This work presents a simulation study of several Ca-Cu looping variants with CO(2)capture,aiming at both parameter optimization and exergy analysis of these Ca-Cu looping systems.Three kinds of Ca-Cu looping are consi...This work presents a simulation study of several Ca-Cu looping variants with CO(2)capture,aiming at both parameter optimization and exergy analysis of these Ca-Cu looping systems.Three kinds of Ca-Cu looping are considered:(1)carbonation-calcination/reduction-oxidation;(2)carbonation-oxidation-calcination/reduction and (3)carbona tion/oxidation-calcination/reduction.A conventional Ca looping is also simulated for comparison.The influences of the calcination temperature on the mole fractions of CO(2)and CaO at the calciner outlet,the CaCO3 flow rate on the carbonator performance and the Cu/Ca ratio on the calciner performance are analyzed.The second kind of Ca-Cu looping has the highest carbonation conversion.At 1×10^5 Pa and 820℃,complete decomposition of CaCO3 can be achieved in three Ca-Cu looping systems,while the operation condition of 1×10^5 Pa,840℃is required for the conventional Ca looping system.Furthermore,the Cu/Ca molar ratio of 5.13-5.19 is required for the Ca-Cu looping.Exergy analyses show that the maximum exergy destruction occurs in the calciner for the four modes and the second Ca-Cu looping system(i.e.,carbonation-oxidation-calcination/reduction)performs the highest exergy efficiency,up to 65.04%,which is about 30%higher than that of the conventional Ca looping.展开更多
Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome t...Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome the limitations of single ironbased oxygen carriers,including poor cycling stability,low reactivity and susceptibility to sintering,this study employed a dipcoating method to modify Fe_(2)O_(3)/Al_(2)O_(3)oxygen carriers by incorporating three distinct metal additives:Cu,La and Ce.The composite oxygen carriers were systematically characterized and evaluated under redox conditions to investigate the structure-activity relationships between the physicochemical properties,reactivity,and hydrogen production performance.Results revealed that the spinel-phase CuFe_(2)O_(4)exhibited higher reactivity than the perovskite-phase LaFeO_(3)and CeO_(2),promoting the deeper reduction of Fe_(2)O_(3).Fe58Cu2Al exhibited an oxygen storage capacity as high as 6.5 mmol/g.During the CH4 reaction stage,Fe58Cu2Al achieved the highest oxygen loss of 12.1 g/100 g oxygen carrier,accompanied by a syngas yield of 5.15 mmol/g-1.33 times and 1.59 times greater than that of Fe60Al.In the hydrogen production stage,the 2%Cu-modified oxygen carrier demonstrated optimal performance,yielding 5.13 mmol/g of hydrogen,which was 1.51 times that of the pristine sample.Even after ten cycles,the H_(2)yield remained at 3.61 mmol/g,surpassing the single-cycle output of the pristine sample and the H2 purity consistently exceeded 98%.展开更多
The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping...The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping is the primary method to enhance the reaction characteristics of calcium-based materials over multiple cycles.In particular,co-doping with variable-valence metal oxides(VVMOs)can effectively increase the oxygen vacancy content in calcium-based materials,significantly improving their cyclic reaction characteristics.However,there are so numerous VVMOs co-doping schemes that the experimental screening process is complex,consuming considerable time and economic costs.Density functional theory(DFT)calculations have been widely used to reveal the impact of metal oxide doping on the cyclic reaction characteristics of calcium-based materials,with calculation results showing good agreement with experimental conclusions.Nevertheless,there is still a lack of research on utilizing DFT to screen calcium-based materials,and a systematic research methodology has not yet been established.In this study,a systematic DFT-based screening methodology for calcium-based materials was proposed.A series of key parameters for DFT calculations including CO_(2)adsorption energy,oxygen vacancy formation energy,and sintering resistance were proposed.Furthermore,a preliminary mathematical model to predict the CaL TCES and CO_(2)capture performance of calcium-based materials was introduced.The aforementioned DFT method was employed to screen for VVMOs co-doped calcium-based materials.The results revealed that Mn and Ce co-doped calcium-based materials exhibited superior DFT-predicted reaction characteristics.These DFT predictions were validated through experimental assessments of cyclic thermochemical energy storage,CO_(2)capture,and relevant characterization.The outcomes demonstrate a high degree of consistency among DFT-based predictions,experimental results,and characterization.Hence,the DFT-based screening methodology for calcium-based materials proposed herein is a viable solution,poised to offer theoretical insights for the efficient design of calcium-based materials.展开更多
Advanced oxygen carrier plays a pivotal role in various chemical looping processes,such as CO_(2)splitting.However,oxygen carriers have been restricted by deactivation and inferior oxygen transferability at low temper...Advanced oxygen carrier plays a pivotal role in various chemical looping processes,such as CO_(2)splitting.However,oxygen carriers have been restricted by deactivation and inferior oxygen transferability at low temperatures.Herein,we design an Fe-Ov-Ce-triggered phase-reversible CeO_(2)−x·Fe·CaO↔CeO_(2)·Ca_(2)Fe_(2)O_(5)oxygen carrier with strong electron-donating ability,which activates CO_(2)at low temperatures and promotes oxygen transformation.Results reveal that the maximum CO_(2)conversion and CO yield obtained with 50 mol%CeO_(2)−x·Fe·CaO are,respectively,426%and 53.6 times higher than those of Fe·CaO at 700℃.This unique multiphase material also retains exceptional redox durability,with no obvious deactivation after 100 splitting cycles.The addition of Ce promotes the formation of the Fe-Ov-Ce structure,which acts as an activator,triggers CO_(2)splitting,and lowers the energy barrier of C═O dissociation.The metallic Fe plays a role in consuming O_(2)−lattice transformed from Fe-Ov-Ce,whereas CaO acts as a structure promoter that enables phase-reversible Fe0↔Fe3+looping.展开更多
Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention...Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention.CLHP demands redox catalysts with high oxygen capacity,regulatable reactivity,and structural integrity even under harsh operational conditions.Currently,sintering,agglomeration,and inactivation of redox catalysts during cyclic lattice oxygen release and restoration are challenging,hindering the wide industrialization of the chemical looping(CL)process.Moreover,the precise control of activity and reaction rate of the redox catalysts to flexibly accommodate the demands of various reaction substrates remains unclear.This paper introduces the design of a nano-scaled redox catalyst featuring a unique core-shell structure.By precisely controlling the shell thickness,a series of hierarchical Fe_(2)O_(3)@SiO_(2)redox catalysts were successfully synthesized.Building on this achievement,an in-depth investigation was conducted into the impact of the thickness and spatial structure of the inert support on the stability and mass transfer rate of the redox catalyst,aiming to achieve a perfect balance between these two factors during the CLHP process.A thin shell(70 nm)exhibits excellent cyclic stability,maintaining consistent performance in 30 consecutive redox cycles,while a thicker shell(200 nm)undergoes rapid deactivation due to the formation of a substantial amount of iron silicate.In-situ transmission electron microscopy(TEM)reveals that the SiO_(2)shell effectively restricts the agglomeration of Fe_(2)O_(3).The unique core-shell structure and controllable shell thickness offer novel insights into the flexible design of efficient and durable hierarchical redox catalysts with spatial structure.展开更多
Repurposing of carbon dioxide to valuable chemicals and fuels with the assistance of renewable energy is essential for balanced carbon cycle.Here,a new CO_(2)conversion strategy was demonstrated that utilized concentr...Repurposing of carbon dioxide to valuable chemicals and fuels with the assistance of renewable energy is essential for balanced carbon cycle.Here,a new CO_(2)conversion strategy was demonstrated that utilized concentrated solar energy to directly drive chemical looping reverse water gas shift process,which simultaneously coupled the photothermal and photochemical effects to achieve enhanced CO_(2)reduction reactivity and 100%CO selectivity.The solar-driven chemical looping CO_(2)reduction on Ni-Fe_(2)O_(3/)La_(0.8)Sr_(0.2)FeO_(3)exhibited great activity,with an average CO production rate of up to 0.28 mmol/g_(oc)/min at 283℃The product yield of the solar-driven reaction was almost 600%higher than that of the thermal reaction at the same temperature.The CO production overcame the thermodynamic equilibrium limitation under the combined impact of thermal and non-thermal effects of direct-light illumination.Light irradiation reinforced reactive gas adsorption and dissociation of carbonate intermediates,and stimulated oxygen ion migration and lattice oxygen transformation,thus promoting the reactivity.The concept of concentrated solar energy to drive chemical looping reverse water gas shift opens a new avenue for effective CO_(2)resource utilization and solar fuel production.展开更多
Coal-direct chemical looping(CDCL) is a promising CO_(2) capture technology with low costs.Potassium modification can significantly enhance the reactivity of iron-based oxygen carriers and coal.However,potassium loss ...Coal-direct chemical looping(CDCL) is a promising CO_(2) capture technology with low costs.Potassium modification can significantly enhance the reactivity of iron-based oxygen carriers and coal.However,potassium loss causes a decline in cyclic stability.To address this,we prepared a potassium hexatitanate-modified iron-based OC and conducted CDCL experiments in a fixed-bed reactor using Zhundong coal coke as fuel.The study examined the impact of potassium hexatitanate on carbon conversion,OC activity stability,and potassium maintenance.Additionally,Fact Sage was used to calculate potassium fugacity patterns at different temperatures,Fe_(2)O_(3)/C molar ratios,and OC reduction degrees.Results showed that potassium hexatitanate increased carbon conversion,achieving 50%conversion at 40% potassium addition.In multi-cycle tests,carbon conversion rose with increased cycle times,reaching 84%.This improvement is attributed to ion exchange between Fe^(3+) and Ti^(4+),which induces lattice distortion and creates oxygen vacancies,enhancing OC reactivity.Potassium content remained stable during multi-cycle tests,indicating the effective potassium retention capacity of potassium hexatitanate.展开更多
For loops with UV divergences,assuming that the physical contributions of loops from UV regions are insignificant,a UV-free scheme method described by an equation is introduced to derive loop results without UV diverg...For loops with UV divergences,assuming that the physical contributions of loops from UV regions are insignificant,a UV-free scheme method described by an equation is introduced to derive loop results without UV divergences in the calculations,i.e.,a route of the analytic continuation T_(F)→T_(P)besides the traditional route∞-∞in the mathematical structure.This scheme provides a new perspective to an open question of the hierarchy problem of Higgs mass,i.e.,an alternative interpretation without fine-tuning within the standard model.展开更多
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 w...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.展开更多
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 m...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.展开更多
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. Thre...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.展开更多
Chemical looping combustion （CLC） of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operatio...Chemical looping combustion （CLC） of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier （OC） was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi （LZ） bituminous coal, was performed in a thermogravimetric analyzer （TGA）-Fourier transform infrared （FT-IR） spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFeaO40C was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn304 or Fe203, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe304 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4.展开更多
The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with Ca SO4 as ox...The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with Ca SO4 as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO2 into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value.Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseous media. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium(steam or CO2) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, the mechanism using steam as the gasifying medium differs from that using CO2. With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO2 as the gasifying medium.展开更多
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-oxidat...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.展开更多
This study evaluated the release characteristics of mercury from bituminous coal in chemical looping combustion(CLC)using Australian iron ore as the oxygen carrier in a fixed bed reactor.The effects of several paramet...This study evaluated the release characteristics of mercury from bituminous coal in chemical looping combustion(CLC)using Australian iron ore as the oxygen carrier in a fixed bed reactor.The effects of several parameters,such as temperature in the fuel reactor(FR)and air reactor(AR),gasification medium in the FR,and reaction atmosphere in the AR,on mercury release characteristics,were investigated.The mercury speciation and release amount in the FR and AR under different conditions were further explored.The results indicate that most of the mercury in coal was released in the FR,while the rest of it was released in the AR.Hg0 was found to be the major species in the released mercury.The results also indicate that a higher temperature in the FR led to an increase in the total mercury release amount and a decrease in Hg0 proportion.However,a higher temperature in the AR resulted in a decrease in the total mercury release amount and Hg 0 proportion.The increase in the H2O/CO2 ratio of gasification mediums in the FR was beneficial for the increase in the total mercury release amount and Hg 0 proportion.A higher O2 concentration in reaction atmosphere in AR had a negligible effect on the total mercury release amount,but a positive effect on Hg0 oxidization.展开更多
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)perovs...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.展开更多
基金financially supported by National Key R&D Program of China(2019YFE0100100)。
文摘This work presents a simulation study of several Ca-Cu looping variants with CO(2)capture,aiming at both parameter optimization and exergy analysis of these Ca-Cu looping systems.Three kinds of Ca-Cu looping are considered:(1)carbonation-calcination/reduction-oxidation;(2)carbonation-oxidation-calcination/reduction and (3)carbona tion/oxidation-calcination/reduction.A conventional Ca looping is also simulated for comparison.The influences of the calcination temperature on the mole fractions of CO(2)and CaO at the calciner outlet,the CaCO3 flow rate on the carbonator performance and the Cu/Ca ratio on the calciner performance are analyzed.The second kind of Ca-Cu looping has the highest carbonation conversion.At 1×10^5 Pa and 820℃,complete decomposition of CaCO3 can be achieved in three Ca-Cu looping systems,while the operation condition of 1×10^5 Pa,840℃is required for the conventional Ca looping system.Furthermore,the Cu/Ca molar ratio of 5.13-5.19 is required for the Ca-Cu looping.Exergy analyses show that the maximum exergy destruction occurs in the calciner for the four modes and the second Ca-Cu looping system(i.e.,carbonation-oxidation-calcination/reduction)performs the highest exergy efficiency,up to 65.04%,which is about 30%higher than that of the conventional Ca looping.
基金Supported by the National Natural Science Foundation of China(52266008,52464057)Applied Basic Research Program of Yunnan Province(202301AT070067)the Yunnan Revitalization Talent Support Program Young Talent Project(XDYC-QNRC-2022-0060)。
文摘Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome the limitations of single ironbased oxygen carriers,including poor cycling stability,low reactivity and susceptibility to sintering,this study employed a dipcoating method to modify Fe_(2)O_(3)/Al_(2)O_(3)oxygen carriers by incorporating three distinct metal additives:Cu,La and Ce.The composite oxygen carriers were systematically characterized and evaluated under redox conditions to investigate the structure-activity relationships between the physicochemical properties,reactivity,and hydrogen production performance.Results revealed that the spinel-phase CuFe_(2)O_(4)exhibited higher reactivity than the perovskite-phase LaFeO_(3)and CeO_(2),promoting the deeper reduction of Fe_(2)O_(3).Fe58Cu2Al exhibited an oxygen storage capacity as high as 6.5 mmol/g.During the CH4 reaction stage,Fe58Cu2Al achieved the highest oxygen loss of 12.1 g/100 g oxygen carrier,accompanied by a syngas yield of 5.15 mmol/g-1.33 times and 1.59 times greater than that of Fe60Al.In the hydrogen production stage,the 2%Cu-modified oxygen carrier demonstrated optimal performance,yielding 5.13 mmol/g of hydrogen,which was 1.51 times that of the pristine sample.Even after ten cycles,the H_(2)yield remained at 3.61 mmol/g,surpassing the single-cycle output of the pristine sample and the H2 purity consistently exceeded 98%.
基金supported by the National Natural Science Foundation of China(52276204 and U22A20435)。
文摘The reaction characteristics of calcium-based materials during calcium looping(CaL)process are pivotal in the efficiency of CaL thermochemical energy storage(TCES)and CO_(2)capture systems.Currently,metal oxide doping is the primary method to enhance the reaction characteristics of calcium-based materials over multiple cycles.In particular,co-doping with variable-valence metal oxides(VVMOs)can effectively increase the oxygen vacancy content in calcium-based materials,significantly improving their cyclic reaction characteristics.However,there are so numerous VVMOs co-doping schemes that the experimental screening process is complex,consuming considerable time and economic costs.Density functional theory(DFT)calculations have been widely used to reveal the impact of metal oxide doping on the cyclic reaction characteristics of calcium-based materials,with calculation results showing good agreement with experimental conclusions.Nevertheless,there is still a lack of research on utilizing DFT to screen calcium-based materials,and a systematic research methodology has not yet been established.In this study,a systematic DFT-based screening methodology for calcium-based materials was proposed.A series of key parameters for DFT calculations including CO_(2)adsorption energy,oxygen vacancy formation energy,and sintering resistance were proposed.Furthermore,a preliminary mathematical model to predict the CaL TCES and CO_(2)capture performance of calcium-based materials was introduced.The aforementioned DFT method was employed to screen for VVMOs co-doped calcium-based materials.The results revealed that Mn and Ce co-doped calcium-based materials exhibited superior DFT-predicted reaction characteristics.These DFT predictions were validated through experimental assessments of cyclic thermochemical energy storage,CO_(2)capture,and relevant characterization.The outcomes demonstrate a high degree of consistency among DFT-based predictions,experimental results,and characterization.Hence,the DFT-based screening methodology for calcium-based materials proposed herein is a viable solution,poised to offer theoretical insights for the efficient design of calcium-based materials.
基金supported by the National Key R&D Program of China(2022YFE0105900)the National Natural Science Foundation of China(52436006,52476144,52311530339,42441835)the Innovation-Driven Project of Central South University(2023ZZTS0721).
文摘Advanced oxygen carrier plays a pivotal role in various chemical looping processes,such as CO_(2)splitting.However,oxygen carriers have been restricted by deactivation and inferior oxygen transferability at low temperatures.Herein,we design an Fe-Ov-Ce-triggered phase-reversible CeO_(2)−x·Fe·CaO↔CeO_(2)·Ca_(2)Fe_(2)O_(5)oxygen carrier with strong electron-donating ability,which activates CO_(2)at low temperatures and promotes oxygen transformation.Results reveal that the maximum CO_(2)conversion and CO yield obtained with 50 mol%CeO_(2)−x·Fe·CaO are,respectively,426%and 53.6 times higher than those of Fe·CaO at 700℃.This unique multiphase material also retains exceptional redox durability,with no obvious deactivation after 100 splitting cycles.The addition of Ce promotes the formation of the Fe-Ov-Ce structure,which acts as an activator,triggers CO_(2)splitting,and lowers the energy barrier of C═O dissociation.The metallic Fe plays a role in consuming O_(2)−lattice transformed from Fe-Ov-Ce,whereas CaO acts as a structure promoter that enables phase-reversible Fe0↔Fe3+looping.
基金financial support from the National Natural Science Foundation of China(52076209,22179027,22469006)the Foundation and Applied Foundation Research of Guangdong Province(2022B1515020045)the Heilongjiang Key Research and Development Project of China(JD22A026)。
文摘Hydrogen energy,as the ultimate clean energy,effectively avoids the greenhouse effect.Chemical looping hydrogen production(CLHP),a versatile energy conversion and production technology,has garnered extensive attention.CLHP demands redox catalysts with high oxygen capacity,regulatable reactivity,and structural integrity even under harsh operational conditions.Currently,sintering,agglomeration,and inactivation of redox catalysts during cyclic lattice oxygen release and restoration are challenging,hindering the wide industrialization of the chemical looping(CL)process.Moreover,the precise control of activity and reaction rate of the redox catalysts to flexibly accommodate the demands of various reaction substrates remains unclear.This paper introduces the design of a nano-scaled redox catalyst featuring a unique core-shell structure.By precisely controlling the shell thickness,a series of hierarchical Fe_(2)O_(3)@SiO_(2)redox catalysts were successfully synthesized.Building on this achievement,an in-depth investigation was conducted into the impact of the thickness and spatial structure of the inert support on the stability and mass transfer rate of the redox catalyst,aiming to achieve a perfect balance between these two factors during the CLHP process.A thin shell(70 nm)exhibits excellent cyclic stability,maintaining consistent performance in 30 consecutive redox cycles,while a thicker shell(200 nm)undergoes rapid deactivation due to the formation of a substantial amount of iron silicate.In-situ transmission electron microscopy(TEM)reveals that the SiO_(2)shell effectively restricts the agglomeration of Fe_(2)O_(3).The unique core-shell structure and controllable shell thickness offer novel insights into the flexible design of efficient and durable hierarchical redox catalysts with spatial structure.
基金support by National Natural Science Foundation of China(NSFC)under Grant No.52488201(Basic Science Center Program),Grant No.52241601and 52176026。
文摘Repurposing of carbon dioxide to valuable chemicals and fuels with the assistance of renewable energy is essential for balanced carbon cycle.Here,a new CO_(2)conversion strategy was demonstrated that utilized concentrated solar energy to directly drive chemical looping reverse water gas shift process,which simultaneously coupled the photothermal and photochemical effects to achieve enhanced CO_(2)reduction reactivity and 100%CO selectivity.The solar-driven chemical looping CO_(2)reduction on Ni-Fe_(2)O_(3/)La_(0.8)Sr_(0.2)FeO_(3)exhibited great activity,with an average CO production rate of up to 0.28 mmol/g_(oc)/min at 283℃The product yield of the solar-driven reaction was almost 600%higher than that of the thermal reaction at the same temperature.The CO production overcame the thermodynamic equilibrium limitation under the combined impact of thermal and non-thermal effects of direct-light illumination.Light irradiation reinforced reactive gas adsorption and dissociation of carbonate intermediates,and stimulated oxygen ion migration and lattice oxygen transformation,thus promoting the reactivity.The concept of concentrated solar energy to drive chemical looping reverse water gas shift opens a new avenue for effective CO_(2)resource utilization and solar fuel production.
基金fnancially supported by the Open Research Fund Program of Anhui Provincial Institute of Modern Coal Processing Technology,Anhui University of Science and Technology (MTY202201)。
文摘Coal-direct chemical looping(CDCL) is a promising CO_(2) capture technology with low costs.Potassium modification can significantly enhance the reactivity of iron-based oxygen carriers and coal.However,potassium loss causes a decline in cyclic stability.To address this,we prepared a potassium hexatitanate-modified iron-based OC and conducted CDCL experiments in a fixed-bed reactor using Zhundong coal coke as fuel.The study examined the impact of potassium hexatitanate on carbon conversion,OC activity stability,and potassium maintenance.Additionally,Fact Sage was used to calculate potassium fugacity patterns at different temperatures,Fe_(2)O_(3)/C molar ratios,and OC reduction degrees.Results showed that potassium hexatitanate increased carbon conversion,achieving 50%conversion at 40% potassium addition.In multi-cycle tests,carbon conversion rose with increased cycle times,reaching 84%.This improvement is attributed to ion exchange between Fe^(3+) and Ti^(4+),which induces lattice distortion and creates oxygen vacancies,enhancing OC reactivity.Potassium content remained stable during multi-cycle tests,indicating the effective potassium retention capacity of potassium hexatitanate.
基金supported by the open project of the theoretical physics academic exchange platform of Chongqing University。
文摘For loops with UV divergences,assuming that the physical contributions of loops from UV regions are insignificant,a UV-free scheme method described by an equation is introduced to derive loop results without UV divergences in the calculations,i.e.,a route of the analytic continuation T_(F)→T_(P)besides the traditional route∞-∞in the mathematical structure.This scheme provides a new perspective to an open question of the hierarchy problem of Higgs mass,i.e.,an alternative interpretation without fine-tuning within the standard model.
基金The National Natural Science Foundation of China(No.51276064)the Natural Science Foundation of Beijing City(No.3132028)
文摘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.
基金Supported by the National Natural Science Foundation of China (No.50574046 and 50164002, )Natural Science Foun-dation of Yunnan Province (No. 2004E0012Q).
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China(No.51276210,50906030,50936001)the financial grant of North China University of Water Conservancy and Electric Power(No.201012)the National Basic Research Program(973)of China(No.2011CB707301)
文摘Chemical looping combustion （CLC） of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier （OC） was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi （LZ） bituminous coal, was performed in a thermogravimetric analyzer （TGA）-Fourier transform infrared （FT-IR） spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFeaO40C was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn304 or Fe203, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe304 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4.
基金Supported by the Research and Development Program of the Korea Institute of Energy Research(KIER)(B4-2431-04)the National Natural Science Foundation of China(21276129,20876079)the Natural Science Funds for Distinguished Young Scholar in Shandong Province(JQ200904)
文摘The chemical looping gasification uses an oxygen carrier for solid fuel gasification by supplying insufficient lattice oxygen. The effect of gasifying medium on the coal chemical looping gasification with Ca SO4 as oxygen carrier is investigated in this paper. The thermodynamical analysis indicates that the addition of steam and CO2 into the system can reduce the reaction temperature, at which the concentration of syngas reaches its maximum value.Experimental result in thermogravimetric analyzer and a fixed-bed reactor shows that the mixture sample goes through three stages, drying stage, pyrolysis stage and chemical looping gasification stage, with the temperature for three different gaseous media. The peak fitting and isoconversional methods are used to determine the reaction mechanism of the complex reactions in the chemical looping gasification process. It demonstrates that the gasifying medium(steam or CO2) boosts the chemical looping process by reducing the activation energy in the overall reaction and gasification reactions of coal char. However, the mechanism using steam as the gasifying medium differs from that using CO2. With steam as the gasifying medium, parallel reactions occur in the beginning stage, followed by a limiting stage shifting from a kinetic to a diffusion regime. It is opposite to the reaction mechanism with CO2 as the gasifying medium.
基金The financial support of the National Natural Science Foundation of China(51406208,51406214)supported by the Science&Technology Research Project of Guangdong Province(2015A010106009)the support of Key Laboratory of Renewable Energy,Chinese Academy of Sciences(Y607j51001)
文摘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.
基金This work was supported by the National Natural Science Foundation of China(Nos.51676101,51806107).
文摘This study evaluated the release characteristics of mercury from bituminous coal in chemical looping combustion(CLC)using Australian iron ore as the oxygen carrier in a fixed bed reactor.The effects of several parameters,such as temperature in the fuel reactor(FR)and air reactor(AR),gasification medium in the FR,and reaction atmosphere in the AR,on mercury release characteristics,were investigated.The mercury speciation and release amount in the FR and AR under different conditions were further explored.The results indicate that most of the mercury in coal was released in the FR,while the rest of it was released in the AR.Hg0 was found to be the major species in the released mercury.The results also indicate that a higher temperature in the FR led to an increase in the total mercury release amount and a decrease in Hg0 proportion.However,a higher temperature in the AR resulted in a decrease in the total mercury release amount and Hg 0 proportion.The increase in the H2O/CO2 ratio of gasification mediums in the FR was beneficial for the increase in the total mercury release amount and Hg 0 proportion.A higher O2 concentration in reaction atmosphere in AR had a negligible effect on the total mercury release amount,but a positive effect on Hg0 oxidization.
基金support of this research work by the National Natural Science Foundation of China(51761135119)the Scientific Research foundation of Graduate school of Southeast University(YBPY1906,YBJJ1606,YBJJ1703).
文摘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.
