Modeling of a 120 kW chemical looping combustion reactor system using a Ni-based oxygen carrier

A modeling tool for the investigation of chemical looping combustion (CLC) in a dual circulating fluidized bed (DCFB) reactor system is introduced. CLC is a novel combustion process with inherent CO₂ separation, consisting of two fluidized bed reactors, an air reactor (AR) and a fuel reactor (FR). A solid oxygen carrier (OC) that circulates between the reactors, transports the necessary oxygen for the combustion. In the DCFB concept both AR and FR are designed as circulating fluidized beds (CFBs). Each CFB is modeled using a very simple structure in which the reacting gas is only in contact with a defined fraction of the well mixed solids. The solids distribution along the height axis is defined by a void fraction profile. Different parameters that characterize the gas-solids contact are merged into only one parameter: the fraction of solids exposed to the gas passing in plug flow (φ_s,core). Using this model, the performance of the 120 kW DCFB chemical looping combustor at Vienna University of Technology is investigated. This pilot rig is designed for a Ni-based OC and natural gas as fuel. The influence of the reactor temperatures, solids circulation rate, air/fuel ratio and fuel power are determined. Furthermore, it is shown that with the applied kinetics data, the OC is only fully oxidized in the AR when the AR solids inventory is much larger than the FR solids inventory or when both reactors are very large. To compare different reactor systems, the effect of the solids distribution between AR and FR is studied and both gas and solids conversions are reported.     

Migration and emissions of selenium during chemical looping combustion of coal

Selenium is one of the most volatile toxic elements in coal, and its emissions must be strictly controlled. Chemical looping combustion (CLC) is a clean and efficient technology for coal. Herein, the iron-based oxygen carrier (OC) was used as an adsorbent to study the migration and emissions of selenium during the CLC of coal. Due to the oxidation and adsorption of selenium by iron-based OC, most of the selenium was retained in OC or distributed in the CO₂ stream. The proportion of gaseous selenium released into the atmosphere was less than 10%—significantly lower than that from the traditional combustion process of coal, which had a value of 91.79%. The presence of OC increased the distribution phase of selenium, promoted the conversion of gaseous selenium to solid selenium, and reduced selenium emissions in flue gas. During CLC of coal, the fuel reactor (FR) temperature and the number of OC re-oxidation cycles played an important role in the emissions and retention of selenium. The increasing FR temperature increased the gaseous selenium in the CO₂ stream, reduced the particulate selenium absorbed by OC, and reduced the selenium emissions in the atmosphere. After 10 continuous CLC cycles, the selenium concentration in OC increased from 0.889 to 8.20 mg kg⁻¹. The continuous cycling of CLC could realize the enrichment of selenium from coal to OC. Furthermore, the migration and transformation mechanism of selenium during CLC was deduced by experiments and thermodynamic simulation. This research provides a suitable reference for reducing selenium emissions and developing CLC technology.     

Integrating desulfurization with CO2-capture in chemical-looping combustion

Chemical looping combustion (CLC) is an emerging technology for clean combustion. We have previously demonstrated that the embedding of metal nanoparticles into a nanostructured ceramic matrix can result in unusually active and sinter-resistant nanocomposite oxygen carrier materials for CLC which maintain high reactivity and high-temperature stability even when sulfur contaminated fuels are used in CLC. Here, we propose a novel process scheme for in situ desulfurization of syngas with simultaneous CO₂-capture in chemical looping combustion by using these robust nanocomposite oxygen carriers simultaneously as sulfur-capture materials. We found that a nanocomposite Cu-BHA carrier can indeed strongly reduce the H₂S concentration in the fuel reactor effluent. However, during the process the support matrix is also sulfidized and takes part in the redox process of CLC. This results in SO₂ production during the reduction of the oxygen carrier and thus limits the degree of desulfurization attainable with this kind of carrier. Nevertheless, the results suggest that simultaneous desulfurization and CO₂ capture in CLC is feasible with Cu as oxygen carrier as long as appropriate carrier support materials are chosen, and could result in a novel, strongly intensified process for low-emission, high efficiency combustion of sulfur contaminated fuel streams.     

Comparison of Large‐Scale Production Methods of Fe2O3/Al2O3 Oxygen Carriers for Chemical‐Looping Combustion

Oxygen carrier (OC) particles for chemical‐looping combustion (CLC) may be produced in large scale by a number of methods such as freeze granulation, spray drying, impregnation, and mechanical mixing methods. To select the most appropriate technology for large‐scale preparation, the four preparation methods were adopted to prepare Fe₂O₃/Al₂O₃ OCs and compared with each other in terms of productivity, preparation period, physical and chemical characterization, and reactivity in CLC of lignite. Freeze granulation and spray drying methods were found to be more suitable for large‐scale production of OCs for CLC. The results of the comparative studies may provide guidelines for selecting appropriate methods for preparing OCs on industrial scale.     

High performance of la‐promoted Fe2O3/α‐Al2O3 oxygen carrier for chemical looping combustion

Iron oxide supported oxygen carrier (OC) is regarded to a promising candidate for chemical looping combustion (CLC). However, phase separation between Fe₂O₃ and supports often occurs resulted from the severe sintering of supports during calcination, which leads to the sintering and breakage of Fe₂O₃ thus the decrease of redox reactivity. In this article, La‐promoted Fe₂O₃/α‐Al₂O₃ were used as OCs for CLC of CH₄ and for the first time found that the OC with the addition of 18 wt % La exhibited outstanding reactivity and redox stability during 50 cycles of CLC of CH₄. Such a superior performance originated from the formation of LaAl₁₂O₁₉ hexaaluminate (La‐HA) phase with not only small particle size but also excellent thermal stability at CLC conditions, which worked as a binder to prevent the phase separation thereby the sintering and breakage of active species α‐Fe₂O₃ were avoided during reaction. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2827–2838, 2017     

Experimental investigation of some metal oxides for chemical looping combustion in a fluidized bed reactor

Chemical looping combustion (CLC) is the process in which metal oxides, rather than air or pure oxygen, supply the oxygen required for combustion. In this process, different gaseous fuels can be burnt with the inherent separation of CO₂. The feasibility of the CLC system depends greatly on the selection of appropriate metal oxides as oxygen carriers (OC). In this study, NiO-NiAl₂O₄, Cu_0.95Fe_1.05AlO₄, and CuO-Cu_0.95Fe_1.05AlO₄ were tested experimentally in a fluidized bed reactor as a function of oxidation-reduction cycles, temperature, bed inventory and superficial gas velocity. The results showed that flue gases with a CO₂ concentration as high as 97% can be obtained. The flue gases should be suitable for transport and storage after clean-up and purification. With an increase in the bed inventory or a decrease in superficial gas velocity, the flue gas characteristics improved i.e. more CO₂ and fewer secondary components or less unreacted fuel were obtained. Carbon formation could occur during the reduction phase but it decreased with an increase in temperature and inventory and could be completely avoided by mixing steam with the fuel. The reactivity of NiO/NiAl₂O₄ was higher than the Cu- and Fe-based oxygen carriers. Increasing the CuO fraction in the oxygen carrier led to defluidization of the bed during the reduction and oxidation phases.     

Simulating and Optimizing Auto-Thermal Reforming of Methane to Synthesis Gas Using a Non-Dominated Sorting Genetic Algorithm II Method

Conventional synthesis gas production plants consist of a natural gas steam reforming to CO + 3H₂ on Ni catalysts in a furnace. An alternative method for highly endothermic steam reforming is auto-thermal reforming. In this work, synthesis gas production by auto-thermal reforming was simulated based on a heterogeneous and one-dimensional model in two cases. The first case was the auto-thermal reformer of Dias and Assaf's study. The present work was validated by the reported experimental results. The second case was the fixed-bed catalytic auto-thermal reactor operated at high pressure, which was suitable for methanol production and Fischer–Tropsch reactions (baseline case). Then, the effect of operating variables on the system behavior was studied. Finally, Pareto-optimal solutions were determined by non-dominated sorting genetic algorithm II. The objectives included obtaining a H₂/CO ratio of 2 in the produced synthesis gas and the maximum methane conversion. The adjustable parameters were the feed temperature, mass flux, and O₂/CH₄ and H₂O/CH₄ ratios in the feed.     

Methane dry reformer by application of chemical looping combustion via Mn-based oxygen carrier for heat supplying and carbon dioxide providing

In this study, the production of H₂ utilizing chemical looping combustion (CLC) in a methane dry reformer assisted by H₂ perm-selective membranes in a CLC-DRM configuration has been investigated. CLC via employment of a Mn-based oxygen carrier generates large amounts of heat in addition to providing CO₂ as the raw material for the dry reforming (DR) reaction. The main advantage of the CLC-DRM configuration is the simultaneous capturing and consuming of CO₂ as a greenhouse gas for H₂ production.A steady state one dimensional heterogeneous catalytic reaction model is applied to analyze the performance and applicability of the proposed CLC-DRM configuration. Simulation results show that CH₄ is completely consumed in the fuel reactor (FR) of the CLC-DRM and pure CO₂ is captured by condensation of H₂O. Also, CH₄ conversion and H₂ yield reach 73.46% and 1.459 respectively at the outlet of the DR side in the CLC-DRM. Additionally, 4562 kmol h⁻¹ H₂ is produced in the DR side of the CLC-DRM.Finally, results indicate that by increasing the FR feed temperature up to 880 K, CH₄ conversion and H₂ production are enhanced to 81.15% and 4790 kmol h⁻¹ respectively.     

Oxygen carriers for chemical looping combustion of solid fuels

A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe₂O₃ powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe₂O₃ powder was used to oxidize a high carbon coal char in an inert gas removing 88% of the carbon from the char. Other properties such as cost and durability indicated iron oxide OCs potential use for CLC of solid fuels.     

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.     

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.     

Multicycle investigation of a sol‐gel‐derived Fe2O3/ATP oxygen carrier for coal chemical looping combustion

Fe‐based oxygen‐carrier particles with attapulgite (ATP) as a support material for coal chemical looping combustion (CLC) have been prepared using a sol‐gel approach. The multiredox characteristics of the prepared Fe4ATP6 (Fe₂O₃ to ATP mass ratio of 40:60) were experimentally examined in a batch fluidized bed reactor at 900°C. The experimental results indicated that the synergistic reactions between ATP and Fe₂O₃ increased the coal conversion. Fe4ATP6 exhibited high reactivity, particularly for low‐rank coals, in the CLC process. The improved pore structure and surface area were responsible for the high reactivity of Fe4ATP6. In 60 redox cycles, H₂ was mainly generated in the outlet gas as the carbon conversion efficiency had reached 95%, and both the coal combustion efficiency and CO₂ capture efficiency were greater than 95%. © 2015 American Institute of Chemical Engineers AIChE J, 62: 996–1006, 2016     

Multiphase CFD-based models for chemical looping combustion process: Fuel reactor modeling

Chemical looping combustion (CLC) is a flameless two-step fuel combustion that produces a pure CO₂ stream, ready for compression and sequestration. The process is composed of two interconnected fluidized bed reactors. The air reactor which is a conventional circulating fluidized bed and the fuel reactor which is a bubbling fluidized bed. The basic principle is to avoid the direct contact of air and fuel during the combustion by introducing a highly-reactive metal particle, referred to as oxygen carrier, to transport oxygen from the air to the fuel. In the process, the products from combustion are kept separated from the rest of the flue gases namely nitrogen and excess oxygen. This process eliminates the energy intensive step to separate the CO₂ from nitrogen-rich flue gas that reduce the thermal efficiency.Fundamental knowledge of multiphase reactive fluid dynamic behavior of the gas-solid flow is essential for the optimization and operation of a chemical looping combustor.Our recent thorough literature review shows that multiphase CFD-based models have not been adapted to chemical looping combustion processes in the open literature. In this study, we have developed the reaction kinetics model of the fuel reactor and implemented the kinetic model into a multiphase hydrodynamic model, MFIX, developed earlier at the National Energy Technology Laboratory. Simulated fuel reactor flows revealed high weight fraction of unburned methane fuel in the flue gas along with CO₂ and H₂O. This behavior implies high fuel loss at the exit of the reactor and indicates the necessity to increase the residence time, say by decreasing the fuel flow rate, or to recirculate the unburned methane after condensing and removing CO₂.     

Oxygen uncoupling behaviour for ilmenite ore oxygen carrier generated from a calcination treatment mixed with natural manganese ore

Chemical looping with O₂ uncoupling aims at using an oxygen carrier (OC) with O₂ uncoupling behaviour to promote fuel conversion. Natural ilmenite ores have been considered highly promising OCs for chemical looping technology; however, they do not possess any O₂ uncoupling behaviour. Mn-modified ilmenite ores as OCs are capable of O₂ uncoupling, while most of them are synthesized via complicated procedures by using costly chemicals. In this study, a strategy of calcination treatment on ilmenite ores mixed with manganese ores has been established to introduce Mn into the ilmenite OCs, endowing them with O₂ uncoupling behaviour in a simple and low-cost manner. The O₂ uncoupling behaviour from Mn-modified ilmenite ores is mainly due to the newly formed (Fe_1−xMn_x)₂O₃/(Fe_1−xMn_x)₃O₄ crystal phases generated during the calcination treatment, which also alleviate the thermodynamic limit of the Mn₂O₃-Mn₃O₄ redox pair. As a result, the Mn-modified ilmenite ore OCs can release O₂ at high temperatures when decreasing the oxygen partial pressure. But more importantly, the reduced OCs can be restored in the air isothermally. This established simple calcination treatment method can be used as a low-cost strategy for producing ilmenite-based OCs with O₂ uncoupling behaviour. The O₂ uncoupling behaviour is expected to be beneficial to chemical looping combustion of fuels, promote fuel conversion, minimize OC loading, and reduce energy consumption.     

Effect of solid residence time on CO<Subscript>2</Subscript> selectivity in a semi-continuous chemical looping combustor

Chemical looping combustion (CLC) is a promising technology for fossil fuel combustion with inherent CO₂ capture and sequestration, which is able to mitigate greenhouse gases (GHGs) emission. In this study, to design a 0.5MW_th pressurized chemical looping combustor for natural gas and syngas the effects of solid residences time on CO₂ selectivity were investigated in a novel semi-continuous CLC reactor using Ni-based oxygen carrier particle. The semi-continuous chemical looping combustor was designed to simulate the fuel reactor of the continuous chemical looping combustor. It consists of an upper hopper, a screw conveyor, a fluidized bed reactor, and a lower hopper. Solid circulation rate (G _s ) was controlled by adjusting the rotational speed of the screw conveyor. The measured solid circulation rate increased linearly as the rotational speed of the screw increased and showed almost the same values regardless of temperature and fluidization velocity up to 800°C and 4 U _mf , respectively. The solid circulation rate required to achieve 100% CH₄ conversion was varied to change G _s -fuel ratio (oxygen carrier feeding rate/fuel feeding rate, kg/Nm³). The measured CO₂ selectivity was greater than 98% when the Gs-fuel ratio was higher than 78 kg/Nm³.     

基于赤铁矿载氧体的煤化学链燃烧试验

化学链燃烧是一种具有CO₂内分离特性的燃烧方式。以赤铁矿为载氧体,在1 kW_th级串行流化床上进行了煤化学链燃烧试验。讨论了燃料反应器温度对气体产物组分的影响;比较了各反应参数对煤气化效率、煤气化产物的转化效率及碳捕集效率的影响情况,分析了煤中硫的排放问题。试验结果表明：温度由900℃升高到985℃,燃料反应器中CO体积份额逐渐增加,CO₂体积份额逐渐减小,空气反应器中CO₂浓度呈线性下降。燃料反应器温度的升高促进煤气化效率及碳捕集效率大大提高。载氧体量和系统负荷是煤气化产物转化效率的主要影响因素,载氧体量的增加和负荷的增加分别会使煤气化产物转化效率提高和下降。燃料反应器中的硫主要以SO₂形式存在于燃料反应器,随温度的升高,SO₂浓度由515×10^-6逐渐增加到562×10^-6相似文献   

The gas—solid trickle-flow reactor for the catalytic oxidation of hydrogen sulphide: A trickle-phase model

The oxidation of H₂S by O₂ producing elemental sulphur has been studied at temperatures of 100–300°C and at atmospheric pressure in a laboratory-scale gas-solid trickle-flow reactor. In this reactor one of the reaction products, i.e. sulphur, is removed continuously by flowing solids. A porous, free-flowing catalyst carrier has been used which contains a NaX zeolite acting as a catalyst as well as a sulphur adsorbent. In order to describe mass transfer in the trickle-flow reactor, a reactor model has been developed in which a particle-free, upflowing gas phase and a dense, downflowing gas-solids suspension, the so-called trickle phase, are distinguished. Within the trickle phase, diffusion of the reactants parallel to reaction in the catalyst particles takes place. The mass transfer rate from the gas phase to the trickle phase has been evaluated by the reaction of H₂S with SO₂, which is a much faster reaction than the reaction with O₂. From the experiments and from the reactor model calculations it appears that for the H₂S-O₂ reaction no mass transfer limitations occur at temperatures up to about 200°C, whereas at 300°C gas-phase mass transfer and diffusion within the dense solids suspension offer resistance to reaction.     

RECENT ADVANCES IN CaSO4 OXYGEN CARRIER FOR CHEMICAL-LOOPING COMBUSTION (CLC) PROCESS

Chemical-looping combustion (CLC) is a novel combustion technology with inherent separation of the greenhouse gas CO₂ and low NOx (NO, NO₂, N₂O) emissions. In CLC, the solid oxygen carrier supplies the stoichiometric oxygen needed for CO₂ and water formation, resulting in a free nitrogen mixture. The performance of oxygen carrier is the key to CLC's application. A good oxygen carrier for CLC should readily react with the fuel (fuel reactor) and should be re-oxidized upon being contacted with oxygen (air reactor). In this case, the behavior of CaSO₄ as an oxygen carrier for a CLC process, reacting with gas fuels (e.g., CO, H₂, and CH₄) and solid fuels (e.g., coal and biomass), has been analyzed. The performance of the oxygen carrier can be improved by changing the preparation method or by making mixed oxides. Generally, Al₂O₃, SiO₂, etc., which act a porous support providing a higher surface area for reaction, are used as the inert binder to increase the reactivity, durability, and fluidizability of the oxygen carrier particles. Further, simulation analysis of a CLC process based on CaSO₄ oxygen carrier was also analyzed. Finally, some important tendencies related to CaSO₄ oxygen carrier in CLC technology are put forward.     

Innovative Internally Circulating Reactor Concept for Chemical Looping‐Based CO2 Capture Processes: Hydrodynamic Investigation

An experimental hydrodynamic investigation has been carried out for a novel internally circulating chemical looping (ICCL) reactor concept proposed to reduce the technical complexities encountered in conventional chemical looping combustion (CLC) and reforming (CLR) technologies. The concept consists of a single reactor with internal physical separations dividing it into two sections, i.e., the fuel and air sections. The trade‐off for this reduction in process complexity is increased gas leakage between the two reactor sections, so a pseudo‐2D cold‐flow experimental unit was designed. The ICCL concept remains highly efficient in terms of CO₂ separation while ensuring significant process simplifications. The solids circulation rate also proved easy to control by adjusting the fluidization velocity ratio and the bed loading. In the light of the excellent hydrodynamic performance, the ICCL concept appears to be well‐suited for further development as a CLC/CLR reactor model.     

Carbon capture and utilization via chemical looping dry reforming

Chemical looping combustion (CLC) is a clean energy technology for CO₂ capture that uses periodic oxidation and reduction of an oxygen carrier with air and a fuel, respectively, to achieve flameless combustion and yield sequestration-ready CO₂ streams. While CLC allows for highly efficient CO₂ capture, it does not, however, provide a solution for CO₂ sequestration.Here, we propose chemical looping dry reforming (CLDR) as an alternative to CLC by replacing air with CO₂ as the oxidant. CLDR extends the chemical looping principle to achieve CO₂ reduction to CO, which opens a pathway to CO₂ utilization as an alternative to sequestration. The feasibility of CLDR is studied through thermodynamic screening calculations for oxygen carrier selection, synthesis and kinetic experiments of nanostructured carriers using cyclic thermogravimetric analysis (TGA) and fixed-bed reactor studies, and a brief model-based analysis of the thermal aspects of a fixed-bed CLDR process.Overall, our results indicate that it is indeed possible to reduce CO₂ to CO with high reaction rates through the use of appropriately designed nanostructured carriers, and to integrate this reaction into a cyclic redox (“looping”) process.