Rapid and stable calcium-looping solar thermochemical energy storage via co-doping binary sulfate and Al–Mn–Fe oxides

Solar thermochemical energy storage based on calcium looping(CaL)process is a promising technology for next-generation concentrated solar power(CSP)systems.However,conventional calcium carbonate(CaCO_(3))pellets suffer from slow reaction kinetics,poor stability,and low solar absorptance.Here,we successfully realized high power density and highly stable solar thermochemical energy storage/release by synergistically accelerating energy storage/release via binary sulfate and promoting cycle stability,mechanical strength,and solar absorptance via Al–Mn–Fe oxides.The energy storage density of proposed CaCO_(3)pellets is still as high as 1455 kJ kg^(-1)with only a slight decay rate of 4.91%over 100 cycles,which is higher than that of state-of-the-art pellets in the literature,in stark contrast to 69.9%of pure CaCO_(3)pellets over 35 cycles.Compared with pure CaCO_(3),the energy storage power density or decomposition rate is improved by 120%due to lower activation energy and promotion of Ca^(2+)diffusion by binary sulfate.The energy release or carbonation rate rises by 10%because of high O^(2-)transport ability of molten binary sulfate.Benefiting from fast energy storage/release rate and high solar absorptance,thermochemical energy storage efficiency is enhanced by more than 50%under direct solar irradiation.This work paves the way for application of direct solar thermochemical energy storage techniques via achieving fast energy storage/release rate,high energy density,good cyclic stability,and high solar absorptance simultaneously.

Chemical looping reforming of the micromolecular component from biomass pyrolysis via Fe_(2)O_(3)@SBA-16

To solve the problems of low gasification efficiency and high tar content caused by solid–solid contact between biomass and oxygen carrier in traditional biomass chemical looping gasification process.The decoupling strategy was adopted to decouple the biomass gasification process,and the composite oxygen carrier was prepared by embedding Fe_(2)O_(3) in molecular sieve SBA-16 for the chemical looping reforming process of pyrolysis micromolecular model compound methane,which was expected to realize the directional reforming of pyrolysis volatiles to prepare hydrogen-rich syngas.Thermodynamic analysis of the reaction system was carried out based on the Gibbs free energy minimization method,and the reforming performance was evaluated by a fixed bed reactor,and the kinetic parameters were solved based on the gas–solid reaction model.Thermodynamic analysis verified the feasibility of the reaction and provided theoretical guidance for experimental design.The experimental results showed that the reaction performance of Fe_(2)O_(3)@SBA-16 was compared with that of pure Fe_(2)O_(3) and Fe_(2)O_(3)@SBA-15,and the syngas yield was increased by 55.3%and 20.7%respectively,and it had good cycle stability.Kinetic analysis showed that the kinetic model changed from three-dimensional diffusion to first-order reaction with the increase of temperature.The activation energy was 192.79 kJ/mol by fitting.This paper provides basic data for the directional preparation of hydrogen-rich syngas from biomass and the design of oxygen carriers for pyrolysis of all-component chemical looping reforming.

Optimizing the sulfur-resistance and activity of perovskite oxygen carrier for chemical looping dry reforming of methane

Perovskite oxides has been attracted much attention as high-performance oxygen carriers for chemical looping reforming of methane,but they are easily inactivated by the presence of trace H_(2)S.Here,we propose to modulate both the activity and resistance to sulfur poisoning by dual substitution of Mo and Ni ions with the Fe-sites of LaFeO_(3)perovskite.It is found that partial substitution of Ni for Fe substantially improves the activity of LaFeO_(3)perovskite,while Ni particles prefer to grow and react with H_(2)S during the long-term successive redox process,resulting in the deactivation of oxygen carriers.With the presence of Mo in LaNi_(0.05)Fe_(0.95)O_(3−σ)perovskite,H_(2)S preferentially reacts with Mo to generate MoS_(2),and then the CO_(2)oxidation can regenerate Mo via removing sulfur.In addition,Mo can inhibit the accumulation and growth of Ni,which helps to improve the redox stability of oxygen carriers.The LaNi_(0.05)Mo_(0.07)Fe_(0.88)O_(3−σ)oxygen carrier exhibits stable and excellent performance,with the CH_(4)conversion higher than 90%during the 50 redox cycles in the presence of 50 ppm H_(2)S at 800℃.This work highlights a synergistic effect in the perovskite oxides induced by dual substitution of different cations for the development of high-performance oxygen carriers with excellent sulfur tolerance.

CO_(2)capture costs of chemical looping combustion of biomass:A comparison of natural and synthetic oxygen carrier

Chemical looping combustion has the potential to be an efficient and low-cost technology capable of contributing to the reduction of the atmospheric concentration of CO_(2) in order to reach the 1.5/2°C goal and mitigate climate change.In this process,a metal oxide is used as oxygen carrier in a dual fluidized bed to generate clean CO_(2) via combustion of biomass.Most commonly,natural ores or synthetic materials are used as oxygen carrier whereas both must meet special requirements for the conversion of solid fuels.Synthetic oxygen carriers are characterized by higher reactivity at the expense of higher costs versus the lower-cost natural ores.To determine the viability of both possibilities,a techno-economic comparison of a synthetic material based on manganese,iron,and copper to the natural ore ilmenite was conducted.The synthetic oxygen carrier was characterized and tested in a pilot plant,where high combustion efficiencies up to 98.4%and carbon capture rates up to 98.5%were reached.The techno-economic assessment resulted in CO_(2) capture costs of 75 and 40€/tCO_(2) for the synthetic and natural ore route respectively,whereas a sensitivity analysis showed the high impact of production costs and attrition rates of the synthetic material.The synthetic oxygen carrier could break even with the natural ore in case of lower production costs and attrition rates,which could be reached by adapting the production process and recycling material.By comparison to state-of-the-art technologies,it is demonstrated that both routes are viable and the capture cost of CO_(2) could be reduced by implementing the chemical looping combustion technology.

Unraveling the atomic interdiffusion mechanism of NiFe_(2_)O_(4) oxygen carriers during chemical looping CO_(2) conversion

By employing metal oxides as oxygen carriers,chemical looping demonstrates its effectiveness in transferring oxygen between reduction and oxidation environments to partially oxidize fuels into syngas and convert CO_(2) into CO.Generally,NiFe_(2_)O_(4) oxygen carriers have demonstrated remarkable efficiency in chemical looping CO_(2) conversion.Nevertheless,the intricate process of atomic migration and evolution within the internal structure of bimetallic oxygen carriers during continuous high‐temperature redox cycling remains unclear.Consequently,the lack of a fundamental understanding of the complex ionic migration and oxygen transfer associated with energy conversion processes hampers the design of high‐performance oxygen carriers.Thus,in this study,we employed in situ characterization techniques and theoretical calculations to investigate the ion migration behavior and structural evolution in the bulk of NiFe_(2_)O_(4) oxygen carriers during H_(2) reduction and CO_(2)/lab air oxidation cycles.We discovered that during the H_(2) reduction step,lattice oxygen rapidly migrates to vacancy layers to replenish consumed active oxygen species,while Ni leaches from the material and migrates to the surface.During the CO_(2) splitting step,Ni migrates toward the core of the bimetallic oxygen carrier,forming Fe–Ni alloys.During the air oxidation step,Fe–Ni migrates outward,creating a hollow structure owing to the Kirkendall effect triggered by the swift transfer of lattice oxygen.The metal atom migration paths depend on the oxygen transfer rates.These discoveries highlight the significance of regulating the release–recovery rate of lattice oxygen to uphold the structures and reactivity of oxygen carriers.This work offers a comprehensive understanding of the oxidation/reduction‐driven atomic interdiffusion behavior of bimetallic oxygen carriers.

Mn-doped SrCoO_(3-δ) Perovskite Oxides for Ethylene Production via Chemical Looping Oxidative Dehydrogenation of Ethane

Chemical looping oxidative dehydrogenation (CL-ODH) is an economically promising method for convertingethane into higher value-added ethylene utilizing lattice oxygen in redox catalysts, also known as oxygen carriers. Inthis study, perovskite-type oxide SrCoO_(3-δ) and B-site Mn ion-doped oxygen carriers (SrCo_(1-x)MnxO_(3-δ), x=0.1, 0.2, 0.3)were prepared and tested for the CL-ODH of ethane. The oxygen-deficient perovskite SrCoO_(3-δ) exhibited high ethyleneselectivity of up to 96.7% due to its unique oxygen vacancies and lattice oxygen migration rates. However, its low ethyleneyield limits its application in the CL-ODH of ethane. Mn doping promoted the reducibility of SrCoO_(3-δ) oxygen carriers,thereby improving ethane conversion and ethylene yield, as demonstrated by characterization and evaluation experiments.X-ray diffraction results confirmed the doping of Mn into the lattice of SrCoO_(3-δ), while X-ray photoelectron spectroscopy(XPS) indicated an increase in lattice oxygen ratio upon incorporation of Mn into the SrCoO_(3-δ) lattice. Additionally, H2temperature-programmed reduction (H2-TPR) tests revealed more peaks at lower temperature reduction zones and a declinein peak positions at higher temperatures. Among the four tested oxygen carriers, SrCo0.8Mn0.2O_(3-δ) exhibited satisfactoryperformance with an ethylene yield of 50% at 710 °C and good stability over 20 redox cycles. The synergistic effect of Mnplays a key role in increasing ethylene yields of SrCoO_(3-δ) oxygen carriers. Accordingly, SrCo0.8Mn0.2O_(3-δ) shows promisingpotential for the efficient production of ethylene from ethane via CL-ODH.

Ethane Chemical Looping Oxidative Dehydrogenation to Ethylene over Co_(2)O_(3)(Fe_(2)O_(3),NiO)/LaCoO_(3) Oxygen Carriers

Ethane chemical looping oxidative dehydrogenation(CL-ODH)to ethylene is a new technology for converting ethane to ethylene.In the current study MeO/LaCoO_(3)(MeO=Fe_(2)O_(3),NiO or Co_(2)O_(3))composite metal oxides were prepared via citrate gel and impregnation methods,and used as oxygen carriers for CL-ODH.X-ray diffraction results indicated that all oxygen carriers had a perovskite structure even after eight redox cycles.Under a reaction temperature of 650°C,a reaction pressure of 0.1 MPa,and a weight hourly space velocity(WHSV)of 7500 mL/(g·h),ethane conversion over Co_(2)O_(3)/LaCoO_(3) reached 100%and ethylene selectivity reached 60%,both of which were better than corresponding values attained over Fe_(2)O_(3)/LaCoO_(3) and NiO/LaCoO_(3).Ethylene selectivity remained stable for 80 cycles over Co_(2)O_(3)/LaCoO_(3),then decreased gradually after 80 cycles.X-ray photoelectron spectroscopy results and evaluation results indicated that lattice oxygen and O_(2)2-had a direct relationship with ethane conversion and ethylene selectivity.Co_(2)O_(3)/LaCoO_(3) exhibited a strong capacity to release and absorb oxygen,mainly due to interaction between Co_(2)O_(3) and LaCoO_(3).

NiO-Doped Fe_(2)O_(3)/MgO Properties for the Chemical Looping Oxidative Dehydrogenation of Ethane

Ethane chemical looping oxidative dehydrogenation(CL-ODH)to ethylene is a new technology for ethylene preparation.Fe_(2)O_(3)/MgO oxygen carrier was prepared using the co-precipitation method.The influence of added NiO and its different loadings on Fe_(2)O_(3)/MgO were investigated.Then,a series of oxygen carriers were applied in the CL-ODH of the ethane cycle system.Brunauer-Emmett-Teller(BET),X-ray diffractometry(XRD),X-ray photoelection spectroscopy(XPS),and H2-temperature programmed reduction(TPR)were used to characterize the physicochemical properties of these oxygen carriers.It was confirmed that an interaction between NiO and Fe_(2)O_(3) occurred based on the XPS and H2-TPR results.Based on the CL-ODH activity performance tests conducted in a fixed-bed reactor,it was revealed that ethylene selectivity was significantly improved after NiO addition.Fe_(2)O_(3)-10%NiO/MgO showed the best activity performance with 93%ethane conversion and 50%ethylene selectivity at a reaction temperature of 650℃,atmospheric pressure,and space velocity of 7500 mL/(g·h).

Advancements in biomass gasification research utilizing iron-based oxygen carriers in chemical looping:A review

Biomass,recognized as renewable green coal,is pivotal for energy conservation,emission reduction,and dualcarbon objectives.Chemical looping gasification,an innovative technology,aims to enhance biomass utilization efficiency.Using metal oxides as oxygen carriers regulates the oxygen-to-fuel ratio to optimize synthesis product yields.This review examines various oxygen carriers and their roles in chemical looping biomass gasification,including natural iron ore types,industrial by-products,cerium oxide-based carriers,and core-shell structures.The catalytic,kinetic,and phase transfer properties of iron-based oxygen carriers are analyzed,and their catalytic cracking capabilities are explored.Molecular interactions are elucidated and system performance is optimized by providing insights into chemical looping reaction mechanisms and strategies to improve carrier efficiency,along with discussing advanced techniques such as density functional theory(DFT)and reactive force field(ReaxFF)molecular dynamics(MD).This paper serves as a roadmap for advancing chemical looping gasification towards sustainable energy goals.

Techno-economic assessment of a chemical looping splitting system for H2 and CO Co-generation

The natural gas(NG)reforming is currently one of the low-cost methods for hydrogen production.However,the mixture of H2 and CO_(2) in the produced gas inevitably includes CO_(2) and necessitates the costly CO_(2) separation.In this work,a novel double chemical looping involving both combustion(CLC)and sorption-enhanced reforming(SE-CLR)was proposed towards the co-production of H2 and CO(CLC-SECLRHC)in two separated streams.CLC provides reactant CO_(2) and energy to feed SECLRHC,which generates hydrogen in a higher purity,as well as the calcium cycle to generate CO in a higher purity.Techno-economic assessment of the proposed system was conducted to evaluate its efficiency and economic competitiveness.Studies revealed that the optimal molar ratios of oxygen carrier(OC)/NG and steam/NG for reforming were recommended to be 1.7 and 1.0,respectively.The heat integration within CLC and SECLRHC units can be achieved by circulating hot OCs.The desired temperatures of fuel reactor(FR)and reforming reactor(RR)should be 850
C and 600
C,respectively.The heat coupling between CLC and SECLRHC units can be realized via a jacket-type reactor,and the NG split ratio for reforming and combustion was 0.53:0.47.Under the optimal conditions,the H2 purity,the H2 yield and the CH4 conversion efficiency were 98.76%,2.31 mol mol-1 and 97.96%,respectively.The carbon and hydrogen utilization efficiency respectively were 58.60% and 72.45%in terms of the total hydrogen in both steam and NG.The exergy efficiency of the overall process reached 70.28%.In terms of the conventional plant capacity(75 × 103 t y^(-1))and current raw materials price(2500$t^(-1)),the payback period can be 6.2 years and the IRR would be 11.5,demonstrating an economically feasible and risk resistant capability.

Chemical looping oxidative propane dehydrogenation controlled by oxygen bulk diffusion over FeVO_(4)oxygen carrier pellets

The oxygen distribution and evolution within the oxygen carrier exert significant influence on chemical looping processes.This paper describes the influence of oxygen bulk diffusion within FeVO4 oxygen carrier pellets on the chemical looping oxidative propane dehydrogenation(CL-ODH).During CL-ODH,the oxygen concentration at the pellet surface initially decreased and then maintained stable before the final decrease.At the stage with the stable surface oxygen concentration,the reaction showed a stable C3H6 formation rate and high C3H6 selectivity.Therefore,based on Fick’s second law,the oxygen distribution and evolution in the oxygen carrier at this stage were further analyzed.It was found that main reactions of selective oxidation and over-oxidation were controlled by the oxygen bulk diffusion.C3H8 conversion rate kept decreasing during this stage due to the decrease of the oxygen flux caused by the decline of oxygen gradient within the oxygen carrier,while C3H6 selectivity increased due to the decrease of overoxidation.In addition,reaction rates could increase with the propane partial pressure due to the increase of the oxygen gradient within the oxygen carrier until the bulk transfer reached its limit at higher propane partial pressure.This study provides fundamental insights for the diffusion-controlled chemical looping reactions.

Microscopic mechanism study and process optimization of dimethyl carbonate production coupled biomass chemical looping gasification system

Biomass chemical looping gasification technology is one of the essential ways to utilize abundant biomass resources.At the same time,dimethyl carbonate can replace phosgene as an environmentfriendly organic material for the synthesis of polycarbonate.In this paper,a novel system coupling biomass chemical looping gasification with dimethyl carbonate synthesis with methanol as an intermediate is designed through microscopic mechanism analysis and process optimization.Firstly,reactive force field molecular dynamics simulation is performed to explore the reaction mechanism of biomass chemical looping gasification to determine the optimal gasification temperature range.Secondly,steady-state simulations of the process based on molecular dynamics simulation results are carried out to investigate the effects of temperature,steam to biomass ratio,and oxygen carrier to biomass ratio on the syngas yield and compositions.In addition,the main energy indicators of biomass chemical looping gasification process including lower heating value and cold gas efficiency are analyzed based on the above optimum parameters.Then,two synthesis stages are simulated and optimized with the following results obtained:the optimal temperature and pressure of methanol synthesis stage are 150℃ and 4 MPa;the optimal temperature and pressure of dimethyl carbonate synthesis stage are 140℃ and 0.3 MPa.Finally,the pre-separation-extraction-decantation process separates the mixture of dimethyl carbonate and methanol generated in the synthesis stage with 99.11%purity of dimethyl carbonate.Above results verify the feasibility of producing dimethyl carbonate from the perspective of multi-scale simulation and realize the multi-level utilization of biomass resources.

Chemical looping conversion of methane via Fe_(2)O_(3)-LaFeO_(3)calcined from LaFe-MOF precursor

The effective utilization of natural gas resources is a promising option for the implementation of the"dual carbon"strategy.However,the capture of carbon dioxide with relatively lower concentration after the combustion of natural gas is the crucial step.Fortunately,the lattice oxygen is used for chemical cycle conversion of methane to overcome the shortcomings mentioned above.A method was proposed to synthesize perovskite for methane cycle conversion using metal organic framework as a precursor.Morphology and pore structure of Fe_(2)O_(3)-LaFeO_(3)composite oxides were regulated by precursor synthesis conditions and calcination process.Moreover,the chemical looping conversion performance of methane was evaluated.The results showed that the pure phase precursor of La[Fe(CN)_(6)]·5H_(2)O was synthesized with the specific surface area of 23.91 m^(2)·g^(-1)under the crystallization of 10 h and the pH value of10.5.Fe_(2)O_(3)-LaFeO_(3)was obtained by controlled calcination of La[Fe(CN)_(6)]·5H_(2)O and Fe_(2)O_(3)with variable mass ratio.The selectivity of CO_(2)can reach more than 99%under the optimal parameters of methane chemical looping conversion:m(Fe_(2)O_(3)):m(LaFeO_(3))=2:1,the reaction temperature is 900℃,the lattice oxygen conversion is less than 40%.Fe_(2)O_(3)-LaFeO_(3)still has good phase and structure stability after five redox reaction and regeneration cycles.

Effect of sulfation during carbonation on CO_2 capture in calcium looping cycle

Abstract： Two Canadian limestones with different properties were tested to determine the effect of SO2 during the carbonation of sorbent on the CO2 capture performance in Ca- looping. When the reaction gas is mixed with SO2, the carbonation ratio of the sorbent is always lower than that without SO2 for each cycle under the same conditions, and the sulfation ratio increases almost linearly with the increase in the cycle times. At 650 ℃, there is little difference in the carbonation ratio of the sorbent during the first four cycles for the two carbonation time, 5 and 10 rain at 0. 18% SO2. The indirect sulfation reaction that occurs simultaneously with the carbonation of CaO is responsible for the degradation of the sorbent for CO2 capture, and the carbonation duration is not the main factor that affects the ability of the sorbent. 680℃ is the best carbonation temperature among the three tested temperatures and the highest carbonation ratio can be obtained. Also, the sulfation ratio is the highest. The probable cause is the different effects of temperature on the carbonation rate and sulfation rate. A higher SO2 concentration will decrease the carbonation ratio clearly, but the decrease in the carbonation capability of the sorbent is not proportional to the increase of the SO2 concentration in flue gases.

Detection of cyclonic eddy generated by looping tropical cyclone in the northern South China Sea: a case study

A case study on the cyclonic eddy generated by the tropical cyclone looping over the northern South China Sea (NSCS) is presented, using TOPEX/POSEIDON altimeter data and AVHRR sea surface temperature (SST) data. Three cases relating to the tropical cyclone events (Typhoon Kai-Tak in July 2000, Tropical Storm Russ in June 1994 and Tropical Storm Maria in August-September 2000) over the NSCS have been analyzed. For each looping tropical cyclone case, the cyclonic eddy with an obvious sea level depression appears in the sea area where the tropical cyclone takes a loop form, and lasts for about 2 weeks with a slight variation in location. The cold core with the SST difference greater than 2℃against its surrounding areas is also observed by the satellite-derived SST data.

Application of Fe_2O_3/Al_2O_3 Composite Particles as Oxygen Carrier of Chemical Looping Combustion

Chemical looping combustion （CLC） of carbonaceous compounds has been proposed, in the past decade, as an efficient method for CO2 capture without cost of extra energy penalties. The technique involves the use of a metal oxide as an oxygen carrier that transfers oxygen from combustion air to fuels. The combustion is carried out in a two-step process： in the fuel reactor, the fuel is oxidized by a metal oxide, and in the air reactor, the reduced metal is oxidized back to the original phase. The use of iron oxide as an oxygen carrier has been investigated in this article. Particles composed of 80 wt% Fe2O3, together with Al2O3 as binder, have been prepared by impregnation methods. X-ray diffraction （XRD） analysis reveals that Fe2O3 does not interact with the Al2O3 binder after multi-cycles. The reactivity of the oxygen carrier particles has been studied in twenty-cycle reduction-oxidation tests in a thermal gravimetrical analysis （TGA） reactor. The components in the outlet gas have been analyzed. It has been observed that about 85% of CH4 converted to CO2 and H2O during most of the reduction periods. The oxygen carrier has kept quite a high reactivity in the twenty-cycle reactions. In the first twenty reaction cycles, the reaction rates became slightly higher with the number of cyclic reactions increasing, which was confirmed by the scanning electron microscopy （SEM） test results. The SEM analysis revealed that the pore size inside the particle had been enlarged by the thermal stress during the reaction, which was favorable for diffusion of the gaseous reactants into the particles. The experimental results suggested that the Fe2O3/Al2O3 oxygen carrier was a promising candidate for a CLC system.

Simultaneous CO_(2) capture and thermochemical heat storage by modified carbide slag in coupled calcium looping and CaO/Ca(OH)2 cycles

The simultaneous CO_(2) capture and heat storage performances of the modified carbide slag with byproduct of biodiesel were investigated in the process coupled calcium looping and CaO/Ca(OH)2 thermochemical heat storage using air as the heat transfer fluid.The modified carbide slag with by-product of biodiesel exhibits superior CO_(2) capture and heat storage capacities in the coupled calcium looping and heat storage cycles.The hydration conversion and heat storage density of the modified carbide slag after 30 heat storage cycles are 0.65 mol·mol^(-1) and 1.14 GJ·t^(-1),respectively,which are 1.6 times as high as those of calcined carbide slag.The negative effect of CO_(2) in air as the heat storage fluid on the heat storage capacity of the modified carbide slag is overcome by introducing CO_(2) capture cycles.In addition,the CO_(2) capture reactivity of the modified carbide slag after the multiple calcium looping cycles is enhanced by the introduction of heat storage cycles.By introducing 10 heat storage cycles after the 10th and 15th CO_(2) capture cycles,the CO_(2) capture capacities of the modified carbide slag are subsequently improved by 32%and 43%,respectively.The porous and loose structure of modified carbide slag reduces the diffusion resistances of CO_(2) and steam in the material in the coupled process.The formed CaCO_(3)in the modified carbide slag as a result of air as the heat transfer fluid in heat storage cycles decomposes to regenerate CaO in calcium looping cycles,which improves heat storage capacity.Therefore,the modified carbide slag with by-product of biodiesel seems promising in the coupled calcium looping and CaO/Ca(OH)_(2) heat storage cycles.

Chemical looping catalytic gasification of biomass over active LaNixFe1-xO_(3)perovskites as functional oxygen carriers

Oxygen carriers(OCs)with perovskite structure are attracting increasing interests due to their redox tunability by introducing various dopants in the structure.In this study,LaNixFe1-xO3(x=0,0.1,0.3,0.5,0.7,1.0)perovskite OCs have been prepared by a citric acid–nitrate sol–gel method,characterized by means of X-ray diffraction(XRD)analysis and tested for algae chemical looping gasification in a fixed bed reactor.The effects of perovskite types,OC/biomass mass ratio(O/B),gasification temperature and water injection rate on the gasification performance were investigated.Lower Ni-doped(0≤x≤0.5)perovskites crystalized in the rhombohedra system which was isostructural with LaNiO3,while those with composition 0.5≤x≤1 crystalized in the orthorhombic system.Despite the high reactivity for LaNiO_(3),LaNi_(0.5)Fe_(0.5)O_(3)(LN5F5)was found to be more stable at a high temperature and give almost as good results as LaNiO_(3)in the formation of syngas.The relatively higher syngas yield of 0.833 m^(3)·kg^(-1) biomass was obtained under the O/B of 0.4,water injection rate of 0.3 ml·min^(-1) and gasification temperature at 850C.Continuous high yield of syngas was achieved during the first 5 redox cycles,while a slight decrease in the reactivity for LN5F5 after 5 cycles was observed due to the adhesion of small grains occurring on the surface of OCs.However,an obvious improvement in the gasification performance was attained for LN5F5 compared to raw biomass direct gasification,indicating that LN5F5 is a promising functional OC for chemical looping catalytic gasification of biomass.

Different oxidation routes for lattice oxygen recovery of double-perovskite type oxides LaSrFeCoO6 as oxygen carriers for chemical looping steam methane reforming

Double-perovskite type oxide LaSrFeCoO（LSFCO） was used as oxygen carrier for chemical looping steam methane reforming（CL-SMR） due to its unique structure and reactivity. Two different oxidation routes,steam-oxidation and steam-air-stepwise-oxidation, were applied to investigate the recovery behaviors of the lattice oxygen in the oxygen carrier. The characterizations of the oxide were determined by X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, hydrogen temperature-programmed reduction（H-TPR） and scanning electron microscopy（SEM）. The fresh sample LSFCO exhibits a monocrystalline perovskite structure with cubic symmetry and high crystallinity, except for a little impurity phase due to the antisite defect of Fe/Co disorder. The deconvolution distribution of XPS patterns indicated that Co,and Fe are predominantly in an oxidized state(Feand Fe) and(Coand Co), while O 1s exists at three species of lattice oxygen, chemisorbed oxygen and physical adsorbed oxygen. The double perovskite structure and chemical composition recover to the original state after the steam and air oxidation, while the Co ion cannot incorporate into the double perovskite structure and thus form the CoO just via individual steam oxidation. In comparison to the two different oxidation routes, the sample obtained by steam-oxidation exhibits even higher CHconversion, CO and Hselectivity and stronger hydrogen generation capacity.

Hydrogen production via chemical looping reforming of coke oven gas

Coke oven gas(COG)is one of the most important by-products in steel industry,and the conversion of COG to value-added products has attracted much attention from both economic and environmental views.In this work,we use the chemical looping reforming technology to produce pure H_(2) from COG.A series of La1-xSrxFeO_(3)(x?0,0.2,0.3,0.4,0.5,0.6)perovskite oxides were prepared as oxygen carriers for this purpose.The reduction behaviors of La1-xSrxFeO_(3) perovskite by different reducing gases(H_(2),CO,CH4 and the mixed gases)are investigated to discuss the competition effect of different components in COG for reacting with the oxygen carriers.The results show that reduction temperatures of H_(2) and CO are much lower than that of CH4,and high temperatures(>800℃)are requested for selective oxidation of methane to syngas.The co-existence of CO and H_(2) shows weak effect on the equilibrium of methane conversion at high temperatures,but the oxidation of methane to syngas can inhibit the consumption of CO and H_(2).The doping of suitable amounts of Sr in LaFeO_(3) perovskite(e.g.,La0.5Sr0.5FeO_(3))significantly promotes the activity for selective oxidation of methane to syngas and inhibits the formation of carbon deposition,obtaining both high methane conversion in the COG oxidation step and high hydrogen yield in the water splitting step.The La0.5Sr0.5FeO_(3) shows the highest methane conversion(67.82%),hydrogen yield(3.34 mmol g^(-1))and hydrogen purity(99.85%).The hydrogen yield in water splitting step is treble as high as the hydrogen consumption in reduction step.These results reveal that chemical looping reforming of COG to produce pure H_(2) is feasible,and an O_(2)-assistant chemical looping reforming process can further improves the redox stability of oxygen carrier.