Oxide Based Oxygen Carrier Research Articles

Recent progress in the development of synthetic oxygen carriers for chemical looping combustion applications

Continuously rising concentrations of CO2 in the atmosphere has led to significant negative impacts on the environment which propelled research efforts to replace fossil fuel-based energy with clean energy sources. However, the reliance on fossil fuel as the main energy source is projected to stay for many years to come, and therefore developing cleaner pathways to utilize fossil fuels for energy generation is paramount. Chemical looping combustion (CLC) has emerged in recent years as a promising technology for CO2 capture in power plants and other CO2 intensive industries. A key cornerstone for CLC is the development of efficient oxygen carriers with high oxygen capacity, fast kinetics, cyclic stability, mechanical strength, and low cost. The research progress in this field is rapidly growing to tackle the major materials and operational challenges to advance the knowledge toward a commercial scale CLC application. This work provides an overview of the significant advancements achieved over the past seven years in the development of synthetic metal oxide-based oxygen carriers. A summary of key performance indicators used to evaluate oxygen carriers is presented in this study to enable for a systematic assessment of the oxygen carriers’ properties and performance. This work is focused on summarizing and critically reviewing the literature on the development of oxygen carriers such as Ni, Cu, Fe, Mn, Co-based metal oxides and combined/mixed oxygen carriers in the past seven years. Studies of naturally occurring materials and waste materials used as oxygen carriers are excluded from this review which is mainly focused on synthetically prepared materials. Significant efforts were dedicated to investigating the role of the supports, synthesis methods, promotors, and other factors affecting the CLC performance of synthetic oxygen carriers using solid, liquid, and gaseous fuels. This review also outlines the main challenges, research needs and opportunities for future progress to highlight potential pathways to develop synthetic oxygen carriers in an environmentally friendly, and cost-effective manner.

Techno-economic analysis of e-waste based chemical looping reformer as hydrogen generator with co-generation of metals, electricity and syngas

Chemical looping reforming (CLR) is an efficient technology to convert hydrocarbon fuels into CO 2 and H 2 using metal oxide based oxygen carriers. The novelty of the present study is to utilize electronic waste such as printed circuit board (PCB) to generate high quality syngas and metallic components for the CLR process. A portion of the syngas generated during e-waste pyrolysis is used with coal and polypropylene for effective combustion. A techno-economic analysis is performed for the production of hydrogen and electricity in the CLR method. The levelized costs for electricity (LCOE), hydrogen (LCOH), syngas (LCOS), and metal (LCOM) production using e-wastes are estimated as 92.28 $/MWh, 3.67 $/kg, 0.0034 $/kWh, and 24.32 $/ton, respectively. The LCOH is found to be the least of 2.90 $/kg under the co-feed conditions of PCB syngas-PP. The integration of the e-waste based CLR with a steam turbine system achieved a net efficiency of 50%. • E-waste based chemical looping reformer (CLR) is proposed for hydrogen generation. • Mixture of PCB based syngas, coal, and polypropylene (PP) is used as feedstock. • Techno-economic analysis is conducted for CLR integrated steam turbine system. • Levelized costs for hydrogen, electricity, syngas and metal oxides are assessed. • PCB syngas with coal and PP produced a net efficiency of 48.8% with LCOH of 3 $/kg.

CuO/ZrO2 modified by WO3 oxygen carriers for chemical looping with oxygen uncoupling

The use of mixed metal oxides as oxygen carriers for chemical looping with oxygen uncoupling (CLOU) applications has shown great potential compared to single metal oxide-based oxygen carriers. In this work, the effects of adding WO3 to CuO/ZrO2 oxygen carriers on the oxygen capacity and rate indices for CLOU applications are investigated using nitrogen gas environment. Two synthesis methods were used to prepare the CuO-WO3/ZrO2 oxygen carriers, namely the coimpregnation and sequential impregnation, to evaluate the role of the oxygen carriers’ preparation method. The resulting oxygen carriers were thoroughly characterized using XRD, ICP-OES, SEM-EDS and H2-TPR characterization techniques to evaluate the physicochemical properties of the mixed oxide oxygen carriers. The oxygen transport capacity was found to significantly increase for the WO3-modified oxygen carriers compared with the single metal oxide CuO/ZrO2 which was due to the formation of a Cu-W intermediate phases that was found to enhance the redox characteristics of the oxygen carriers. Moreover, the sample synthesized via coimpregnation method displayed higher oxygen release capacity than the sequentially impregnated sample. This was ascribed to the formation a Cu-rich intermediate phase (Cu3WO6) possessing higher Cu/W ratio on the coimpregnated sample compared with a CuWO4-x phase with lower Cu/W ratio and larger crystallite structure formed on the sequentially impregnated oxygen carrier. The mixed metal oxide oxygen carriers also showed a stable redox performance which highlights the potential of WO3 as a modifier to Cu-based oxygen carriers to enhance the oxygen capacity and subsequently decrease the solids inventory. The proposed WO3-based promotors offer significant trait to synthesize Cu-based oxygen carriers with excellent properties for CLOU applications.

Isothermal Splitting of CO2 to CO Using Cobalt-Ferrite Redox Looping

Abstract Rising atmospheric CO2 levels from significant imbalance between carbon emissions from fossil fuel utilization, especially for energy and chemicals, and natural carbon sequestration rates is known to drive-up the global temperatures and associated catastrophic climate changes, such as rising mean sea level, glacial melting, and extinction of ecosystems. Carbon capture and utilization techniques are necessary for transition from fossil fuel infrastructure to renewable energy resources to help delay the dangers of reaching to the point of positive feedback between carbon emissions and climate change which can drive terrestrial conditions to uninhabitable levels. CO2 captured from the atmosphere directly or from flue gases of a power plant can be recycled and transformed to CO and syngas for use as energy and value-added chemicals. Utilizing renewable energy resources to drive CO2 conversion to CO via thermochemical redox looping can provide a carbon negative renewable energy conversion pathway for sustainable energy production as well as value-added products. Substituted ferrites such as Co-ferrite, Mn-ferrite were found to be promising materials to aid the conversion of CO2 to CO at lower reduction temperatures. Furthermore, the conversion of these materials in the presence of Al2O3 provided hercynite cycling, which further lowered the reduction temperature. In this paper, Co-ferrite and Co-ferrite-alumina prepared via co-precipitation were investigated to understand their potential as oxygen carriers for CO2 conversion under isothermal redox looping. Isothermal reduction looping provided improved feasibility in redox conversion since it avoids the need for temperature swinging which improves thermal efficiency. These efforts alleviate the energy losses in heat recovery while also reducing thermal stresses on both the materials and the reactor. Lab-scale testing was carried out at 1673 K on these materials for extended periods and multiple cycles to gain insights into cyclic performance and the feasibility of sintering, which is a common issue in iron oxide-based oxygen carriers. Cobalt doping provided with lowering of reduction temperature requirement at the cost of oxidation thermodynamic spontaneity that required increased oxidation temperature. At the concentrations examined, these opposing phenomena made isothermal redox operation feasible by providing high CO yields comparable with oxygen carriers in the literature, which were operated at different temperatures for reduction and oxidation. Significantly high CO yields (∼750 µmol/g) were obtained from Co-ferrite isothermal redox looping. Co-ferrite-alumina provided lower CO yields compared with Co-ferrite. The oxygen storage was similar to those reported in the literature on isothermal H2O splitting, but with improved morphological stability at high temperature, especially compared with ferrite. This pathway of oxygen carrier development is considered suitable with further requirement in optimization for scaling of renewable CO2 conversion into valuable products.

High-pressure hydrogen production with inherent sequestration of a pure carbon dioxide stream via fixed bed chemical looping

The proof of concept for the production of pure pressurized hydrogen from hydrocarbons in combination with the sequestration of a pure stream of carbon dioxide with the reformer steam iron cycle is presented. The iron oxide based oxygen carrier (95% Fe2O3, 5% Al2O3) is reduced with syngas and oxidized with steam at 1023 K. The carbon dioxide separation is achieved via partial reduction of the oxygen carrier from Fe2O3 to Fe3O4 yielding thermodynamically to a product gas only containing CO2 and H2O. By the subsequent condensation of steam, pure CO2 is sequestrated. After each steam oxidation phase, an air oxidation was applied to restore the oxygen carrier to hematite level. Product gas pressures of up to 30.1 bar and hydrogen purities exceeding 99% were achieved via steam oxidations. The main impurities in the product gas are carbon monoxide and carbon dioxide, which originate from solid carbon depositions or from stored carbonaceous molecules inside the pores of the contact mass. The oxygen carrier samples were characterized using elemental analysis, BET surface area measurement, XRD powder diffraction, SEM and light microscopy. The maximum pressure of 95 bar was demonstrated for hydrogen production in the steam oxidation phase after the full oxygen carrier reduction, significantly reducing the energy demand for compressors in mobility applications.

Perovskite Promoted Mixed Cobalt–Iron Oxides for Enhanced Chemical Looping Air Separation

Chemical looping air separation (CLAS) is a promising approach to produce high purity oxygen from air. Redox kinetics and oxygen carrying capacity of oxide-based oxygen carrier materials play a cri...

Performance of Iron Oxide-Based Oxygen Carrier in Biomass Pyrolysis

Performance of Iron Oxide-Based Oxygen Carrier in Biomass Pyrolysis

The effect of copper on the redox behaviour of iron oxide for chemical-looping hydrogen production probed by in situ X-ray absorption spectroscopy.

The production of high purity hydrogen with the simultaneous capture of CO2, can be achieved through a chemical looping (CL) cycle relying on an iron oxide-based oxygen carrier. Indeed, the availability of active and cyclically stable oxygen carriers is a key criterion for the practical implementation of this technology. In this regard, improving our understanding of the reduction pathway(s) of iron-based oxygen carriers and the development of concepts to increase the reduction kinetics are important aspects. The aim of this work is to evaluate the effect of the addition of copper on the redox behaviour of iron oxide based oxygen carriers stabilized on ZrO2. In situ pulsed-H2 XANES (Fe K-edge) experiments allowed for the determination of the reduction pathways in these materials, viz. the reduction of both Fe2O3 and CuFe2O4 proceeded via a Fe2+ intermediate: Fe2O3 (CuFe2O4) → Fe3O4 (Cu0) → FeO (Cu0) → Fe0 (Cu0). In the first step CuFe2O4 is reduced to Cu0 and Fe3O4, whereby Cu0 promotes the further reduction of iron oxide, increasing their rate of formation. In particular, the rate of reduction of FeO → Fe0 is accelerated most dramatically by Cu0. This is an encouraging result as the FeO → Fe0 transition is the slowest reduction reaction.

Particulate Formation from a Copper Oxide-Based Oxygen Carrier in Chemical Looping Combustion for CO2 Capture.

Attrition behavior and particle loss of a copper oxide-based oxygen carrier from a methane chemical looping combustion (CLC) process was investigated in a fluidized bed reactor. The aerodynamic diameters of most elutriated particulates, after passing through a horizontal settling duct, range between 2 and 5 μm. A notable number of submicrometer particulates are also identified. Oxygen carrier attrition was observed to lead to increased CuO loss resulting from the chemical looping reactions, i.e., Cu is enriched in small particles generated primarily from fragmentation in the size range of 10-75 μm. Cyclic reduction and oxidation reactions in CLC have been determined to weaken the oxygen carrier particles, resulting in increased particulate emission rates when compared to those of oxygen carriers without redox reactions. The generation rate for particulates <10 μm was found to decrease with progressive cycles over as-prepared oxygen carrier particles and then reach a steady state. The surface of the oxygen carrier is also found to be coarsened due to a Kirkendall effect, which also explains the enrichment of Cu on particle surfaces and in small particles.

Morphology evolution and nanostructure of chemical looping transition metal oxide materials upon redox processes

Transition metal are heavily used in chemical looping technologies because of their high oxygen carrying capacity and high thermal reactivity. These oxygen activities result in the oxide formation and oxygen vacancy formation that affect the nanoscale crystal phase and morphology within these materials and their subsequent bulk chemical behavior. In this study, two selected earlier transition metals manganese and cobalt as well as two selected later transition metals copper and nickel that are important to chemical looping reactions are investigated when they undergo cyclic redox reactions. We found Co microparticles exhibited increased CoO impurity presence when oxidized to Co3O4 upon cyclic oxidation; CuO redox cycles prefer to be limited to a reduced form of Cu2O and an oxidized form of CuO; Mn microparticles were oxidized to a mixed phases of MnO and Mn3O4, which causes delamination during oxidation. For Ni microparticles, a dense surface were observed during the redox reaction. The atomistic thermodynamics methods and density functional theory (DFT) calculations are carried out to elucidate the effect of oxygen dissociation and migration on the morphological evolution of nanostructures during the redox processes. Our results indicate that the earlier transition metals (Mn and Co) tend to have stronger interaction with O2 than the later transition metals (Ni and Cu). Also, our modified Brønsted−Evans−Polanyi (BEP) relationship for reaction energies and total reaction barriers reveals that reactions of earlier transition metals are more exergonic and have lower oxygen dissociation barriers than those of later transition metals. In addition, it was found that for these transition metal oxides the oxygen vacancy formation energies increase with the depth. The oxide in the higher oxidation state of transition metal has lower vacancy formation energy, which can facilitate forming the defective nanostructures. The fundamental understanding of these metal oxide reactions is essential to designing the metal oxide-based oxygen carriers for chemical looping applications.

Li-Promoted LaxSr2–xFeO4−δ Core–Shell Redox Catalysts for Oxidative Dehydrogenation of Ethane under a Cyclic Redox Scheme

Chemical looping oxidative dehydrogenation (CL-ODH) of ethane utilizes a transition metal oxide based oxygen carrier, also known as a redox catalyst, to convert ethane into ethylene under an autothermal cyclic redox scheme. The current study investigates a Li-promoted LaxSr2–xFeO4−δ (LaSrFe) redox catalyst for CL-ODH reactions. While LaSrFe without Li promoter exhibits low ethylene selectivity, addition of Li leads to high selectivity/yield and good regenerability. Up to 61% ethane conversion and 90% ethylene selectivity are achieved with Li-promoted LaSrFe. Further characterization indicates that the Li-promoted LaSrFe redox catalyst consists of LiFeO2 (disordered rock salt) and LaSrFe (Ruddlesden–Popper) phases. Moreover, the surface of the redox catalysts is enriched with Li cations. It is also determined the LaSrFe phase contributes to oxygen storage and donation, whereas the activity and selectivity of the redox catalysts are modified by the Li promoter: while oxygen for the CL-ODH reaction is suppli...

Iron oxide looping for natural gas conversion in a countercurrent moving bed reactor

Chemical looping technologies have the potential to reduce the natural-gas conversion cost in a carbon-constrained scenario. Given the increasing importance of natural gas to global energy supply, this work investigates the application of an iron oxide based chemical looping technology for natural gas conversion. A thermodynamic criterion for selecting iron oxide based oxygen carrier material and designing the reaction system is developed using an adapted Ellingham diagram. Equilibrium modeling for detailed thermodynamic analysis is conducted for verifying the Ellingham diagram analysis. The thermodynamic equilibrium model also establishes a system baseline performance, and experimental proof of concept bench-scale demonstration is investigated. The bench-scale testing is used to characterize the effect of parameters like solids to gas ratio and temperature of the reactor on system performance. An optimal set of operating conditions is identified for further testing on a larger scale.

Chemical looping combustion of high-sulfur coal with NiFe2O4-combined oxygen carrier

Chemical looping combustion (CLC) of coal has gained increasing attention as a novel combustion technology for its attractive advantage in the inherent separation of CO2. In relative to the single metal oxide-based oxygen carrier (OC), combined OC owned superiority for CLC of coal. In this research, combined NiFe2O4 OC was synthesized using sol–gel combustion synthesis method, and its reaction with a typical Chinese high-sulfur coal as Liuzhi (LZ) coal was performed in a thermogravimetric analyzer (TG). And then, systematic investigation was carried out to explore the evolution of sulfur species and minerals involved in coal and their interaction with the reduced NiFe2O4 OC through different means, including fourier transform infrared (FTIR), field scanning electron microscopy/energy-dispersive X-ray spectrometry, X-ray diffraction, and thermodynamic simulation. TG–FTIR analysis of LZ reaction with NiFe2O4 indicated that two reaction stages were experienced at 350–550 and 800–900 °C, respectively, far different from LZ pyrolysis, and SO2 occurred mainly related to oxidization of H2S with NiFe2O4 over 550 °C. Meanwhile, lattice oxygen transfer rates of NiFe2O4 involved at the two reaction stages were higher than that of directly mixed NiO with Fe2O3 OC and thus more beneficial for LZ coal conversion. Both experimental means and thermodynamic simulation of the solid-reduced residues of NiFe2O4 with LZ coal indicated that the main-reduced counterparts of NiFe2O4 were Ni and Fe3O4. In addition, though good regeneration of the reduced NiFe2O4 was reached, the side products Ni3S2 and Ni2SiO4 should be noted as well for its detrimental effect on the reactivity of NiFe2O4 OC.

Investigation of perovskite supported composite oxides for chemical looping conversion of syngas

In typical chemical looping processes, a transition metal oxide based oxygen carrier is used to indirectly convert carbonaceous fuels into concentrated CO2 and carbon free products through cyclic redox reactions. Among the various oxygen carrier candidates, iron oxide represents a promising option due to its abundance, low cost, and unique thermodynamic properties. A key challenge for ferrite based oxygen carriers resides in their low redox activity. In the current study, composite iron oxides with three types of mixed ionic–electronic conductive (MIEC) supports, i.e. lanthanum strontium ferrite (Sr-substituted lanthanum ferrite or LSF), barium cerium ferrite (Ce-substituted barium ferrite, BCF) and calcium titanate ferrite (Fe-substituted calcium titanate, CTF), are synthesized using solid state reaction (SSR) and sol–gel methods. Among the three MIEC materials, CTF support is found to possess superior structural stability. MIEC supported oxygen carriers are found to be significantly more active than a reference, yttrium-stabilized zirconia (YSZ) supported oxygen carrier. Higher support conductivity and smaller iron oxide precursor sizes generally lead to enhanced oxygen carrier activity. In contrast, surface area of the oxygen carrier is weakly correlated with its redox activity. CTF, although less conductive compared to BCF and LSF, is stable and sufficiently effective in shuttling active O2− and electrons for syngas oxidation and iron oxide regeneration. Therefore, CTF supported ferrites can potentially be a cost-effective oxygen carrier candidate for chemical looping processes. Further improvements in redox activity of the oxygen carriers can be achieved through iron oxide particle size reduction and support conductivity enhancement.

CaMnO3-δ Made from Low Cost Material Examined as Oxygen Carrier in Chemical-looping Combustion

Carbon Capture and Storage is a promising method to limit the increasing amount of greenhouse gases in the atmosphere. In this method high purity carbon dioxide is captured at large emission sources, e. g. fossil fuelled power plants. The carbon dioxide can then be transported to a long term storage site, rather than being emitted to the atmosphere. Among the different alternatives for obtaining high purity carbon dioxide during combustion of fossil fuels, Chemical-looping Combustion (CLC) is one of the most promising. Here, the oxygen needed to oxidize a fuel is provided by a solid oxygen carrier. The oxygen carrier is subsequently circulated to another reactor where it is reoxidized with air. By separating these two operations mixing of the combustion products and the nitrogen in the air is avoided. An energy demanding gas separation is thus not necessary.The most crucial part of Chemical-looping Combustion is the solid oxygen carrier. The oxygen carrier should have high reactivity with fuel and oxygen, sufficient oxygen carrying capacity and preferably also low cost. Furthermore it is important that it is able to withstand the tough conditions it is exposed to in a hot fluidizing environment, both with respect to physical attrition and chemical degradation. The most commonly suggested setup of Chemical- looping Combustion is a dual fluidized bed system where gas velocities and mechanical abrasion can be high. When the technology was first demonstrated, nickel oxide based oxygen carriers were typically used. But as nickel is quite costly as well as potentially harmful, alternatives have been sought after.In 2009 Leion et al. [1] investigated an oxygen carrier based on calcium manganite of perovskite structure CaMnO3-δ for chemical looping combustion. The results were very promising and similar materials have since then been successfully tested in pilot rigs up to 120 kWth, including extended operation in continuously operating 10 kWth reactor with very positive results, see Källén et al. [2]. A key feature of these materials is that they are able to release gas phase oxygen at relevant conditions, so called Chemical-looping with Oxygen Uncoupling, see Rydén et al. [3]. Having gas phase oxygen available for fuel oxidation makes gas-solid mixing less critical and thus makes it easier to reach complete fuel conversion.2Most studies in which CaMnO3-δ based oxygen carriers have been examined have been using particles manufactured from high quality chemicals. While that is reasonable in the early stages of development, cheaper raw materials would be favourable for industrial applications. Promising oxygen carriers based on manganese ores have been manufactured and characterized by Fossdal et al. [4] and Mohammad Pour et al. [5].This study aims to further examine CaMnO3-δ based oxygen carriers made from low cost, commercial raw materials available in large quantities such as manganese ore. The materials are examined during continuous Chemical- looping Combustion and Oxygen Uncoupling in an experimental reactor with the nominal fuel power 300 Wth. The reactor has previously been used in numerous studies which make comparisons with materials made from high purity chemicals straightforward. During operation several gas concentrations as well as temperatures and pressure drops are measured which allows monitoring of the chemical reactions and fluidization behaviour in the reactor.Fines (particles <45μm) are collected from exiting gas streams which gives an indication of the degree of attrition of the particles. Attrition was also studied in separate jet cup attrition test.The study show that it is possible to manufacture CaMnO3-δ based oxygen carrier with appropriate properties for continuous operation from low-cost materials. The ability to release gas phase oxygen to an inert atmosphere and high conversion of natural gas is demonstrated. The results indicate that this approach should be feasible also for large-scale applications.

Syngas chemical looping process: Dynamic modeling of a moving‐bed reducer

The syngas chemical looping process coproduces hydrogen and electricity with iron oxide based oxygen carriers in a circulating moving bed system. In this article, a one‐dimensional (1‐D) dynamic model is developed to simulate the countercurrent gas–solid reactive flow in the moving‐bed reducer. This model is validated by TGA and bench‐scale experiments. Both the steady state and dynamic composition profiles are obtained to help understand the reaction and reactor behaviors. Numerical simulation on the effects of reactor length is conducted to optimize the moving‐bed reducer design. It is also found that minor variations in the feed rate ratio near a critical point that is represented by the reaction equilibrium could yield a significant difference in the time required for the reactions to reach a steady‐state operation. Such a difference has an important practical implication in that the moving‐bed reducer should be designed and operated to circumvent the critical point. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3432–3443, 2013

Coal-Direct Chemical Looping Gasification for Hydrogen Production: Reactor Modeling and Process Simulation

A novel process scheme for hydrogen production from coal with in situ CO2 capture, known as the coal-direct chemical looping (CDCL) gasification process, is discussed in this article. The CDCL process utilizes an iron oxide based oxygen carrier as a chemical looping medium to indirectly gasify coal into separate streams of H2 and CO2. ASPEN Plus reactor simulation models based on both thermodynamic equilibrium limitations and kinetic limitations are developed to analyze individual CDCL reactors. Process simulations are subsequently performed to estimate the performance of the CDCL process under various mass and energy management schemes. Reactor modeling results indicate that a moving bed reducer can effectively convert coal while reducing the oxygen carrier. The reduced oxygen carrier can in turn be oxidized by steam to produce hydrogen in a moving bed oxidizer. The fates of pollutants as well as the effects of various process operating parameters such as carbon and iron oxide conversions are also evalua...

200-MW chemical looping combustion based thermal power plant for clean power generation

SUMMARY The present study demonstrates a possible configuration of a 200 MW chemical looping combustion (CLC) system with methane (CH4) as fuel. Iron oxide-based oxygen carriers were used because of its non-toxic nature, low-cost, and wide availability. We analyzed the effects of different variables on the design of the system. For the air reactor (oxidizer), bed mass is independent, and for the fuel reactor (reducer), it decreases with increase in the conversion difference between the air and fuel reactors. On the other hand, the pressure drop in the air reactor is unchanged, whereas for the fuel reactor, it decreases with the same increase of conversion difference between air and fuel reactors. Also, entrained solid mass flow rate from the air to fuel reactor shows a decreasing trend. Bed mass, bed height, pressure drop, and residence time of the bed materials decrease with increase in the conversion rates in the air and fuel reactors. Residence time of bed material in the air and fuel reactor reduces with increase in the temperature of the air reactor. Copyright © 2011 John Wiley & Sons, Ltd.

Characterization and kinetics of reduction of CaSO 4 with carbon monoxide for chemical-looping combustion

Chemical-looping combustion (CLC) of fuels via the cyclic reduction and oxidation of an oxygen carrier is a novel process for CO 2 capture. CaSO 4 has emerged as an alternative material with much lower cost and higher oxygen storage capacity compared to metal oxide based oxygen carrier. In principle, CaSO 4 is reduced by CO and H 2 (coal gasification products) generating CaS, CO 2 and H 2O, and then the solid product CaS is regenerated back to CaSO 4 in air. Research on the reactions of CaSO 4 and CaS is not only important for understanding the reaction mechanism and parameters for the new CLC technology but also of high interest in understanding the sulfur chemistry in fluidized bed combustion and gasification. This paper focuses on the reduction reaction of CaSO 4 with CO to CaS and CO 2 (CaSO 4 + 4CO → CaS + 4CO 2) by thermodynamics, characterization and kinetics analysis. Phase diagram of CaSO 4–CaO–CaS indicates the operation regime of reduction–oxidation cycle by delicate control of temperature and partial pressure of reaction gases. The kinetics of the reduction reaction of a low cost natural anhydrite as oxygen carrier was investigated in an isothermal differential bed reactor where a thin layer of CaSO 4 particles were exposed to a plug flow of CO balanced by N 2. Prior to the kinetics modeling, extensive physical and chemical characterization analyses, such as X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDX), and N 2 adsorption–desorption were carried out to understand the reaction mechanism. External mass transfer and heat effects were minimized and the operation regime for intrinsic kinetics was determined. The experimental data was described with a gas–solid shrinking unreacted core model (SCM) with both chemical reaction control and product layer diffusion resistance considered.

Syngas chemical looping gasification process: Bench‐scale studies and reactor simulations

AbstractThe syngas chemical looping process co‐produces hydrogen and electricity from syngas through the cyclic reduction and regeneration of an iron oxide based oxygen carrier. In this article, the reducer, which reduces the oxygen carrier with syngas, is investigated through thermodynamic analysis, experiments, and ASPEN Plus® simulation. The thermodynamic analysis indicates that the countercurrent moving‐bed reducer offers better gas and solids conversions when compared to the fluidized‐bed reducer. The reducer is continuously operated for 15 h in a bench scale moving‐bed reactor. A syngas conversion in excess of 99.5% and an oxygen carrier conversion of nearly 50% are obtained. An ASPEN Plus® model is developed which simulates the reducer performance. The results of simulation are consistent with those obtained from both the thermodynamic analysis and experiments. Both the experiments and simulation indicate that the proposed SCL reducer concept is feasible. © 2009 American Institute of Chemical Engineers AIChE J, 2010