CO2 gasification kinetics of two alberta coal chars

CO₂ gasification kinetics of chars from two Alberta coals (Obed Mountain, high volatile bituminous and Highvale, subbituminous) have been studied using a thermogravimetric analyzer (TGA) and a fixed bed reactor. Charification and gasification reactions were performed sequentially in both the TGA instrument and in the fixed bed reactor to simulate real gasifier operating conditions. TGA and fixed bed data were processed numerically to evaluate the kinetic rate of CO₂ gasification of the chars. Calculated gasification kinetics could be correlated using both the volume reaction and the grain models. Activation energies of the kinetic rate constants were near 200 kJ/mol for both Highvale and Obed Mountain coal chars using the TGA data. The activation energies calculated for the Obed Mountain coal char using the fixed bed reactor were about 250 kJ/mol. For all the cases studied the calculated activation energies were nearly the same for both the volume and grain reaction models.     

Fundamentals of coal topping gasification: Characterization of pyrolysis topping in a fluidized bed reactor

Coal topping gasification refers to a process that extracts the volatiles contained in coal into gas and tar rich in chemical structures in advance of gasification. The technology can be implemented in a reactor system coupling a fluidized bed pyrolyzer and a transport bed gasifier in which coal is first pyrolyzed in the fluidized bed before being forwarded into the transport bed for gasification. The present article is devoted to investigating the pyrolysis of lignite and bituminite in a fluidized bed reactor. The results showed that the highest tar yield appeared at 823 to 923 K for both coals. When coal ash from CFB boiler was used as the bed material, obvious decreases in the yields of tar and pyrolysis gas were observed. Pyrolysis in a reaction atmosphere simulating the pyrolysis gas composition of coal resulted in a higher production of tar. Under the conditions of using CFB boiler ash as the bed material and the simulated pyrolysis gas as the reaction atmosphere, the tar yields for pyrolytic topping in a fluidized bed reactor was about 11.4 wt.% for bituminite and 6.5 wt.% for lignite in dry ash-free coal base.     

Factors affecting steam gasification rate of low rank coal char in a pressurized fluidized bed

A high-pressure bubbling fluidized bed reactor was used to study the steam gasification of coal char under pressure. Indonesian sub-bituminous coal char (Adaro) and Australian lignite char (Loy Yang) were gasified with steam in the reactor at temperatures below 1173 K and at total pressures ranging from 0.1 to 0.5 MPa. The steam gasification rates of the coal chars were determined by analysis of the gaseous products. Activation energies for the steam gasification of the chars were as high as about 250 kJ/mol, which suggests that the temperature dependence of the gasification was substantial. The apparent gasification rates under the study conditions were described by a Langmuir–Hinshelwood (L–H)-type equation. Analysis of the reaction kinetics on the basis of the L–H equation indicated that increasing steam pressure effectively increased the gasification rate.     

An Eulerian modeling approach of wood gasification in a bubbling fluidized bed reactor using char as bed material

We present an Eulerian multiphase approach for modeling the gasification of wood in fluidized beds. The kinetic theory of granular material is used to evaluate constitutive properties of the dispersed solid phase. Comprehensive models for wood pyrolysis, char gasification and homogeneous gas phase reactions are taken into account. The dispersed solid phase within the reactor is modeled as three continuous phases, i.e., one phase representing wood and two char phases with different diameters. In contrast to most other studies we investigate a fluidized bed which consists of wood and char particles without additional inert particles such as limestone or olivine. 2D simulation results for a lab-scale bubbling fluidized bed reactor are presented and compared with experimental data for product gas and tar concentrations and temperature. We investigate the influence of two different classes of parameters on product gas concentrations and temperature: (i) operating conditions such as initial bed height, wood feeding rate, and reactor throughput and (ii) model parameters like thermal boundary conditions, primary pyrolysis kinetics, and secondary pyrolysis model. Two different pyrolysis models are implemented and are compared against each other. The numerical results indicate (i) a relatively low influence of the investigated operating conditions on the main product gas components, (ii) a high sensitivity of main product gas components CO and CO₂ on the thermal boundary condition, and (iii) a very strong influence of operating conditions and model parameters on the tar content in the product gas.     

Pyrolysis of municipal solid waste

A state-of-the-art review describing the characteristics of municipal solid waste (MSW) and assessing the chemistry and technology of pyrolysis of municipal solid waste is presented. The economics of the pyrolysis process are outlined. Combustibles constitute on average about 60% of the weight of MSW and result in an average heating value (“as received” basis) of about 3,000 to 6,000 Btu/Ib. This makes MSW attractive for thermal treatment. Municipal solid waste can be converted to gas, liquid and solid products by pyrolysis. Due to the complexity in composition of MSW the exact mechanism of pyrolysis is not known. Both homogeneous and heterogeneous reactions occur at the same time and both heat and mass transfer take place during the process. The relative yields of different products depends on the temperature of pyrolysis and the rate of heating. High pyrolysis temperatures and high heating rates favour the production of gases indicating high energies of activation for gasification reactions. At low temperatures, below 800°C, the pyrolysis process is reaction-rate controlled, while at high temperatures, above 1,200°C, the process is diffusion-rate controlled. Conditions of good heat and mass transfer are required for gasification of MSW. The residual char after pyrolysis can be gasified by further treatment with steam, hydrogen or carbon monoxide and water. The heat available from the products of pyrolysis is sufficient to sustain the process and yield some excess energy. Three types of reactor design have been generally used in the investigation of pyrolysis of MSW; fixed bed reactor, fluidized bed reactor and rotary kiln reactor. The advantages and weak points of each of these are briefly discussed. The costs of disposal of MSW by pyrolysis appear to be competitive with incineration.     

循环灰条件下1-甲基萘催化裂解的实验研究

热解气化过程中 ,促进焦油的裂解使之转化为高热值煤气 ,对高挥发分劣质煤和生物质燃料的清洁高效利用具有重要的意义 .在固定床反应器上 ,以石英砂和两种烟煤在循环流化床锅炉上燃烧形成的循环灰为床料 ,实验研究了焦油中含量较高的 1 -甲基萘的裂解反应 ,测定了反应动力学参数 .结果表明 ,与石英砂条件下相比 ,循环灰促进了 1 -甲基萘的裂解 ,反应活化能降低 ,裂解气体的总产率提高     

生物质流化床空气-水蒸气气化模型研究

根据流化床反应器特点,结合生物质气化动力学反应机理,建立了生物质在流化床内气化的等温稳态、一维二相动力学模型。该模型所做的主要假定如下:流化床分为气泡相和乳相,在气泡相和乳相内均存在化学反应,考虑二相内的轴向气体扩散,生物质热解过程瞬时完成,主要考虑焦碳以及CO,CO2,H2,H2O,CH4等在流化床内发生的8个主要化学反应。数学模型属于常微分方程组边值问题,利用数值计算软件M atlab7.0进行编程求解。以木粉为原料,将模型结果与实验结果进行了对比,模拟结果与试验数据符合良好,在一定程度上证明了模型的有效性和可靠性。     

A simplified model for biomass pyrolysis in a fluidized bed reactor

A reaction scheme of a set of three parallel reactions followed by a set of two parallel reactions has been used to describe the primary and secondary reactions of biomass pyrolysis in a fluidized bed reactor. A simple first-order kinetic approach has been applied to predict the product yields. The pyrolysis model detailed in this paper is actually a sub-model. The effects of operating parameters on biomass pyrolysis product yield were simulated. Results show that reaction temperature plays an important role in the yield of bio-oil. The model is robust and can predict good results in a gasification environment as well. Good agreement between predicted and published results was obtained.     

ON THE ANALYSIS OF NONCATALYTIC GAS-SOLID KINETICS DATA HAVING WEAK TEMPERATURE DEPENDENCE

Noncatalytic gas-solid reactions should exhibit strong temperature dependence when the rate is controlled by surface kinetics. However, there are a number of examples in the literature where apparent activation energies less than 10 kcal/mol have been reported as being representative of intrinsic kinetics. This conclusion is often based on electrobalance data in which large gas Row rates were used to eliminate mass transfer resistance and the fact that fractional conversion-time results are consistent with the surface kinetics control version of a gas-solid reaction model.

The oxidation of FeS was studied in an electrobalance reactor as a function of O₂ mol fraction, temperature, and gas flow rate. The global rate was first-order in O₂ and weakly dependent on temperature and flow rate. Data analysis used the approximate solution to the grain model. The single-resistance surface kinetics variation of the model provided good match with the conversion-time data, but the apparent activation energy was only about 7 kcal/mol. A two-resistance mass transfer-product layer diffusion variation provided equally good match with the data, and the dependence of reaction coefficients on reaction variables was in general agreement with theory.     

ON THE ANALYSIS OF NONCATALYTIC GAS-SOLID KINETICS DATA HAVING WEAK TEMPERATURE DEPENDENCE

Noncatalytic gas-solid reactions should exhibit strong temperature dependence when the rate is controlled by surface kinetics. However, there are a number of examples in the literature where apparent activation energies less than 10 kcal/mol have been reported as being representative of intrinsic kinetics. This conclusion is often based on electrobalance data in which large gas Row rates were used to eliminate mass transfer resistance and the fact that fractional conversion-time results are consistent with the surface kinetics control version of a gas-solid reaction model.

The oxidation of FeS was studied in an electrobalance reactor as a function of O₂ mol fraction, temperature, and gas flow rate. The global rate was first-order in O₂ and weakly dependent on temperature and flow rate. Data analysis used the approximate solution to the grain model. The single-resistance surface kinetics variation of the model provided good match with the conversion-time data, but the apparent activation energy was only about 7 kcal/mol. A two-resistance mass transfer-product layer diffusion variation provided equally good match with the data, and the dependence of reaction coefficients on reaction variables was in general agreement with theory.     

高铝矾土改性对稻草热解与气化特性的影响

在固定床中研究了高铝矾土改性剂及其浓度和反应温度对稻草热解产气特性的影响,选取固定床中最佳实验条件,在流化床中研究了改性高铝矾土床料对稻草气化特性及焦油产率的影响。结果表明,不同物质改性的高铝矾土对稻草热解产气特性的影响不同,4种物质提高稻草热解产气能力的顺序为CaCl2相似文献   

Nickel-catalysed gasification of brown coal in a fluidized bed reactor at atmospheric pressure

Pyrolysis and steam gasification of nickel-loaded Yallourn coal were carried out in a fluidized bed reactor at ambient pressure. The pyrolysis mode was influenced by the addition of nickel catalyst. The yield of total volatile matter decreased whereas the gas yield markedly increased, when compared with uncatalysed pyrolysis. This is considered to result from tar decomposing on the catalyst and being converted to gases and deposited carbon. For the catalysed steam gasification, ≈ 80 wt% of coal conversion was achieved at 873 K and the gas yield was twelve times as much as that for the uncatalysed reaction. The homogeneous equilibrium in the gas phase controlled the composition of the product gas. The product gas contained little tarry material and a negligible amount of hydrogen sulphide. Nickel was efficiently recovered from the residue by an ammonia-leaching method.     

炼焦煤尾煤热重动力学分析及热解产氢

基于热重分析和固定床热解实验,研究了升温速率和温度对高矿物质含量的炼焦煤尾煤热解特性的影响. 尾煤热解过程可分为室温至400, 400~600及600~950℃三个阶段. 尾煤与焦煤热解曲线基本吻合,尾煤热解特征温度略向高温区推移. 采用Coats-Redfern积分法拟合计算了尾煤热解的动力学参数,得出反应活化能为22.6~66.2 kJ/mol,热解过程可用3个二级反应描述. 30 g尾煤固定床实验结果表明,氢气在低于400℃析出很少,400~600℃缓慢析出,之后随温度升高析出增加,600℃后大量析出,900℃左右达到最大析出量. 终温950℃时,30 g尾煤热解产气4300 mL,氢气产量1722 mL;焦煤产气7950 mL,氢气产量2716 mL. 尾煤热解富氢气体产量达焦煤热解气产量的54%,具有较高的再利用价值.     

加压流化床煤气化炉衬里材料的选择与烘制

加压流化床煤气化技术是近年来随着洁净煤技术的兴起而发展起来的新一代大型、先进煤气化技术。就加压流化床煤气化炉耐火衬里的特殊要求进行了耐火材料的选型,并根据所选耐火材料特性制定了烘炉工作曲线,并比较了烘炉所需实际燃料气量和估算值,结果表明计算值与实际值吻合较好,并为大型流化床反应器的烘炉工艺制定和实施提供一种理论参考和估算方法。     

A mathematical model of fluidized bed biomass gasification

A mathematical model of biomass gasification in a fluidized bed has been developed. It considers axial variations of concentrations and temperature in the bubble and emulsion phases. The mass balance involves instantaneous oxidation and equilibrium devolatilization of the biomass, kinetics of solid-gas gasification reactions as well as of gaseous phase reactions and interphase mass transfer and gas convection. The energy balance is solved locally for each vertical volume element, and globally on the reactor by iteration on the temperature at the bottom of the bed. Three parameters have been adjusted based on the experimental results: the heat transfer coefficient at the wall, the weighting of the kinetics of the water-gas shift reaction and the fraction of biomass carbon remaining as char after devolatilization. The model is used to simulate a pilot scale (50 kg/h) biomass gasifier, and its predictions compared to experimental measurements. The temperature and gaseous concentrations are estimated with good accuracy for the experiments using a wood feedstock, except for the concentration of hydrogen which is overestimated.     

Thermogravimetric study of coal and petroleum coke for co-gasification

As a preliminary study of gasification of coal and petroleum coke mixtures, thermogravimetric analyses were performed at various temperatures (1,100, 1,200, 1,300, and 1,400 °C) and the isothermal kinetics were analyzed and compared. The activation energies of coal, petroleum coke and coal/petroleum coke mixture were calculated by using both a shrinking core model and a modified volumetric model. The results showed that the activation energies for the anthracite and petroleum coke used in this study were 9.56 and 11.92 kcal/mol and reaction times were 15.8 and 27.0 min. In the case of mixed fuel, however, the activation energy (6.97 kcal/mol) and reaction time (17.0 min) were lower than the average value of the individual fuels, confirming that a synergistic effect was observed in the coprocessing of coal and petroleum coke. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Comprehensive study of the influence of total pressure on products yields in fluidized bed gasification of wood sawdust

Wood sawdust gasification experiments were performed in a steam fluidized bed at 800 °C between 2 and 10 bar. An evolution of gas yields with time was measured during the tests, and especially an increase of hydrogen and carbon dioxide yields. This test duration effect was ascribed to char build-up in the bed. As tests proceed, the contribution of char steam gasification to gas yield increases, and the catalytic effect of char on hydrocarbons and tar conversion and on water-gas shift reaction is enhanced.As total pressure increases from 2 to 10 bar, hydrogen, carbon dioxide and methane yields increase by 16%, 53% and 38% respectively, whereas carbon monoxide yield decreases by 33%. The changes in gaseous yields with pressure can be partly explained by the influence of pressure on gas phase reactions (acceleration of water-gas shift kinetics and change in hydrocarbon reactions). The increase of methane yield with pressure is rather suggested to be linked to a change in secondary pyrolysis reactions scheme under high pressure.     

微型流化床反应动力学分析仪的研制与应用

本文首次研发了一种用于测定气固反应速度、求算反应动力学参数的微型流化床反应分析仪器（MFBK）。该仪器利用流化床强化反应过程的热量与质量传递过程,通过气体脉冲输送在给定温度下瞬时进样,根据在线监测的气体组分浓度变化,测试反应速度、推导反应动力学参数和分析反应机理。利用该仪器测定氩气气氛中碳酸钙的分解反应表明：其表观活化能与指前因子分别为142.73kJ.mol^-1和399777s^-1,活化能在文献报道范围之内,且小于热重分析仪测定的184.3kJ.mol^-1,并建立了反应模式函数f(α)=(1-α)0.86,对应的拟合线性相关系数达到0.99。测定煤和生物质热解反应过程表明：MFBK测试的反应完成时间在15s左右,且揭示了生成气关键组分具有不同的释放时间和生成量,为深入探讨热解反应机理提供了新的证据。     

黏结性碎煤射流预氧化破黏与流化

具有黏结性（黏结性指数10~30）并高灰的劣质煤,如洗中煤难于适应于现有气化技术,但焦化等行业对这些煤的气化高价值利用具有极大的需求。中国科学院过程工程研究所提出了黏结性煤射流预氧化流化床气化技术,采用含氧气体向流化床气化炉稀相区喷射供料,有效破除煤的黏结性,同时强化气固接触和气化反应,实现对黏结性劣质煤的高效转化。采用小型射流预氧化流化床反应器,研究了黏结性指数为20的一种煤通过射流预氧化的破黏与实现流化的效果。分别考察了射流气过量空气系数（ER）和氧浓度（C_O2）、加热炉设定温度（T）对预氧化破黏及煤颗粒流化的影响效果,分析了反应器内射流区的温度分布与生成气组成随时间的变化规律,并对预氧化后的半焦进行了电镜观测和气化反应活性测试及傅里叶红外分析。结果表明,在流化床中通过射流预氧化有效破黏、实现黏结性煤颗粒流化的工艺条件为：T > 950℃,C_O2=21%,ER > 0.1。在有效破黏的条件下射流区内的温度变化平稳,生成气中H₂与CO含量较低,波动较小,而结焦条件下射流区内温度逐渐下降,生成气中H₂与CO含量增加。经历结焦的半焦表面生成了黏结性物质,而经过预氧化成功破黏后的半焦其表面大部分官能团消失。     

Modeling a low pressure steam-oxygen fluidized bed coal gasifying reactor

A comprehensive model accounting for the jetting region and homogeneous dilute phase reactions is developed for the adiabatic and continuous gasification of coal particles in a fluidized bed. The division of flows in the bed is determined by means of a modified two-phase theory which considers inlet gas jets, bubbles, free of particles, which develop at the top of the jets and grow in size as they rise, and an emulsion phase consisting of particles and the surrounding interstitial gas. The model describes the gasification of coal particles by pyrolytic devolatilization and three heterogeneous chemical reactions: oxidation by oxygen and steam, and reduction of carbon dioxide. Carbon monoxide and hydrogen produced by the heterogeneous reactions can be oxidized to carbon dioxide and steam by incoming oxygen within the dilute phase jets and bubbles. Furthermore, the water-gas shift reaction can occur in the dilute phase and interstitial gas. Simulations both with and without homogeneous reactions occurring in the jets and bubbles indicate that dilute phase homogeneous reactions have considerable influence on carbon conversion, bed temperature, and product gas composition. It has also been found that the jetting-emulsion mass and beat interchange has a substantial effect on overall bed performance and the temperature of the bed close to the inlet gas distributor. Results indicate that water-gas shift equilibrium is established rapidly and significant quantities of hydrogen and carbon monoxide and a nonuniform steam concentration are present within the combustion zone.