Influence of reaction atmosphere (H2O, N2, H2, CO2, CO) on fluidized-bed fast pyrolysis of biomass using detailed tar vapor chemistry in computational fluid dynamics

Secondary pyrolysis in fluidized bed fast pyrolysis of biomass is the focus of this work. A novel computational fluid dynamics (CFD) model coupled with a comprehensive chemistry scheme (134 species and 4169 reactions, in CHEMKIN format) has been developed to investigate this complex phenomenon. Previous results from a transient three-dimensional model of primary pyrolysis were used for the source terms of primary products in this model. A parametric study of reaction atmospheres (H2O, N2, H2, CO2, CO) has been performed. For the N2 and H2O atmosphere, results of the model compared favorably to experimentally obtained yields after the temperature was adjusted to a value higher than that used in experiments. One notable deviation versus experiments is pyrolytic water yield and yield of higher hydrocarbons. The model suggests a not overly strong impact of the reaction atmosphere. However, both chemical and physical effects were observed. Most notably, effects could be seen on the yield of various compounds, temperature profile throughout 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 liquid yield. With the aid of acceleration techniques, most importantly dimension reduction, chemistry agglomeration, and in-situ tabulation, a converged solution could be obtained within a reasonable time (∼30 h). As such, a new potentially useful method has been suggested for numerical analysis of fast pyrolysis.

Comprehensive secondary pyrolysis in fluidized-bed fast pyrolysis of biomass, a fluid dynamics based modelling effort

Homogenous secondary pyrolysis is category of reactions following the primary pyrolysis and presumed important for fast pyrolysis. For the comprehensive chemistry and fluid dynamics, a probability density functional (PDF) approach is used; with a kinetic scheme comprising 134 species and 4169 reactions being implemented. With aid of acceleration techniques, most importantly Dimension Reduction, Chemistry Agglomeration and In-situ Tabulation (ISAT), a solution within reasonable time was obtained. More work is required; however, a solution for levoglucosan (C6H10O5) being fed through the inlet with fluidizing gas at 500 °C, has been obtained. 88.6% of the levoglucosan remained non-decomposed, and 19 different decomposition product species were found above 0.01% by weight. A homogenous secondary pyrolysis scheme proposed can thus be implemented in a CFD environment and acceleration techniques can speed-up the calculation for application in engineering settings.

Geometrical optimization of a fast pyrolysis bubbling fluidized bed reactor using comutational fluid dynamics

This paper analyzes the physical phenomena that take place inside an 1 kg/h bubbling fluidized bed reactor located at Aston University and presents a geometrically modified version of it, in order to improve certain hydrodynamic and gas flow characteristics. The bed uses, in its current operation, 40 L/min of N2 at 520 °C fed through a distributor plate and 15 L/min purge gas stream, i.e., N2 at 20 °C, via the feeding tube. The Eulerian model of FLUENT 6.3 is used for the simulation of the bed hydrodynamics, while the k - ε model accounts for the effect of the turbulence field of one phase on the other. The three-dimensional simulation of the current operation of the reactor showed that a stationary bubble was formed next to the feeding tube. The size of the permanent bubble reaches up to the splash zone of the reactor, without any fluidizaton taking place underneath the feeder. The gas flow dynamics in the freeboard of the reactor is also analyzed. A modified version of the reactor is presented, simulated, and analyzed, together with a discussion on the impact of the flow dynamics on the fast pyrolysis of biomass. © 2010 American Chemical Society.

Heat-Transfer Study of External Superheater of CFB Incinerator

The heat transfer coefficients for horizontally immersed tubes have been studied in model internally circulating fluidized bed (ICFB) and pilot ICFB incinerators. The characteristics in the ICFB were found to be significantly different from those in a bubbling bed. In ICFB, there is a flowing zone with high velocity, a heat exchange zone, and a moving zone with low velocity. The controllable heat transfer coefficients in ICFB strongly depend on the fluidized velocity in the flowing zone, and also the flow condition in the moving zone. The heat exchange process and suitable bed temperature can be well controlled according to this feature. Based on the results of experiments, a formulation for heat transfer coefficient has been developed. These results were applied to an external superheater of a CFB incinerator with a 450 degreesC steam outlet in a waste-to-energy pilot cogeneration plant of 12 MW in Jiaxing City, China.

Characterizing Particle Dispersion by Image Analysis in ICFB

A new particle image technique was developed to analyze the dispersion of tracer particles in an internally circulating fluidized bed (ICFB). The movement course and the concentration distribution of tracer particles in the bed were imaged and the degree of inhomogeneity of tracer particles was analyzed. The lateral and axial dispersion coefficients of particles were calculated for various zones in ICFB. Results indicate that the lateral diffusion coefficient in the fluidized bed with uneven air distribution is significantly higher than that in uniform bubbling beds with even air distribution. The dispersion coefficients are different along bed length and height.

内旋流流化床内颗粒运动规律的试验与数值研究

通过冷态试验与数值模拟研究了不同布风下装有∧字型布风板的内旋流流化床的流动特性，并进行了对比．气固两相数值模拟结果表明，固相流场产生了大尺度旋流，而且与试验观察到的现象相似．对固相颗粒速度分析表明非均匀布风使内旋流流化床的底部和顶部产生了气、固两相强烈的横向和纵向运动．相比较来说，对称的非均匀布风扩散能力要比均匀布风的扩散能力强．

Influence of HCl on CO and NO emissions in combustion

The influence of HCl on CO and NO emissions was experimentally investigated in an entrained flow reactor (EFR) and an internally circulating fluidized bed (ICFB). The results in EFR show the addition of HCl inhibits CO oxidation and NO formation at 1073 K and 1123 K. At the lower temperature (1073 K) the inhibition of HCl becomes more obvious. In ICFB, chlorine-containing plastic (PVC) was added to increase the concentration of HCl during the combustion of coal or coke. Results show that HCl is likely to enhance the reduction of NO and N2O. HCl greatly increases CO and CH4 emission in the flue gas. A detailed mechanism of CO/NO/HCl/SO2 system was used to model the effect of HCl in combustion. The results indicate that HCl not only promotes the recombination of radicals O, H, and OH, but also accelerates the chemical equilibration of radicals. The influence of HCl on the radicals mainly occurs at 800-1200 K. (C) 2009 Elsevier Ltd. All rights reserved.

Estudo de pirólise catalítica de biomassa em escala piloto para melhoramento da qualidade do bio-óleo

A pirólise rápida é um processo para conversão térmica de uma biomassa sólida em altos rendimentos de um produto líquido chamado de bio-óleo. Uma das alternativas para geração de um bio-óleo com menor teor de oxigênio é uso de catalisadores nos reatores de pirólise, ao invés de um inerte, num processo chamado de pirólise catalítica. O objetivo deste trabalho foi testar catalisadores comerciais, um ácido e outro básico, em uma unidade piloto de leito fluidizado circulante. O catalisador ácido utilizado foi o Ecat, proveniente de uma unidade industrial de craqueamento catalítico fluido (FCC), e como catalisador básico foi utilizado uma hidrotalcita. Os resultados foram comparados com testes utilizando um material inerte, no caso uma sílica. Uma unidade piloto de FCC do CENPES foi adaptada para realizar os testes de pirólise catalítica. Após fase de modificação e testes de condicionamento, foi comprovada a viabilidade na utilização da unidade piloto adaptada. Contudo, devido a limitações operacionais, maiores tempos de residência tiveram que ser aplicados no reator, configurando o processo como pirólise intermediária. Foram então realizados testes com os três materiais nas temperaturas de 450C e 550C. Os resultados mostraram que o aumento do tempo de residência dos vapores de pirólise teve um impacto significativo nos rendimentos dos produtos quando comparada com o perfil encontrado na literatura para pirólise rápida, pois devido ao incremento das reações secundárias, produziu maiores rendimentos de coque e água, e menores rendimentos de bio-óleo. O Ecat e a hidrotalcita se apresentaram mais efetivos em termos de desoxigenação. O primeiro apresentou maiores taxas de desoxigenação via desidratação e a hidrotalcita apresentou maior capacidade para descarboxilação. Contudo, o uso de Ecat e hidrotalcita não se mostrou adequado para uso em reatores de pirólise intermediária, pois acentuou ainda mais as reações secundárias, gerando um produto com alto teor de água e baixo teor de compostos orgânicos no bio-óleo, além de produzirem mais coque. À temperatura de 450C estes efeitos foram mais pronunciados. Em termos de caracterização química, a condição de pirólise intermediária apontou para a produção de bio-óleos com perfil fenólico, sendo a sílica o que proporcionou os melhores rendimentos, principalmente a temperatura de 550C, sendo superiores aos encontrados na literatura. Analisando as composições dos bio-óleos sob a ótica da produção de biocombustíveis, nenhum dos materiais testados apresentou rendimentos consideráveis em hidrocarbonetos. De maneira geral, a sílica foi o que proporcionou os melhores resultados em termos de rendimento e qualidade do bio-óleo. Sua menor área superficial e sua característica de inerte se mostraram mais adequados para o processo de pirólise intermediária, onde a contribuição das reações secundárias em fase gasosa é elevada em função do tempo de residência no reator

内循环流化床生物质气化过程的神经网络模型

基于BP人工神经网络原理，利用MATLAB神经网络工具箱，以实验得到的57组气化实验数据作为样本，建立了一个以加料量和送风量为输入变量，以燃气热值、产气率、碳转化率和气化效率为输出变量，用于描述连续稳定气化过程的内循环流化床生物质气化模型。对模型的隐层节点数和训练周期改变对模拟结果的影响进行了分析，发现当隐层节点数为20，训练步骤为50步，模型的4个输出变量的模拟结果与实验结果相关系数均超过0．95；同时对该模型的预测能力进行了考察，模型预测结果与实验结果吻合良好，证明了该模型具有较强的泛化能力，为生物质内循环流化床气化系统的优化设计和自动控制提供新思路。

Operational characteristics of a 1.2-MW biomass gasification and power generation plant

In this study, we analyzed the operational characteristics of a 1.2-MW rice husk gasification and power generation plant located in Changxing, Zhejiang province, China. The influences of gasification temperature, equivalence ratio (ER), feeding rate and rice husk water content on the gasification characteristics in a fluidized bed gasifier were investigated. The axial temperature profile in the dense phase of the gasifier showed that inadequate fluidization occurred inside the bed, and that the temperature was closely related to changes in ER and feeding rate. The bed temperature increased linearly with increasing ER when the feeding rate was kept constant, while a higher feeding rate corresponded to a lower bed temperature at fixed ER. The gas heating value decreased with increasing temperature, while the feeding rate had little effect. When the gasification temperature was 700-800C, the gas heating value ranged from 5450-6400kJ/Nm3. The water content of the rice husk had an obvious influence on the operation of the gasifier: increases in water content up to 15% resulted in increasing ER and gas yield, while water contents above 15% caused aberrant temperature fluctuations. The problems in this plant are discussed in the light of operational experience of MW-scale biomass gasification and power generation plants.

Bio-syngas production from biomass catalytic gasification

A promising application for biomass is liquid fuel synthesis, such as methanol or dimethyl ether (DME). Previous studies have studied syngas production from biomass-derived char, oil and gas. This study intends to explore the technology of syngas production from direct biomass gasification, which may be more economically viable. The ratio of H-2/CO is an important factor that affects the performance of this process. In this study, the characteristics of biomass gasification gas, such as H-2/CO and tar yield, as well as its potential for liquid fuel synthesis is explored. A fluidized bed gasifier and a downstream fixed bed are employed as the reactors. Two kinds of catalysts: dolomite and nickel based catalyst are applied, and they are used in the fluidized bed and fixed bed, respectively. The gasifying agent used is an air-steam mixture. The main variables studied are temperature and weight hourly space velocity in the fixed bed reactor. Over the ranges of operating conditions examined, the maximum H-2 content reaches 52.47 vol%, while the ratio of H-2/CO varies between 1.87 and 4.45. The results indicate that an appropriate temperature (750 degrees C for the current study) and more catalyst are favorable for getting a higher H-2/CO ratio. Using a simple first order kinetic model for the overall tar removal reaction, the apparent activation energies and pre-exponential factors are obtained for nickel based catalysts. The results indicate that biomass gasification gas has great potential for liquid fuel synthesis after further processing.