Experiments on chemical looping combustion of coal with a NiO based oxygen carrier

A chemical looping combustion process for coal using interconnected fluidized beds with inherent separation of CO₂ is proposed in this paper. The configuration comprises a high velocity fluidized bed as an air reactor, a cyclone, and a spout-fluid bed as a fuel reactor. The high velocity fluidized bed is directly connected to the spout-fluid bed through the cyclone. Gas composition of both fuel reactor and air reactor, carbon content of fly ash in the fuel reactor, carbon conversion efficiency and CO₂ capture efficiency were investigated experimentally. The results showed that coal gasification was the main factor which controlled the contents of CO and CH₄ concentrations in the flue gas of the fuel reactor, carbon conversion efficiency in the process of chemical looping combustion of coal with NiO-based oxygen carrier in the interconnected fluidized beds. Carbon conversion efficiency reached only 92.8% even when the fuel reactor temperature was high up to 970 °C. There was an inherent carbon loss in the process of chemical looping combustion of coal in the interconnected fluidized beds. The inherent carbon loss was due to an easy elutriation of fine char particles from the freeboard of the spout-fluid bed, which was inevitable in this kind of fluidized bed reactor. Further improvement of carbon conversion efficiency could be achieved by means of a circulation of fine particles elutriation into the spout-fluid bed or the high velocity fluidized bed. CO₂ capture efficiency reached to its equilibrium of 80% at the fuel reactor temperature of 960 °C. The inherent loss of CO₂ capture efficiency was due to bypassing of gases from the fuel reactor to the air reactor, and the product of residual char burnt with air in the air reactor. Further experiments should be performed for a relatively long-time period to investigate the effects of ash and sulfur in coal on the reactivity of nickel-based oxygen carrier in the continuous CLC reactor.     

Characterization of chemical looping combustion of coal in a 1 kWth reactor with a nickel-based oxygen carrier

Chemical looping combustion is a novel technology that can be used to meet the demand on energy production without CO₂ emission. To improve CO₂ capture efficiency in the process of chemical looping combustion of coal, a prototype configuration for chemical looping combustion of coal is made in this study. It comprises a fast fluidized bed as an air reactor, a cyclone, a spout-fluid bed as a fuel reactor and a loop-seal. The loop-seal connects the spout-fluid bed with the fast fluidized bed and is fluidized by steam to prevent the contamination of the flue gas between the two reactors. The performance of chemical looping combustion of coal is experimentally investigated with a NiO/Al₂O₃ oxygen carrier in a 1 kW_th prototype. The experimental results show that the configuration can minimize the amount of residual char entering into the air reactor from the fuel reactor with the external circulation of oxygen carrier particles giving up to 95% of CO₂ capture efficiency at a fuel reactor temperature of 985 °C. The effect of the fuel reactor temperature on the release of gaseous products of sulfur species in the air and fuel reactors is carried out. The fraction of gaseous sulfur product released in the fuel reactor increases with the fuel reactor temperature, whereas the one in the air reactor decreases correspondingly. The high fuel reactor temperature results in more SO₂ formation, and H₂S abatement in the fuel reactor. The increase of SO₂ in the fuel reactor accelerates the reaction of SO₂ with CO to form COS, and COS concentration in the fuel reactor exit gas increases with the fuel reactor temperature. The SO₂ in the air reactor exit gas is composed of the product of sulfur in residual char burnt with air and that of nickel sulfide oxidization with air in the air reactor. Due to the evident decrease of residual char in the fuel reactor with increasing fuel reactor temperature, it results in the decrease of residual char entering the air reactor from the fuel reactor, and the decrease of SO₂ from sulfur in the residual char burnt with air in the air reactor.     

Investigation of coal gasification hydrogen and electricity co-production plant with three-reactors chemical looping process

This paper analyzes a novel process for producing hydrogen and electricity from coal, based on chemical looping combustion (CLC) and gas turbine combined cycle, allowing for intrinsic capture of carbon dioxide. The core of the process consists of a three-reactors CLC system, where iron oxide particles are circulated to: (i) oxidize syngas in the fuel reactor (FR) providing a CO₂ stream ready for sequestration after cooling and steam vapor condensation, (ii) reduce steam in the steam reactor (SR) to produce hydrogen, (iii) consume oxygen in the air reactor (AR) from air releasing heat to sustain the thermal balance of the CLC system and to generate electricity. A compacted fluidized bed, composed of two fuel reactors, is proposed here for full conversion of fuel gases in FR. The gasification CLC combined cycle plant for hydrogen and electricity cogeneration with Fe₂O₃/FeAl₂O₄ oxygen carriers was simulated using ASPEN^® PLUS software. The plant consists of a supplementary firing reactor operating up to 1350 °C and three-reactors SR at 815 °C, FR at 900 °C and AR at 1000 °C. The results show that the electricity and hydrogen efficiencies are 14.46% and 36.93%, respectively, including hydrogen compression to 60 bar, CO₂ compression to 121 bar, The CO₂ capture efficiency is 89.62% with a CO₂ emission of 238.9 g/kWh. The system has an electricity efficiency of 10.13% and a hydrogen efficiency of 41.51% without CO₂ emission when supplementary firing is not used. The plant performance is attractive because of high energy conversion efficiency and low CO₂ emission. Key parameters that affect the system performance are also discussed, including the conversion of steam to hydrogen in SR, supplementary firing temperature of the oxygen depleted air from AR, AR operation temperature, the flow of oxygen carriers, and the addition of inert support material to the oxygen carrier.     

Hydrogen,nitrogen and carbon dioxide production through chemical looping using iron-based oxygen carrier – A Green plant for H2 and N2 production

In order to simulate the performance of pure methane in chemical looping using iron-based oxygen carrier, simultaneously production of three pure streams of hydrogen, nitrogen and carbon dioxide has been investigated. For this purpose, proper operating conditions have been discussed for maximum production of hydrogen, complete consumption of oxygen of inlet air and complete combustion of methane. Professional software is used to simulate the chemical looping reactors and optimize their output streams. Results show that in this process each mole of methane fuel can produce 2.533, 2.65 and 0.99 mol of pure N₂, H₂ and CO₂, respectively which contributes 80.2% energy conversion of CH₄ to H₂. Moreover, in order to consume the whole input fuel and maximize hydrogen production, it is necessary to use a supportive material to improve mechanical property of oxygen carrier particles and optimize temperature of streams by thermal integration of three reactors. Also, due to controllable temperature of three reactors, more flow rate of oxygen carrier particles can be used instead of supportive material while the air flow rate should be justified to produce pure nitrogen. Hence, three chemical looping reactors, beside hydrogen and CO₂ production, can directly produce nitrogen, by means of a process simpler than the conventional technologies like air separation unit.     

Gasification inhibition in chemical-looping combustion with solid fuels

Chemical-looping combustion (CLC) is a novel technology that can be used to meet growing demands on energy production without CO₂ emissions. The CLC process includes two reactors, an air and a fuel reactor. Between these two reactors oxygen is transported by an oxygen carrier, which most often is a metal oxide. This arrangement prevents mixing of N₂ from the air with CO₂ from the combustion giving combustion gases that consist almost entirely of CO₂ and H₂O. The technique reduces the energy penalty that normally arises from the separation of CO₂ from other flue gases, hence, CLC could make capture of CO₂ cheaper. For the application of CLC to solid fuels, the char remaining after devolatilization will react indirectly with the oxygen carrier via steam gasification. It has been suggested that H₂, and possibly CO, has an inhibiting effect on steam gasification in CLC. In this work experiments were conducted to investigate this effect. The experiments were conducted in a laboratory fluidized-bed reactor that was operating cyclically with alternating oxidation and reduction periods. Two different oxygen carriers were used as well as an inert sand bed. During the reducing period varying concentrations of CO or H₂ were used together with steam while the oxidation was conducted with 10% O₂ in N₂. The temperature was constant at 970 °C for all experiments. The results show that CO does not directly inhibit the gasification whereas the partial pressure of H₂ had a significant influence on fuel conversion. The results also suggest that dissociative hydrogen adsorption is the predominant hydrogen inhibition mechanism under the laboratory conditions, thus explaining why char conversion is much faster in a bed of oxygen carrying material, compared to an inert sand bed.     

Chemical‐looping combustion — an overview and application of the recirculating fluidized bed reactor for improvement

This paper propose recirculating fluidized bed (RCFB) reactor for chemical‐looping combustion (CLC) to overcome some of the issues associated with the existing interconnected reactors arrangements like low residence time of bed material in the air reactor, high attrition of bed material in the cyclone separator, cluster formation in the air reactor, complex operation involving loop seals and high heat losses. RCFB has high solid circulation rate, long residence time, efficient fuel–oxygen carrier contact, low heat losses and low gas leak in between the reactors, as compared to the existing reactor configurations. A cold model study was performed on a Perspex made, semicircular, transparent RCFB reactor. A single RCFB reactor was operated in the alternate oxidation and fuel burning cycles to simulate the interconnected reactors arrangement for CLC. The generated experimental data has been used to predict the optimal RCFB reactor configuration for a RCFB‐based CLC power plant. Copyright © 2014 John Wiley & Sons, Ltd.     

Sulfur behavior in chemical looping combustion with NiO/Al2O3 oxygen carrier

Chemical looping combustion (CLC) is a novel technology where CO₂ is inherently separated during combustion. Due to the existence of sulfur contaminants in the fossil fuels, the gaseous products of sulfur species and the interaction of sulfur contaminants with oxygen carrier are a big concern in the CLC practice. The reactivity of NiO/Al₂O₃ oxygen carrier reduction with a gas mixture of CO/H₂ and H₂S is investigated by means of a thermogravimetric analyzer (TGA) and Fourier Transform Infrared spectrum analyzer in this study. An X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM) are used to evaluate the phase characterization of reacted oxygen carrier, and the formation mechanisms of the gaseous products of sulfur species are elucidated in the process of chemical looping combustion with a gaseous fuel containing hydrogen sulfide. The results show that the rate of NiO reduction with H₂S is higher than the one with CO. There are only Ni and Ni₃S₂ phases of nickel species in the fully reduced oxygen carrier, and no evidence for the existence of NiS or NiS₂. The formation of Ni₃S₂ is completely reversible during the process of oxygen carrier redox. A liquid phase sintering on the external surface of reduced oxygen carriers is mainly attributed to the production of the low melting of Ni₃S₂ in the nickel-based oxygen carrier reduction with a gaseous fuel containing H₂S. Due to the sintering of metallic nickel grains on the external surface of the reduced oxygen carrier, further reaction of the oxygen carrier with H₂S is constrained, and there is no increase of the sulfidation index of the reduced oxygen carrier with the cyclical reduction number. Also, a continuous operation with a syngas of carbon monoxide and hydrogen containing H₂S is carried out in a 1 kW_th CLC prototype based on the nickel-based oxygen carrier, and the effect of the fuel reactor temperature on the release of gaseous products of sulfur species is investigated.     

A mechanistic investigation of a calcium-based oxygen carrier for chemical looping combustion

Chemical looping combustion (CLC) has been suggested as an energy-efficient method for the capture of carbon dioxide from combustion. It is indirect combustion by the use of an oxygen carrier, which can be used for CO₂ capture in power-generating processes. The possibility of CLC using a calcium-based oxygen carrier is investigated in this paper. In the air reactor air is supplied to oxidize CaS to CaSO₄, where oxygen is transferred from air to the oxygen carrier; the reduction of CaSO₄ to CaS takes place in the fuel reactor. The exit gas from the fuel reactor is CO₂ and H₂O. After condensation of water, almost pure CO₂ could be obtained. The thermodynamic and kinetic problem of the reduction reactions of CaSO₄ with CO and H₂ and the oxidization reactions of CaS with O₂ is discussed in the paper to investigate the technique possibility. To prevent SO₂ release from the process of chemical looping combustion using a calcium-based oxygen carrier, thermochemical CaSO₄ reduction and CaS oxidation are discussed. Thermal simulation experiments are carried out using a thermogravimetric analyzer (TGA). The properties of the products are characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray diffractometry (XRD), and the optimal reaction parameters are evaluated. The effects of reaction temperature, reductive gas mixture, and oxygen partial pressure on the composition of flue gas are discussed. The suitable temperature of the air reactor is between 1050 and 1150 °C and the optimal temperature of the fuel reactor between 900 and 950 °C.     

Iron ore as oxygen carrier improved with potassium for chemical looping combustion of anthracite coal

Chemical looping combustion (CLC) is an innovative combustion technology with inherent separation of CO₂ without energy penalty. When solid fuel is applied in CLC, the gasification of solid fuel is the rate-limiting process for in situ gasification of coal and reduction of oxygen carrier. The K₂CO₃-decorated iron ore after calcinations was used as oxygen carrier in CLC of anthracite coal, and potassium ferrites were formed during the calcinations process. The experiments were performed in a laboratory fluidized bed reactor with steam as a gasification medium. Effects of reaction temperature, K₂CO₃ loading in iron ore and cycle on the gas concentration, carbon conversion, gasification rate and yields of carbonaceous gases were investigated. The carbon gasification was accelerated during the fast reaction stage between 860 °C and 920 °C, and the water–gas shift reaction was significantly enhanced in a wider temperature range of 800 °C to 920 °C. With the K₂CO₃ loading in iron ore increasing from 0% to 20% at 920 °C, the carbon conversion was accelerated in the fast reaction stage, and the fast reaction stage became shorter. The yield of CO₂ reached a maximum of 94.4% and the yield of CO reached a minimum of 3.4% when use the iron ore loaded with 6% K₂CO₃. SEM analysis showed that the K₂CO₃-decorating in iron ore would cause a sintering on the particle surface of oxygen carrier, and the K₂CO₃ loading in iron ore should not be too high. Cycle experiments indicate that the K₂CO₃-decorated iron ore has a relative stable catalytic effect in the CLC process.     

Design of an integrated process for simultaneous chemical looping hydrogen production and electricity generation with CO2 capture

This study was aimed at proposing a novel integrated process for co-production of hydrogen and electricity through integrating biomass gasification, chemical looping combustion, and electrical power generation cycle with CO₂ capture. Syngas obtained from biomass gasification was used as fuel for chemical looping combustion process. Calcium oxide metal oxide was used as oxygen carrier in the chemical looping system. The effluent stream of the chemical looping system was then transferred through a bottoming power generation cycle with carbon capture capability. The products achieved through the proposed process were highly-pure hydrogen and electricity generated by chemical looping and power generation cycle, respectively. Moreover, LNG cold energy was used as heat sink to improve the electrical power generation efficiency of the process. Sensitivity analysis was also carried out to scrutinize the effects of influential parameters, i.e., carbonator temperature, steam/biomass ratio, gasification temperature, gas turbine inlet stream temperature, and liquefied natural gas (LNG) flow rate on the plant performance. Overall, the optimum heat integration was achieved among the sub-systems of the plant while a high energy efficiency and zero CO₂ emission were also accomplished. The findings of the present study could assist future investigations in analyzing the performance of integrated processes and in investigating optimal operating conditions of such systems.     

Reactivity deterioration of NiO/Al2O3 oxygen carrier for chemical looping combustion of coal in a 10 kWth reactor

A relatively long-term experiment for chemical looping combustion of coal with NiO/Al₂O₃ oxygen carrier was carried out in a 10 kW_th continuous reactor of interconnected fluidized beds, and 100 h of operation was reached with the same batch of the oxygen carrier. The reactivity deterioration of the oxygen carriers was present during the experimental period. The reactivity deterioration of reacted oxygen carriers at different experimental stages was evaluated using X-ray diffraction (XRD), scanning electron microscope (SEM), and X-ray fluorescence spectrometer. SEM analysis showed no significant change in the morphology of the nickel-based oxygen carrier at the fuel reactor temperature ?940 °C, but loss of surface area and porosity of reacted oxygen carriers was observed when the fuel reactor temperature exceeded 960 °C. The results show that the sintering effect have mainly contributed to the reactivity deterioration of reacted oxygen carriers in the CLC process for coal, while the effects of coal ash and sulfur can be ignored. The oxidization of reduced oxygen carrier with air was an intensive exothermic process, and the high temperature of oxygen carrier particles led to sintering on the surface of oxygen carrier particles in the air reactor. Attention must be paid to control the external circulation of oxygen carrier particles in the interconnected fluidized beds in order to efficiently transport heat from the air reactor to the fuel reactor, and reduce the temperature of oxygen carrier particles in the air reactor. Improvement of reactivity deterioration of reacted oxygen carriers was achieved by the supplement of steam into the fuel reactor. Nevertheless, NiO/Al₂O₃ is still one of the optimal oxygen carriers for chemical looping combustion of coal if the sintering of oxygen carrier is minimized at the suitable reactor temperature.     

Numerical simulation of fuel reactor for a methane-fueled chemical looping combustion using bubbling fluidized bed with internal particle circulation

Chemical-looping combustion (CLC) is recognized as a promising technique to efficiently and economically capture emitted carbon dioxide in common combustion processes. In this study, the bubbling fluidized bed (BFB) fuel reactor performance of the CLC system was examined through numerical simulation. The reduction reaction performance obtained from conventional BFB fuel reactor and BFB fuel reactor incorporated with internal particle circulation denoted as internal circulation bubbling fluidized bed reactor (ICBFB), were compared under the same fuel flow rate and operating conditions. By using CH₄ as fuel and ilmenite as the oxygen carrier, it was found the reduction reaction can be enhanced by using the ICBFB fuel reactor due to particle circulation. The particle circulation increased the mixing and contact time between fuel and oxygen carrier that produced reduction reaction enhancement. Moreover, the simulation results indicated that higher reduction reaction performance can be achieved by higher reduction reaction temperature and initial oxygen carrier volume fraction.     

Techno-economic analysis of processes with integration of fluidized bed heat exchangers for H2 production – Part 2: Chemical-looping combustion

This work covers a techno-economic assessment for processes with inherent CO₂ separation, where a fluidized bed heat exchanger (FBHE) is used as heat source for steam reforming in a hydrogen production plant. This article builds upon the work presented in Part 1 of this study by Stenberg et al. [1], where a process excluding CO₂ capture was examined. Part 2 suggests two process configurations integrating steam reforming with a chemical-looping combustion (CLC) system, thus providing inherent CO₂ capture. The first system (case CM) uses natural gas as supplementary fuel whereas the second system (case CB) uses solid biomass, which enables net negative CO₂ emissions. In both systems, the reformer tubes are immersed in a bubbling fluidized bed where heat for steam reforming is efficiently transferred to the tubes. The processes include CO₂ compression for pipeline transportation, but excludes transport and storage. The CLC system is designed based on key parameters, such as the oxygen carrier circulation rate and oxygen transport capacity. The first system displays a process with net zero emissions and a hydrogen production efficiency which is estimated to 76.2%, which is almost 8% higher than the conventional process. The levelized production cost is 1.6% lower at below 2.6 €/kg H₂. The second system shows the possibility to reduce the emissions to ?34.1 g CO₂/MJ_H2 compared to the conventional plant which emits 80.7 g CO₂/MJ_H2. The hydrogen production efficiency is above 72% and around 2% higher than the conventional process. The capital investments are higher in this plant and the levelized hydrogen production cost is estimated to around 2.67 €/kg. The cost of CO₂ avoidance, based on a reference SMR plant with CO₂ capture, is low for both cases (?4.3 €/ton_CO2 for case CM and 2.7 €/ton_CO2 for case CB).     

An overview of solar decarbonization processes,reacting oxide materials,and thermochemical reactors for hydrogen and syngas production

Solar decarbonization processes are related to the different thermochemical conversion pathways of hydrocarbon feedstocks for solar fuels production using concentrated solar energy as the external source of high-temperature process heat. The main investigated routes aim to convert gaseous and solid feedstocks (methane, coal, biomass …) into hydrogen and syngas via solar cracking/pyrolysis, reforming/gasification, and two-step chemical looping processes using metal oxides as oxygen carriers, further associated with thermochemical H₂O/CO₂ splitting cycles. They can also be combined with metallurgical processes for production of energy-intensive metals via solar carbothermal reduction of metal oxides. Syngas can be further converted to liquid fuels while the produced metals can be used as energy storage media or commodities. Overall, such solar-driven processes allow for improvements of conversion yields, elimination of fossil fuel or partial feedstock combustion as heat source and associated CO₂ emissions, and storage of intermittent solar energy in storable and dispatchable chemical fuels, thereby outperforming the conventional processes. The different solar thermochemical pathways for hydrogen and syngas production from gaseous and solid carbonaceous feedstocks are presented, along with their possible combination with chemical looping or metallurgical processes. The considered routes encompass the cracking/pyrolysis (producing solid carbon and hydrogen) and the reforming/gasification (producing syngas). They are further extended to chemical looping processes involving redox materials as well as metallurgical processes when metal production is targeted. This review provides a broad overview of the solar decarbonization pathways based on solid or gaseous hydrocarbons for their conversion into clean hydrogen, syngas or metals. The involved metal oxides and oxygen carrier materials as well as the solar reactors developed to operate each decarbonization route are further described.     

In-situ reforming and combustion of liquid fuel using MnOx/Ce-γAl2O3 oxygen carrier in a chemical looping combustion process

A new MnO_x/Ce-γAl₂O₃ oxygen carrier is developed for liquid fuel based fluidized chemical looping combustion (CLC) process. The developed material serves both as a catalyst and as a source of solid phase oxygen for gasification/reforming of liquid fuel followed by the combustion of the gasified products. The support γAl₂O₃ is modified with cerium, improved thermal stability and minimized the interaction with the main active component MnO_x. In order to validate the desired properties, the prepared MnO_x/Ce-γAl₂O₃ samples are characterized using various physicochemical characterizations, including X-ray fluorescence (XRF), nitrogen adsorption, thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscope (SEM), temperature programmed reduction (TPR), and temperature programmed desorption (TPD). TPR, TGA and XRD analysis confirm that the Ce modification improves the thermal stability of γAl₂O₃ and hinders the formation of difficult reducing manganese aluminate. TPR profiles show excellent reduction and re-oxidation performances of the Ce modified samples. Based on characterizations, a selected sample is further evaluated in a fluidized CREC Riser Simulator (CREC: Chemical Reactor Engineering Centre) using n-hexane as a liquid fuel surrogate. Under the studied reaction conditions (500–650 C; 10–45 s reaction time), CO₂ and CO are the main combustion products. At 650 °C, approximately 92% n-hexane combustion and 60% of CO₂ selectivity was achieved, which is very encouraging, given the complexity of the interaction of liquid fuel with the solid metal oxides.     

The thermodynamics of chemical looping combustion applied to the hydrogen economy

Adoption of the hydrogen economy (HE) is one means by which industrial economies can reduce point source CO₂ emissions. At its simplest, H₂ is generated centrally using a primary energy source to split water; the H₂ is then transmitted to end users, thereby ‘carrying’ energy from the central plant to, say, a motor vehicle. Assuming the primary energy input to drive the system comes from fossil fuels, carbon capture at these plants is required to reduce the specific CO₂ emissions of the system to the minimum. However, an additional thermodynamic advantage of the HE is often ignored, as it facilitates a rise in second law efficiency in the utilisation of fossil fuels. The HE can be viewed as an open-loop, chemical looping combustion (CLC) system, with H₂ as the oxygen carrier. In CLC systems, entropy recirculation leads to a reduction in the reversible reaction temperature; in the HE this results in a rise in the efficiency of both H₂ producing and H₂ consuming devices. In consequence, the second law efficiency of internal combustion engines burning H₂ is increased for a given peak cycle temperature. For fuel cells, with notionally higher thermal efficiency than internal combustion (IC) engines, the percentage gain in second law efficiency is even more pronounced. A process flow analysis allowing for likely irreversibilities shows that combining a CLC plant and a fleet of fuel cells, the overall efficiency of the system equals 40.8%, exceeding the performance of competing fuel powered technologies.     

Oxygen-carrier selection and thermal analysis of the chemical-looping process for hydrogen production

The three-reactor chemical-looping process (TRCL) for the production of hydrogen from natural gas is quite attractive for both CO₂ capture and hydrogen production. The TRCL process consists of a fuel reactor, a steam reactor and an air reactor. In the fuel reactor, natural gas is oxidized to CO₂ and H₂O by the lattice oxygen of the oxygen carrier. In the steam reactor, the steam is reduced to hydrogen through oxidation of the reduced oxygen carrier. In the air reactor, the oxygen carrier is fully oxidized by air. In this process, the oxygen carrier is recirculated among the three reactors, which avoids direct contact between fuel, steam and air. In this study, various candidate materials were proposed for the oxygen carrier and support, and a thermal analysis of the process was performed. The oxygen carrier for the process must have the ability to split water into hydrogen in its reduced state, which is a different chemical property from that of the chemical-looping combustion medium. The selection of the oxygen carrier and support require careful consideration of their physical and chemical properties. Fe₂O₃, WO₃ and CeO₂ were selected as oxygen carriers. Thermal analysis indicated an expected hydrogen production of 2.64 mol H₂ per mol CH₄ under thermoneutral process conditions. The results indicated that hydrogen production was affected mainly by the steam-conversion rate. The solid-circulation rate and temperature drop in the fuel reactor were calculated for the selected oxygen carriers with different metal oxide contents and solid-conversion rates.     

Fe2O3为载氧体的煤/秸秆化学链燃烧循环特性研究

对煤、秸秆与Fe2O3以不同质量掺混比混合后化学链燃烧过程中载氧体还原/再生的多循环反应特性进行了研究,重点分析了固体燃料带入的灰分对化学链反应速率的影响以及秸秆的掺入对化学链反应的改善.结果表明：载氧体Fe2O3质量掺混比的增大有利于化学链反应的进行,燃烧起始反应温度降低;Fe2O3作为载氧体受灰分积累的影响较大,其可持续循环能力较差;煤中掺入秸秆改善了煤的化学链燃烧特性,提高了燃烧反应速率和载氧体的再生反应速率.     

Progress in Chemical-Looping Combustion and Reforming technologies

This work is a comprehensive review of the Chemical-Looping Combustion (CLC) and Chemical-Looping Reforming (CLR) processes reporting the main advances in these technologies up to 2010. These processes are based on the transfer of the oxygen from air to the fuel by means of a solid oxygen-carrier avoiding direct contact between fuel and air for different final purposes. CLC has arisen during last years as a very promising combustion technology for power plants and industrial applications with inherent CO₂ capture which avoids the energetic penalty present in other competing technologies. CLR uses the chemical looping cycles for H₂ production with additional advantages if CO₂ capture is also considered.     

Hydrogen production with CO2 capture by coupling steam reforming of methane and chemical-looping combustion: Use of an iron-based waste product as oxygen carrier burning a PSA tail gas

In this work it is analyzed the performance of an iron waste material as oxygen carrier for a chemical-looping combustion (CLC) system. CLC is a novel combustion technology with the benefit of inherent CO₂ separation that can be used as a source of energy for the methane steam reforming process (SR). The tail gas from the PSA unit is used as fuel in the CLC system.The oxygen carrier behaviour with respect to gas combustion was evaluated in a continuous 500 W_th CLC prototype using a simulated PSA off-gas stream as fuel. Methane or syngas as fuel were also studied for comparison purposes. The oxygen carrier showed enough high oxygen transport capacity and reactivity to fully convert syngas at 880 °C. However, lower conversion of the fuel was observed with methane containing fuels. An estimated solids inventory of 1600 kg MW_th⁻¹ would be necessary to fully convert the PSA off-gas to CO₂ and H₂O. An important positive effect of the oxygen carrier-to-fuel ratio up to 1.5 and the reactor temperature on the combustion efficiency was found.A characterization of the calcined and after-used particles was carried out showing that this iron-based material can be used as oxygen carrier in a CLC plant since particles maintain their properties (reactivity, no agglomeration, high durability, etc.) after more than 111 h of continuous operation.