dimensional unsteady heat conservation equations and ternary mass conservation equations in conjunction with the simplified dusty-gas model. Moreover, a multistep kinetic model of coal devolatilization is adopted to predict the generating rates of the lumped pyrolytic products. Validation of the model against experimental and literature data showed that can predict the transient temperature profiles of a coal particle and the yields of volatiles. Finally, the effects of the main process conditions on the intra- and extra-temperature history of lignite during pyrolysis with solid heat carriers are analyzed. The interactions between physical transport and the pyrolysis reaction are also examined.     

松木屑颗粒热解过程中的热/质传递规律

为探索在固定床反应器中有机固废颗粒热解过程中的热量、质量传递机理,本研究从颗粒尺度上对有机固废松木屑颗粒热解过程建模分析,模型中考虑了焦油的二次裂解反应及挥发分在颗粒孔隙中的质量、动量传递过程,并采用达西定律模拟了挥发分在颗粒孔隙内的流动现象,对颗粒热解过程的吸热反应以及挥发分逸出时的对流换热对颗粒温度的影响进行考察。基于两步反应动力学模型,探讨了不同颗粒尺寸、热解温度对有机固废松木屑颗粒热解过程的影响。结果表明,热解吸热反应和挥发分的对流换热阻碍了热量向颗粒中心的传递,延长了颗粒达到均温的时间;松木屑颗粒热解时,颗粒内会存在明显的温度梯度,在颗粒表面主要受化学反应动力学限制,在颗粒内部则主要受热量传递过程限制。此外,热解温度越低,粒径越大,颗粒内部的传热阻力越大。松木屑颗粒完全热解所需时间会随着颗粒粒径的增大而增加,但当颗粒粒径在10mm以上时,随着颗粒粒径的增大,颗粒完全热解所需时间的增量要大于10mm以下颗粒。     

Influence of out‐of‐plane fiber orientation on reaction‐to‐fire properties of carbon fiber reinforced polymer matrix composites

This work investigates the influence of the out‐of‐plane orientation of carbon fibers on the reaction‐to‐fire characteristics of polymer matrix composites. A deep insight into combustion processes is gained, which is necessary to fully understand and assess advantages of composites with out‐of‐plane fiber angles. Epoxy‐based Hexply 8552/IM7 specimens with primarily low fiber angles between 0° and 15° are characterized by cone calorimetry. Heat release during fire is greatly affected by the out‐of‐plane fiber angle because of the thermal boundaries created by the fibers. The advancement of the pyrolysis front during fire was determined from peak heat release rates and validated by temperature measurements along the back surface of the panels, representing a novel method of determining position‐dependent pyrolysis migration velocity. These measurements show a transverse shift in pyrolysis front velocity for increasing out‐of‐plane fiber angles. Pyrolysis pathways between the fiber boundaries facilitate faster combustion through the composite thickness, especially for increasing angles from 0° to 15°. It was determined that under the chosen conditions, the pyrolysis front advances approximately 4 times faster when propagating parallel to the fibers than perpendicular.     

Application of a simple enthalpy‐based pyrolysis model in numerical simulations of pyrolysis of charring materials

A new, simple pyrolysis model for charring materials is applied to several numerical and experimental test cases with variable externally imposed heat fluxes. The model is based on enthalpy. A piecewise linear temperature field representation is adopted, in combination with an estimate for the pyrolysis front position. Chemical kinetics are not accounted for: the pyrolysis process takes place in an infinitely thin front, at the ‘pyrolysis temperature’. The evolution in time of pyrolysis gases mass flow rates and surface temperatures is discussed. The presented model is able to reproduce numerical reference results, which were obtained with the more complex moving mesh model. It performs better than the integral model. We illustrate good agreement with numerical reference results for variable thickness and boundary conditions. This reveals that the model provides good results for the entire range of thermally thin and thermally thick materials. It also shows that possible interruption of the pyrolysis process, due to excessive heat losses, is automatically predicted with the present approach. Finally, an experimental test case is considered. Copyright © 2009 John Wiley & Sons, Ltd.