Computational fluid dynamic simulations of chemical looping fuel reactors utilizing gaseous fuels

A computational fluid dynamic (CFD) model for the fuel reactor of chemical looping combustion technology has been developed, with special focus on accurately representing the heterogeneous chemical reactions. A continuum two-fluid model was used to describe both the gas and solid phases. Detailed sub-models to account for fluid–particle and particle–particle interaction forces were also incorporated. Two experimental cases were analyzed in this study (Son and Kim, 2006; Mattison et al., 2001). Simulations were carried out to test the capability of the CFD model to capture changes in outlet gas concentrations with changes in number of parameters such as superficial velocity, metal oxide concentration, reactor temperature, etc. For the experiments of Mattisson et al. (2001), detailed time varying outlet concentration values were compared, and it was found that CFD simulations provided a reasonable match with this data.     

A 300 W laboratory reactor system for chemical-looping combustion with particle circulation

Chemical-looping combustion (CLC) is a method to burn gaseous fuels with inherent separation of carbon dioxide. A continuously operated laboratory reactor system for chemical-looping combustion with two interconnected fluidized beds was designed and built. This chemical-looping combustor was designed to operate with a fuel flow corresponding to 100–300 W. The CLC system was operated successfully using a highly reactive nickel-based oxygen-carrier. Furthermore, tests were carried out to determine the degree of gas leakage between the reactors. Although there was some leakage between the fuel and air reactors, it is low enough to enable evaluation of the combustion results. The combustion tests showed a high conversion of the natural gas to carbon dioxide, indicating that the particles are suitable for chemical-looping combustion. No methane was detected in the gas from the fuel reactor, and the fraction of carbon monoxide was in the range 0.5–3%.     

Solid fuels in chemical-looping combustion using a NiO-based oxygen carrier

The feasibility of using three different solid fuels in chemical-looping combustion (CLC) has been investigated using NiO as oxygen carrier. A laboratory fluidized-bed reactor system for solid fuel was used, simulating a chemical-looping combustion system by exposing the sample to alternating reducing and oxidizing conditions. In each reducing phase 0.2 g of fuel was added to the reactor containing 20 g oxygen carrier. The experiments were performed at 970 °C. Compared to previously published results with other oxygen carriers the reactivity of the used Ni-particles was considerably lower for the high-sulphur fuel and higher for the low-sulphur fuel. Much more unconverted CO was released and the fuel conversion was much slower for high-sulphur fuel such as petroleum coke, suggesting that the nickel-based oxygen carrier was deactivated by the presence of sulphur. The NiO particles also showed good reactivity with methane and a syngas mixture of 50% H₂ and 50% CO. For all experiments the oxygen carrier showed good fluidizing properties without any signs of agglomeration.     

Carbon deposition characteristics and regenerative ability of oxygen carrier particles for chemical-looping combustion

For gaseous fuel combustion with inherent CO₂ capture and low NO_x emission, chemical-looping combustion (CLC) may yield great advantages for the savings of energy to CO₂ separation and suppressing the effect on the environment. In a chemical-looping combustor, fuel is oxidized by metal oxide medium (oxygen carrier particle) in a reduction reactor. Reduced particles are transported to the oxidation reactor and oxidized by air and recycled to the reduction reactor. The fuel and the air are never mixed, and the gases from the reduction reactor, CO₂ and H₂O, leave the system as separate streams. The H₂O can be easily separated by condensation and pure CO₂ is obtained without any loss of energy for separation. In this study, NiO based particles are examined from the viewpoints of reaction kinetics, carbon deposition, and cyclic use (regenerative ability). The purpose of this study is to find appropriate reaction conditions to avoid carbon deposition and achieve high reaction rate (e.g., temperature and maximum carbon deposition-free conversion) and to certify regenerative ability of NiO/bentonite particles. In this study, 5.04% methane was used as fuel and air was used as oxidation gas. The carbon deposition characteristics, reduction kinetics and regenerative ability of oxygen carrier particles were examined by TGA (Thermal Gravimetrical Analyzer).     

Multiphase CFD Modeling for a Chemical Looping Combustion Process (Fuel Reactor)

There are growing concerns about increasing emissions of greenhouse gases and a looming global warming crisis. CO₂ is a greenhouse gas that affects the climate of the earth. Fossil fuel consumption is the major source of anthropogenic CO₂ emissions. Chemical looping combustion (CLC) has been suggested as an energy‐efficient method for the capture of carbon dioxide from combustion. A chemical‐looping combustion system consists of a fuel reactor and an air reactor. The air reactor consists of a conventional circulating fluidized bed and the fuel reactor is a bubbling fluidized bed. The basic principle involves avoiding direct contact of air and fuel during the combustion. The oxygen is transferred by the oxygen carrier from the air to the fuel. The water in combustion products can be easily removed by condensation and pure carbon dioxide is obtained without any loss of energy for separation. With the improvement of numerical methods and more advanced hardware technology, the time required to run CFD (computational fluid dynamic) codes is decreasing. Hence, multiphase CFD‐based models for dealing with complex gas‐solid hydrodynamics and chemical reactions are becoming more accessible. To date, there are no reports in the literature concerning mathematical modeling of chemical‐looping combustion using FLUENT. In this work, the reaction kinetics models of the (CaSO₄ + H₂) fuel reactor is developed by means of the commercial code FLUENT. The effects of particle diameter, gas flow rate and bed temperature on chemical looping combustion performance are also studied. The results show that the high bed temperature, low gas flow rate and small particle size could enhance the CLC performance.     

Comparison of iron-, nickel-, copper- and manganese-based oxygen carriers for chemical-looping combustion

For combustion with CO₂ capture, chemical-looping combustion (CLC) with inherent separation of CO₂ is a promising technology. Two interconnected fluidized beds are used as reactors. In the fuel reactor, a gaseous fuel is oxidized by an oxygen carrier, e.g. metal oxide particles, producing carbon dioxide and water. The reduced oxygen carrier is then transported to the air reactor, where it is oxidized with air back to its original form before it is returned to the fuel reactor. The feasibility of using oxygen carrier based on oxides of iron, nickel, copper and manganese was investigated. Oxygen carrier particles were produced by freeze granulation. They were sintered at 1300 °C for 4 h and sieved to a size range of 125-180 μm. The reactivity of the oxygen carriers was evaluated in a laboratory fluidized bed reactor, simulating a CLC system by exposing the sample to alternating reducing and oxidizing conditions at 950 °C for all carriers except copper, which was tested at 850 °C. Oxygen carriers based on nickel, copper and iron showed high reactivity, enough to be feasible for a suggested CLC system. However, copper oxide particles agglomerated and may not be suitable as an oxygen carrier. Samples of the iron oxide with aluminium oxide showed signs of agglomeration. Nickel oxide showed the highest reduction rate, but displayed limited strength. The reactivity indicates a needed bed mass in the fuel reactor of about 80-330 kg/MW_th and a needed recirculation flow of oxygen carrier of 4-8 kg/s, MW_th.     

钠修饰铁矿石载氧体的串行流化床煤化学链燃烧试验

利用1 kW_th串行流化床反应器对钠修饰铁矿石载氧体进行试验研究,考察燃料反应器温度对煤化学链催化燃烧特性的影响。结果表明,钠在820～920℃温度下显著促进了煤气化反应的进行,随着燃料反应器温度的提高,使用Na-铁矿石时燃料反应器出口CO₂浓度明显增大,CO浓度明显降低,在920℃时CO₂捕集效率和碳捕集效率分别达到78.60%和80.54%,而使用纯铁矿石时CO₂捕集效率和碳捕集效率仅为40.27%和45.65%。在高温950℃时Na-铁矿石活性下降,出现烧结和团聚现象,燃料反应器出现滞流态化现象,这可能是钠的化合物熔点较低和载氧体过度还原所导致的。XRD和SEM分析结果显示钠修饰铁矿石促使更多的Fe₂O₃被还原为Fe₃O₄。     

基于双级燃料反应器的污泥化学链燃烧特性

化学链燃烧技术是一种可以实现CO₂内分离的新型燃烧技术。本文利用基于双级燃料反应器的新型化学链燃烧反应系统,以赤铁矿为载氧体,对污泥的化学链燃烧进行实验研究,系统连续稳定运行8h,考察燃料反应器温度（800～900℃）、污泥进料量（300～600g/h）对污泥化学链燃烧性能的影响。结果表明,稳定运行过程中,床料大部分位于一级燃料反应器,下降管高度保持稳定;双级燃料反应器的设计极大提高了污泥碳转化率,随温度的增加,碳转化率和碳捕集效率逐渐升高,且额外耗氧量始终低于10%;随着污泥进料量增加,碳转化率和CO₂体积分数逐渐降低。对两级燃料反应器内载氧体进行XRD分析,结果显示,还原后的载氧体在空气反应器再生后进入二级燃料反应器,和一级燃料反应器相比,具有更多的Fe₂O₃成分,保证其具有更高的反应活性。     

Interaction of mineral matter of coal with oxygen carriers in chemical-looping combustion (CLC)

The chemical-looping combustion (CLC) and chemical-looping with oxygen uncoupling (CLOU) processes are novel solutions for efficient combustion with direct separation of carbon dioxide. These processes use a metal oxide as an oxygen carrier to transfer oxygen from an air to a fuel reactor, where the fuel reacts with the solid oxygen carrier. When utilizing coal in CLC, the oxygen carrier particles could be affected through interaction with the ash-forming mineral matter found in coal, causing deactivation and/or agglomeration. In this work, possible interactions between minerals commonly encountered in coal and several promising oxygen carriers that are currently under investigation for their use in CLC are studied by both experiment and thermodynamic equilibrium calculations. Possible interaction was studied for both highly reducing and oxidizing conditions at 900 °C. Under highly reducing conditions pyrite was found to have by far the most deteriorating effect on the oxygen carrier particles, as the sulfur in the pyrite reacted with the oxygen carrier to form sulfides. Quartz and clay minerals were found to have a rather low influence on the oxygen carriers. Out of the oxygen carriers investigated, CuO/MgAl₂O₄ and the Mn₃O₄/ZrO₂ oxygen carriers tended to be quite reactive towards mineral matter whereas ilmenite has been shown to be the most robust oxygen carrier. Although sulfur can clearly deactivate Ni, Cu and Mn based oxygen carriers under sub-stoichiometric conditions, when the fuel is converted fully to CO₂ and H₂O, sulfides are only expected for Ni-based oxygen carriers.     

Long-term integrity testing of spray-dried particles in a 10-kW chemical-looping combustor using natural gas as fuel

Chemical-looping combustion, CLC, is a combustion concept with inherent separation of CO₂. The fuel and combustion air are kept apart by using an oxygen carrier consisting of metal oxide. The oxygen carriers used in this study were prepared from commercially available raw materials by spray-drying. The aim of the study was to subject the particles to long-term operation (>1000 h) with fuel and study changes in particles, with respect to reactivity and physical characteristics. The experiments were carried out in a 10-kW chemical-looping combustor operating with natural gas as fuel. 1016 h of fuel operation were achieved. The first 405 h were accomplished using a single batch of NiO/NiAl₂O₄-particles. The last 611 h were achieved using a 50/50_mass-mixture of (i) particles used for 405 h, and (ii) a second batch of particles similar in composition to the first batch, but with an MgO additive. Thus, at the conclusion of the test series, approximately half of the particles in the reactor system had been subjected to >1000 h of chemical-looping combustion. The reason for mixing the two batches was to improve the fuel conversion. Fuel conversion was better with the mixture of the two oxygen carriers than it was using only the batch of NiO/NiAl₂O₄-particles. The CO fraction was slightly above the equilibrium fraction at all temperatures. Using the oxygen carrier mixture, the methane fraction was typically 0.4-1% and the combustion efficiency was around 98%. The loss of fines decreased slowly throughout the test period, although the largest decrease was seen during the first 100 h. An estimated particle lifetime of 33 000 h was calculated from the loss of fines. No decrease in reactivity was seen during the test period.     

The use of petroleum coke as fuel in chemical-looping combustion

Chemical-looping combustion is a novel technique used for CO₂ separation that previously has been demonstrated for gaseous fuel. This work demonstrates the feasibility of using solid fuel (petroleum coke) in chemical-looping combustion (CLC). Here, the reaction between the oxygen carrier and solid fuel occurs via the gasification intermediates, primarily CO and H₂. A laboratory fluidized-bed reactor system for solid fuel, simulating a CLC-system by exposing oxygen-carrying particles to alternating reducing and oxidizing conditions, has been developed. In each reducing period, 0.2 g of petroleum coke was added to 20 g of oxygen carrier composed of 60% active material of Fe₂O₃ and 40% inert MgAl₂O₄. The effect of steam and SO₂ concentration in the fluidizing gas was investigated as well as effect of temperature. The rate of reaction was found to be highly dependent on the steam and SO₂ concentration as well as the temperature. Also shown was that the presence of a metal oxide enhances the gasification of petroleum coke. A preliminary estimation of the oxygen carrier inventory needed in a real CLC system showed that it would be below 2000 kg/MW_th.     

Effect of fuel particle size on reaction rate in chemical looping combustion

Chemical looping combustion (CLC) uses an oxygen carrier circulating between an air and a fuel reactor to replace direct burning of fuels in air. The very low energy penalty for CO₂ separation in CLC gives it the potential to become an important technology on the way to a CO₂ neutral energy supply. In this work, the influence of the particle size of coal on the rate of reaction of the coal was investigated in a bed of oxygen carrier. In order to do this, a method to quench the reaction of coal with oxygen carriers at a specified time and measure the particle size distribution of the remaining coal was developed. Three size fractions of coal were used in the experiments: 90–125, 180–212 and 250–355 μm. Particle size distributions of the fuel show a decrease in particle size with time. The influence of devolatilisation of the coal on the coal particle size was measured, showing that coal particles do not break in the fluidized bed reactor used for the experiments. Reaction rates based on measurements of gas phase concentrations of CO₂, CO and CH₄ showed that the reaction rate is independent of the particle size. These results are in line with literature findings, as studies have shown that carbon gasification is size-independent at conditions similar to those in the performed CLC experiments.     

基于硫酸钙固体燃料化学链气化过程制备合成气的研究(英文)

Chemical-looping gasification (CLG) is a novel process for syngas generation from solid fuels,sharing the same basic principles as chemical-looping combustion (CLC).It also uses oxygen carriers (mainly metal oxide and calcium sulfate) to transfer heat and oxygen to the fuel.In this paper,the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor.Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process,showing some different features from the CLC.The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios.It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance.The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and experimental results.It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.     

Fluid dynamic simulation in a chemical looping combustion with two interconnected fluidized beds

Flow behavior of gas and particles is simulated in a 2-D chemical-looping combustion (CLC) process with two interconnected fluidized beds. A Eulerian continuum two-fluid model is applied for both the gas phase and the solid phase. Gas turbulence is modeled by using a k-ε turbulent model. The kinetic stress is modeled using the kinetic theory of granular flow, while the friction stress is from the combination of the normal frictional stress model proposed by Johnson and Jackson (1987) and the frictional shear viscosity model proposed by Schaeffer (1987) to account for strain rate fluctuations and slow relaxation of the assembly to the yield surface. Instantaneous and local velocity, concentration of particles and granular temperature are obtained. Predicted time-averaged particle concentrations and velocities reflect the classical core-annular flow structure in the air reactor. Flow behavior of bubbles is predicted in the fuel reactor and pot-seal. Computed leakage qualitatively agrees with experimental data in the fuel reactor and pot-seal.     

Chemical - Looping with oxygen uncoupling using Mn/Mg-based oxygen carriers - Oxygen release and reactivity with methane

Chemical-looping combustion with oxygen uncoupling (CLOU) is a method for combustion of solid and gaseous fossil fuels, which enables easy separation of carbon dioxide from the gaseous product mixture. In contrast to the related chemical-looping combustion (CLC) technology where gaseous or gasified fuels react directly with oxygen carriers, CLOU processes require oxygen carrier materials to be able to release oxygen in the fuel reactor and to regenerate by re-oxidation in oxygen-rich atmosphere in the air reactor at elevated temperature. Oxygen uncoupling properties and reactivities for methane combustion of 12 oxygen carrier particles, produced from mixtures of manganese and magnesium oxides with optional addition of titanium dioxide or calcium hydroxide, are investigated in a quartz batch reactor at 810 °C, 850 °C, 900 °C and 950 °C. All investigated oxygen carriers have oxygen release characteristics. The addition of calcium hydroxide facilitates oxygen release and combustion of methane, whereas addition of titanium dioxide does not have a pronounced effect on either oxygen uncoupling or reactivity of the oxygen carrier. In general, particles with greater extent of oxygen release have superior methane combustion properties.     

A Two‐Compartment Fluidized Bed Reactor for CO2 Capture by Chemical‐Looping Combustion

Chemical‐looping combustion (CLC) is a combustion method for a gaseous fuel with inherent separation of the greenhouse gas carbon dioxide. A CLC system consists of two reactors, an air reactor and a fuel reactor, and an oxygen carrier circulating between the two reactors. The oxygen carrier transfers the oxygen from the air to the fuel. The flue gas from the fuel reactor consists of carbon dioxide and water, while the flue gas from the air reactor is nitrogen from the air. A two‐compartment fluidized bed CLC system was designed and tested using a flow model in order to find critical design parameters. Gas velocities and slot design were varied, and the solids circulation rate and gas leakage between the reactors were measured. The solids circulation rate was found to be sufficient. The gas leakage was somewhat high but could be reduced by altering the slot design. Finally, a hot laboratory CLC system is presented with an advanced design for the slot and also with the possibility for inert gas addition into the downcomer for solids flow increase.     

Heat and Mass Flow Control in an Interconnected Multiphase CFD Model for Chemical Looping Combustion

Chemical looping combustion is a feasible option for carbon capture from fossil fuels. Within the process, the oxygen necessary for combustion is provided by a solid carrier material which alternately undergoes oxidation and reduction reactions. Features of the process are that the oxidation reaction of the particulate carrier in the air reactor is strongly exothermic and that the conversion of both oxidation and reduction reactions has to be in balance for stable operation. Simulations of the transient behavior of chemical looping combustion systems are possible through multiphase CFD. To allow for the modeling of chemical looping at steady state, cooling of the reactors and mass flow between fuel and air reactor must be adequately adjusted. Therefore, an interconnected multiphase CFD model was extended by an adjustment control. In this extended modeling framework variations of the operational load, control set points and carrier materials were performed. These simulations allow detailed insight into the dynamic behavior of chemical looping systems.     

A model on chemical looping combustion of methane in a bubbling fluidized-bed process

We developed a mathematical model to discuss the performance of chemical looping combustion (CLC) of methane in continuous bubbling fluidized-beds. The model considers the particle population balance, oxidation and reduction rate of particles in fluidized beds. It also considers utilization efficiency of oxygen carrier (OC) particles, residence time of particles in each reactor, and particle size in reaction rate. The model was applied for a bubbling coreannulus fluidized-bed process. The core bed was the fuel reactor (0.08 m-i.d., 2.1 m-height) and the annulus bed was the air reactor (0.089 m-i.d., 0.15 m-o.d., 1.6 m-height). The process employed a type of Ni-based OC particles. The present model agrees reasonably well with the combustion efficiency measured in the process. Simulation was performed to investigate the effects of some variables for the process. The present model revealed that the range of circulation rate of OC particles for achieving complete combustion determined the operating range of the CLC system. The minimum circulation rate of OC particles for complete combustion decreased in the considered operating range as temperature or bed mass increased in the fuel reactor. A large mass of the fuel bed was necessary to obtain complete combustion at low fuel reactor temperature. The fresh feed rate of OC particles for steady state operation increased in complete combustion condition as temperature or static bed height or gas velocity increased.     

Chemical-looping combustion in a 300 W continuously operating reactor system using a manganese-based oxygen carrier

Chemical-looping combustion (CLC) is a method for the combustion of fuel gas with inherent separation of carbon dioxide. This technique involves the use of two interconnected reactors. A solid oxygen carrier reacts with the oxygen in air in the air reactor and is then transferred to the fuel reactor, where the fuel gas is oxidized to carbon dioxide and water by the oxygen carrier. Fuel gas and air are never mixed and pure CO₂ can easily be obtained from the flue gas exit. The oxygen carrier is recycled between both reactors in a regenerative process. This paper presents the results from a continuously operating laboratory CLC unit, consisting of two interconnected fluidized beds. The feasibility of the use of a manganese-based oxygen carrier supported on magnesium stabilized zirconia was tested in this work. Natural gas or syngas was used as fuel in the fuel reactor. Fuel flow and air flow was varied, the thermal power was between 100 and 300 W, and the air ratio was between 1.1 and 5.0. Tests were performed at four temperatures: 1073, 1123, 1173 and 1223 K. The prototype was successfully operated at all conditions with no signs of agglomeration or deactivation of the oxygen carrier. The same particles were used during 70 h of combustion and the mass loss was 0.038% per hour, although the main quantity was lost in the first hour of operation. In the combustion tests with natural gas, methane was detected in the exit flue gases, while CO and H₂ were maintained at low concentrations. Higher temperature or lower fuel flows increases the combustion efficiency, which ranged from 0.88 to 0.99. On the other hand, the combustion of syngas was complete for all experimental conditions, with no CO or H₂ present in the gas from the fuel reactor.     

煤/钙基载氧体化学链燃烧操作参数分析

化学链燃烧作为一种新颖的燃烧技术,在化石燃料燃烧释放能量的同时能够有效分离CO2。今以CO2为气化剂气化煤炭,基于Aspen Plus流程模拟软件,研究了煤/钙基载氧体化学链燃烧过程。结果表明,以CO2为煤气化剂,各反应器含水分少,可减少热损失。CaSO4载氧体具有载氧能力大以及反应活性良好等优点。气化炉中CO+H2含量随二氧化碳煤比增大逐渐增加后下降;随温度升高其含量先增加,后趋于平稳。燃料反应器中CO2+H2O含量随载氧体煤比增大,呈现先增大后减小的趋势;随温度升高其含量逐渐下降。空气反应器中CaSO4含量随空载比增大先增加后趋于平稳,随温度升高其含量趋于平稳后下降。气化炉中硫化物和氮化物含量随温度升高而下降,而燃料反应器和空气反应器中硫化物含量随温度升高增加趋势明显,氮化物含量变化不明显。最后确定了关键反应器操作参数:气化炉的二氧化碳煤比为1.8;燃料反应器的载氧体煤比为4.5;空气反应器的空载比为10.5和三反应器的操作温度分别为950、1000和1100℃。