Char‐formation kinetics in the pyrolysis of sawdust in a conical spouted bed reactor

Both the generation of a microporous structure and char formation kinetics have been studied in the pyrolysis of sawdust of Pinus insignis in a conical spouted bed reactor, in the range 350–700 °C. The BET surface area (representative of the physical evolution of the solid) and the C/H ratio of the solid (representative of the chemical structural change) have been taken as conversion indices. From the measurement of the C/H ratio of the solid (the more significant variable), it has been determined that the reaction order is 0.5 and that the kinetic constant is between 0.18 min⁻¹ at 350 °C and 1.26 min⁻¹ at 700 °C. However the value of the constant is almost independent of temperature, at 1 min⁻¹ in the range 500–700 °C. © 2000 Society of Chemical Industry     

Continuous pyrolysis of waste tyres in a conical spouted bed reactor

Continuous pyrolysis of scrap tyres has been carried out in a conical spouted bed reactor and the results (yields, composition of the volatile fraction and carbon black properties) have been compared with those obtained operating in batch mode in a previous study. Continuous operation in the 425-600 °C range gives way to a yield of 1.8-6.8 wt.% of gases, 44.5-55.0 wt.% of liquid fraction (C₅-C₁₀ range hydrocarbons, with a maximum yield of limonene of 19.3 wt.% at 425 °C), 9.2-11.5 wt.% of tar and 33.9-35.8 wt.% of char. The main differences between the continuous and batch processes are in the yield of light aromatics, which is higher in the continuous process, and in that of the heavy liquid fraction or tar, which is higher in the batch process. These are the advantages of the continuous process, although hydrogenation of the liquid fraction is required even in this case in order to use it as fuel. The high yield of limonene, the flexibility in the operating conditions and the capacity for a continuous removal of the residual carbon black from the reactor are the advantages of conical spouted bed technology. The excellent performance of the conical spouted bed reactor for the tyre pyrolysis process is due to the solid cyclic movement, the good contact between phases, the high heating rate and the reduced residence time of the volatile products.     

Investigations on heat transfer and hydrodynamics under pyrolysis conditions of a pilot-plant draft tube conical spouted bed reactor

This paper describes the hydrodynamic and heat transfer performance of a pilot-plant scale conical spouted bed reactor designed for the pyrolysis of biomass wastes. The spouted bed reactor is the core of a fast pyrolysis pilot plant with continuous biomass feed of up to 25 kg/h, located at the Ikerlan-IK4 facilities.The aim of this paper is to obtain a deeper understanding of the spouted bed reactor performance at pyrolysis temperatures, in order to operate under stable conditions, improve the heat transfer rate in the reactor and minimize energy requirements. The influence of temperature on conical spouted bed hydrodynamics has been studied and wall-to-bed and bed-to-surface heat transfer coefficients have been determined.     

生物质快速热解装置研究进展

当今化石能源日渐枯竭和环境压力日益加重是亟待解决的问题,而生物质热解液化技术被认为是解决能源紧张的潜在方法,尤其是生物质快速热解技术。随着生物质快速热解技术与工艺不断成熟,需要快速热解装置不断放大以提高处理量,以实现生物质快速热解的工业化。生物质快速热解装置复杂且多样化,在装置的放大过程中,各系统的合理选择是难点。本文首先对生物质热解机理、快速热解过程的粒径选择和前处理进行了简述,并对快速热解流程中的进料系统、供能系统、热解反应器和快速冷凝系统4个关键系统进行了综述,着重介绍了快速热解反应器的类型及其特点,提供了该4个关键系统的选择及研究趋势。流化床反应器具有易放大、可以较好地实现自热式快速热解的优点,本文总结出流化床式反应器是目前研究的热点。在保证产品品质下,设备易放大、稳定实现自热式、流程能耗低、运行稳定安全等是快速热解装置未来的研究方向。     

生物质快速热解流化床反应器气力进料特性

为探究不同工况下热解流化床反应器的气力进料特性,设计并搭建了流化床反应器气力进料冷态试验装置。生物质原料和床料分别采用落叶松颗粒和石英砂颗粒,通过试验测得了本装置的最小流化速度,研究了流化气速、喷动气速、流量比、初始静床高、石英砂粒径、落叶松粒径对流化床反应器气力进料特性的影响。试验结果表明：流化气速和喷动气速的增加均会提高进料率;流化气使床料流化并为落叶松颗粒提供进料空间,喷动气为落叶松颗粒提供动能,并平衡一部分床层压力;落叶松与石英砂粒径的增加对进料效果不利;流量比在1.9~2.7范围内进料率高且稳定性好。本文构建了生物质、床料与气体的三相流物理及数学模型,开展试验对模型进行验证,结果表明其预测误差为±13%。     

Modelling fast pyrolysis of biomass in a fluidized bed reactor

A compartmental one-dimensional model of a fluidized bed pyrolytic converter of biomass is presented. Reference conditions are those of non-catalytic fast pyrolysis of biomass in a shallow fluidized bed with external regeneration of the bed material. The fate of biomass and of the resulting char has been modelled by considering elutriation of biomass and char particles, char attrition as well as bed drain/regeneration. The course of primary and secondary pyrolitic reactions is modelled according to a semi-lumped reaction network using well-established kinetic parameters taken from the literature. A specific focus of the present study is the role of the heterogeneous volatile–char secondary reactions, whose rate has been modelled by borrowing a kinetic expression from the neighbouring area of tar adsorption/decomposition over char. The results of computations highlight the relevance of heterogeneous volatile–char secondary reactions and of the closely associated control of char loading in the bed. The sensitivity of the reactor performance to char elutriation and attrition, to proper management of bed drain/regeneration, and to control of gas phase backmixing is demonstrated. Model results provide useful guidelines for optimal design and control of fluidized bed pyrolyzers and pinpoint future research priorities.     

Recycling poly-(methyl methacrylate) by pyrolysis in a conical spouted bed reactor

The pyrolysis of poly-(methyl methacrylate) (PMMA) has been studied in a pyrolysis plant provided with a conical spouted bed reactor. This reactor is an interesting technology for the pyrolysis of waste plastics due to its excellent hydrodynamic behaviour and its high heat transfer and versatility. A previous kinetic study was carried out in thermobalance, in which the degradation of this polymer was observed to begin at low temperatures, 553 K. Consequently, the activation energy is low compared to other plastics. The influence of temperature on pyrolysis product distribution in the conical spouted bed reactor has been studied in the 673–823 K range. The products obtained at low temperatures are mainly the monomers of the polymer used for the study methyl methacrylate (MMA) and ethyl acrylate (EA). When the pyrolysis temperature is increased, the yield of monomers is lower due to the higher severity of secondary reactions, and there is a significant increase in the yield of gases. The maximum monomer recovery has been obtained at 673 K, with the yields of MMA and EA being 86.5% and 6.2%, respectively.     

Prediction of spouted bed reactor performance using kinetic models

The form of the equation governing the kinetic model of a reactor depends on the mixing regime of the reacting phases and the conversion kinetics. The formation of detached flow in a spouted-bed reactor results in backmixing of the solid material. Therefore, the processes in a spouted-bed reactor can be described by a diffusion (quasihomogeneous) model equation. The paper compares the values of the production capacity of a spouted-bed reactor calculated using the diffusion model with experimental values of the efficiency of green ultramarine oxidation (kinetic region), of oxidative calcination of some metal sulphides (mixed region), and of the ion exchange extraction of copper from solutions (diffusion region). The kinetics of the corresponding conversions are also described.     

Mathematical modeling of polyethylene terephthalate pyrolysis in a spouted bed

A model has been developed for pyrolysis of polyethylene terephthalate (PET) in a spouted bed reactor based on the conservation equations for heat, mass, and momentum transports. A spouted bed has been constructed and the kinetic parameters have been obtained within the temperature range of 723–833 K, using two particle size ranges, (0.1–1.0) × 10^?3 and (1.0–3.0) × 10^?3 m. The model' predictions for the radial distributions of temperature and concentration confirm the excellent mixing of particles. Thus, spouted beds are appropriate equipments for performing kinetic studies of PET pyrolysis. The inlet gas temperature and the mass of PET highly affect PET conversion. The amount of inert particles has a negligible effect on the conversion and it can be reduced as far as a stable spouting is preserved. The gas flow suffices to eliminate the external heat and mass‐transfer limitations. It can be reduced to the minimum value to decrease the energy consumption. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1900–1911, 2015     

Biomass pyrolysis in a circulating fluid bed reactor for the production of fuels and chemicals

An approach for biomass flash pyrolysis in a circulating fluid bed (CFB) reactor with continuous solids regeneration is described in this study. The unit is capable of performing conventional and catalytic biomass pyrolysis with the proper solid selection. The production of improved quality liquid products in a direct step through catalytic pyrolysis is investigated in this work. Both conventional and catalytic biomass pyrolysis can be effectively performed in this CFB unit. Flash pyrolysis conditions were achieved and liquid product yields of ∼70 wt% (on biomass feed) were obtained. The effect of specific operating variables including the type of inorganic solid material and the solid/biomass ratio was established on the final liquid product quality and yield. Solid materials considered included silica sand, a commercial fluid catalytic cracking catalyst and a ZSM-5 additive. Catalytic biomass pyrolysis generally leads to the production of additional water, coke and gases compared to conventional pyrolysis. However, the obtained liquid product quality and composition is improved.     

Modeling the thermochemical degradation of biomass inside a fast pyrolysis fluidized bed reactor

A fast pyrolysis process in a bubbling fluidized bed has been modeled, thoroughly reproduced and scrutinized with the help of a combined Eulerian/Lagrangian simulation method. The 3‐D model is compared to experimental results from a 100 g/h bubbling fluidized bed pyrolyzer including such variables as particle composition at the outlet and gas/vapor/water yields as a function of fluidization conditions, biomass moisture concentrations, and bed temperatures. Multiprocessor simulations on a high‐end computer have been carried out to enable the tracking of each of the 0.8 million individual discrete sand and biomass particles, making it possible to look at accurate and detailed multiscale information (i.e., any desired particle property, trajectory, particle interaction) over the entire particle life time. The overall thermochemical degradation process of biomass is influenced by local flow and particle properties and, therefore, accurate and detailed modeling reveals unprecedented insight into such complex processes. It has been found, that the superficial fluidization velocity is important while the particle moisture content is less significant for the final bio‐oil yield. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3030–3042, 2012     

Detailed CFD modelling of fast pyrolysis of different biomass types in fluidized bed reactors

In the present study, an Eulerian‐Eulerian computational fluid dynamics (CFD) model, combined with a comprehensive biomass reaction scheme, was used to simulate fast pyrolysis of four different biomass types in the fluidized bed reactors. The study focuses on the influence of biomass components of different biomass types on the yields, formations, and contents of compositions of pyrolysis products. The result showed that the bio‐oil yield of cellulose‐rich biomass was higher than other biomass types, and char was mainly produced by the fast pyrolysis of LIG‐C of biomass. Moreover, the contents of bio‐oil components were affected by the fast pyrolysis of biomass components. Further, the energy recovery coefficient (ERC) of bio‐oil obtained from pyrolysis of different biomass types was also calculated and analyzed in this paper.

     

Ash-agglomerating gasification of coal in a spouted bed reactor

Australian bituminous coal (Hoskisson) was gasified with oxygen and steam in a 0.4m diameter spouted bed reactor at atmospheric pressure and temperatures of 1050–1170 °C to produce medium calorific value gas. High-ash agglomerates fell through the throat of the spouted bed under restricted gasification conditions, with no simultaneous loss of coal. The effects of temperature, steam-oxygen ratio, coal feed rate and coal size on carbon conversion, production of ash agglomerates, gas composition and decompsition of steam were established.     

Catalytic upgrading of woody biomass derived pyrolysis vapours over iron modified zeolites in a dual-fluidized bed reactor

In this paper, the influence of the proton forms of beta, Y and ferrierite zeolites and their iron modified counterparts during upgrading of pine wood pyrolysis vapours under nitrogen atmosphere was investigated. A dual-fluidized bed reactor was used where in the first bed pyrolysis of pine wood occurred, and in the second upgrading of the pyrolysis vapours over zeolites was conducted. The temperature for pyrolysis and upgrading was 400 and 450 °C, respectively. De-oxygenation reactions over the proton form and iron modified zeolites increased compared to the non-catalytic pyrolysis. The increased selectivity towards organic compounds through de-oxygenation could be noticed as a higher water yield and CO formation.     

微型流化床内松木屑和煤泥等温混合热解特性

采用微型流化床反应器对松木屑和煤泥的等温混合热解气体释放行为进行实验研究。探讨不同温度和掺混比例对CH₄、CO、CO₂与H₂释放特性的影响,并通过模型配合法求解其动力学参数,研究松木屑和煤泥混合热解过程的相互作用。通过FT-IR检测发现煤泥的主要成分为含有C-O和C==O键的芳香化合物,松木屑则以带-OH键的长链脂肪烃为主。在等温稳定反应阶段,松木屑热解气体生成速率高于煤泥,随着生物质掺入比例的不断提高,混合原料气体生成反应速率亦呈现不同程度的增加。利用模型积分法求解了松木屑、煤泥及其混合物热解气体生成动力学参数,并通过实验值和计算值对比筛选出了最概然机理函数。通过活化能对比发现,混合热解对4种气体组分生成具有不同的影响作用,其中CO实验活化能明显低于计算值,表现为二者协同作用利于CO的生成释放;对H₂而言,在75%混合比例条件下,混合反应导致其生成活化能呈现协同负效应,使得活化能实验值明显高于计算值;相较而言,CH₄在混合热解过程影响相对较弱,并呈现小幅度的协同负效应,而CO₂的生成特性则受混合比例的影响较为明显。     

Pyrolysis with partial combustion of oil shale fines in a spouted bed

Pyrolysis with partial combustion of oil shale fines from the Irati Formation in Brazil has been investigated in a 30 cm diameter spouted bed reactor. Experiments were carried out at atmospheric pressure and temperatures between 450 and 600°C. The oi] shale particle size was less than 6.35 mm. Spouting gas temperatures ranged from 20 to 565°C. Three inlet gas pipe diameters and two spouted bed heights were studied. Operation of the process was found to be stable over a wide range of test conditions. Results are presented for oil and gas quality, efficiency of retorting and overall performance of the plant.     

流化床粉煤气体热载体快速热解反应器的计算

在冷态模拟实验和煤热解动力学计算的基础上,对粉煤气体热载体快速热解提升管反应器的高度进行了计算。利用高速摄像粒子测速法结合互相关算法研究了不同气体流量和不同颗粒粒径时固体颗粒在热解提升管中的运动速度,通过求解神府煤热解动力学方程,得到了不同粒径神府煤颗粒热解挥发分析出的时间,从而确定了快速热解提升管反应器的高度。研究结果表明:当气体流量在850 m3/h,粉煤的粒径主要集中在0.7—3.0 mm时,提升管的高度应选择在10.0 m。     

微型流化床内碱金属和碱土金属对稻壳热解动力学的影响特性

通过微型流化床反应分析仪（MFBRA）研究两种典型碱金属和碱土金属（AAEM）钠与镁对稻壳热解气体生成动力学的影响,并采用模型积分法求解出4种主要气体组分（H₂、CO、CH₄与CO₂）的生成动力学参数。结果表明：不同气体组分具有不同的开始与终止释放时间,说明4种气体对应不同的生成路径和机理,高温条件和添加钠、镁离子均会提高气体生成的反应速率。采用典型气固反应动力学模型对气体生成过程进行了拟合求解,获取了气体组分在不同条件下的最概然机理函数。通过最概然机理函数求得了4种气体生成动力学参数,对比发现钠离子与镁离子降低了H₂、CO、CH₄与CO₂生成反应的表观活化能,其中CO受钠离子和镁离子的影响最为显著,进而从活化能角度证实了两种金属离子对于生物质热解特性的影响。