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
During the re-entry of a hypersonic aircraft into the earth’s atmosphere,the surrounding air experiences dissociation,ionization,and other complex chemical phenomena due to extreme temperature by shock wave.To ensure...During the re-entry of a hypersonic aircraft into the earth’s atmosphere,the surrounding air experiences dissociation,ionization,and other complex chemical phenomena due to extreme temperature by shock wave.To ensure thermal safety,the thermochemical non-equilibrium effects resulting from real-gas behavior should be taken into account.In this paper,the characteristics of a double-cone hypersonic laminar flow,including distributions of wall pressure,heat flux,and species dissociation are numerically analyzed with incoming enthalpy of 9.65-21.77 MJ/kg.The thermochemical non-equilibrium flow at different enthalpy and wall temperatures is performed with two-temperature model and Park’s seven chemical reaction model.It is found that the doublecone flow features complex shock-shock interactions to form triple points.The flow topology is further brought out from the analysis of streamlines.At the lowest incoming enthalpy with isothermal wall conditions,two foci points appear.While others highlight only one focal point.As the increment of incoming enthalpy,the heat flux and dissociation of nitrogen and oxygen also increase.An increasing wall temperature leads to a larger separation bubble and a lower value of heat flux and pressure peak,while massive dissociation occurs without obvious ionization under considered cases.展开更多
The increasing need for sustainable energy and the environmental impacts of reliance on fossil fuels have sparked greater interest in biomass as a renewable energy source.This review provides an in-depth assessment of...The increasing need for sustainable energy and the environmental impacts of reliance on fossil fuels have sparked greater interest in biomass as a renewable energy source.This review provides an in-depth assessment of biooil and biochar generation through the pyrolysis of sawdust,a significant variety of lignocellulosic biomass.The paper investigates different thermochemical conversion methods,including fast,slow,catalytic,flash,and co-pyrolysis,while emphasizing their operational parameters,reactor designs,and effects on product yields.The influence of temperature,heating rate,and catalysts on enhancing the quality and quantity of bio-oil and biochar is thoroughly analyzed.Additionally,the review examines advanced reactor technologies such as fluidized beds,fixed beds,auger reactors,and plasma pyrolysis systems.It also discusses recent progress in catalyst innovation and product enhancement techniques to overcome the challenges posed by bio-oil,including its high oxygen content and low stability.By synthesizing experimental results and conducting comparative analyses,the paper identifies existing research gaps and provides insights into future paths for effective biomass utilization,thereby aiding in the creation of economically viable and environmentally responsible bioenergy systems.展开更多
Based on Moho and Curie depth,heat flow,and upper mantle S-wave velocity anomaly,we infer the thermo-chemical structure of the lithospheres in Africa and surrounding oceans.The Moho depth is derived from gravity anoma...Based on Moho and Curie depth,heat flow,and upper mantle S-wave velocity anomaly,we infer the thermo-chemical structure of the lithospheres in Africa and surrounding oceans.The Moho depth is derived from gravity anomaly using the Parker-Oldenburg method,with constraints from seismic Moho.Crustal stratification defined by Curie-Moho depth difference shows that thermal and strong compositional processes may have shaped the lithospheric architecture of the African continental plate.Moho and Curie depths indicate the southern and eastern African cratons have thermochemical structures different from the West African Craton.Large Curie-Moho depth difference in southern and eastern Africa aligns with the low velocity anomaly originated from the core-mantle boundary.Mantle upwelling from the African low-velocity anomaly presumably induced partial melting at great depth,and the release of mineral-rich fluid and large amounts of volatile components facilitates a regional metasomatism,and results in a depleted,predominantly felsic,low-density paramagnetic crust.Mantle xenolith in kimberlites and volcanic rocks supports metasomatism by melts transmitted through narrow conduits as an intermittent or continuous upward flux of mineral-rich fluid.Alignment of the Curie-Moho depth difference at the intra-plate volcanic province correlates with weak lithospheric strength along the corridor connecting the intra-plate volcanic province with the Ethiopian plateau,suggesting a pathway for thermochemical asthenospheric flow.Crustal stratification and compositional-driven density layering support crustal buoyancy and uplift in the Hoggar,and southern and eastern Africa.A magnetized uppermost mantle is prevalent in the entire oceanic region,except at large igneous provinces(LIPs),volcanic seamounts,and oceanic plateaus,which have partial paramagnetic crusts.Our results support thermochemical upwelling related to the low velocity anomaly beneath the African plate.展开更多
Hydrogen is recognized as a clean energy carrier that can decarbonize heavy industry and the aviation system.However,the infrastructure is not yet ready for a hydrogen economy and large-scale hydrogen storage is neede...Hydrogen is recognized as a clean energy carrier that can decarbonize heavy industry and the aviation system.However,the infrastructure is not yet ready for a hydrogen economy and large-scale hydrogen storage is needed to balance the mismatch between supply and demand.Therefore,depleted gas fields have been proposed as suitable storage sites,given the presence of infrastructure and pipeline network for distribution and utilization.Attempts have been made to analyze the suitability of these reservoirs for hydrogen storage,with a focus on choosing higher temperature and salinity conditions to neutralize the effects of microbial activities as one of the main sources of hydrogen loss in the depleted gas reservoirs.However,thermochemical sulfate reduction(TSR)is activated at high temperatures and has a huge potential not only to consume hydrogen through abiotic reactions but also to generate a huge amount of H_(2)S.In this study,a onedimensional diffusion-based mass transport model was built using PHREEQC to highlight the potential challenges posed by the TSR in depleted gas fields.The results obtained indicated that the presence of iron minerals(pyrite and hematite)is crucial for H_(2)S generation through TSR reactions.An increase in temperature also leads to an increase in H_(2)S concentration in the brine and gas phase.However,since most of the H_(2)S formation comes from pyrite dissolution and pyrite dissolution is still strong at lower temperatures,a low temperature is not necessarily the best selection criterion to avoid H_(2)S formation.Thus,precautions must be taken to ensure that activation of TSR does not pose significant environmental problems.展开更多
Thiadiamondoids(TDs)have recently attracted increasing attention as molecular proxies for thermochemical sulfate reduction(TSR)reactions in reservoirs.However,their formation mechanisms,as well as the generation and e...Thiadiamondoids(TDs)have recently attracted increasing attention as molecular proxies for thermochemical sulfate reduction(TSR)reactions in reservoirs.However,their formation mechanisms,as well as the generation and evolution processes,remain poorly understood.In this study,simulation experiments with a duration of 160 h were conducted on the model compound 1,3-dimethyladamantane(1,3-DMA)using the CaSO_(4),MgSO_(4),and elemental S systems,with measurements at the 10th,20th,40th,80th and 160th hours during the simulation process being presented.The results indicate that at the end of simulation,the MgSO_(4) system exhibited the lowest residual amounts of 1,3-DMA,suggesting the highest degree of TSR.Four types of non-hydrocarbon compounds with adamantane structures were detected in the liquid products in the three experiment systems:adamantanones,adamantanols,adamantanethiols(ATs),and thiaadamantanes(TAs).Among these,adamantanones exhibited the highest concentrations in the three simulation systems.In addition,TAs were dominated by C_(3)-TAs in the CaSO_(4) and MgSO_(4) systems and by C_(2)-TAs in the elemental S system.The simulation experiments revealed a strong correlation between the concentrations of TAs and adamantanones,suggesting that adamantanones might be the intermediates for TAs.Combined with the synthesis mechanism of TAs from thiaadamamantane-4,8-dione,TDs might have two different genetic mechanisms:(a)low temperature cationic carbon ion rearrangement from diagenesis to early catagenesis stage,and(b)a free sulfur radical mechanism in high-temperature TSR process during middle-late catagenesis.TAs exhibited different generation and evolution processes across different experiment systems.Notably,the MgSO_(4) system revealed that TAs undergo generation,accumulation,and destruction process,corresponding to Easy%Ro values of 0.89%-0.98%,0.98%-1.21%,and>1.21%,respectively.Among these three simulation systems,dibenzothiophenes(DBTs)concentrations consistently trended upwards,indicating TAs have lower thermal stability than DBTs.展开更多
Cerium-aluminum(CeAl)alloy is promising reactive structural materials(RSMs)with significant potential for liner applications.To investigate the thermochemical characteristics of CeAl alloy and the perforation behavior...Cerium-aluminum(CeAl)alloy is promising reactive structural materials(RSMs)with significant potential for liner applications.To investigate the thermochemical characteristics of CeAl alloy and the perforation behavior of its liner impacting steel targets,a CeAl alloy liner with 5 wt%Al content was fabricated,with a cerium(Ce)liner and a copper(Cu)liner used as control.The microstructure and elemental distribution of the CeAl alloy were analyzed using SEM,EDS,and XRD.The thermochemical reaction mechanism of the CeAl alloy was examined through TG-DSC.Penetration experiments were conducted to explore the combined effects of invasion and implosion of CeAl alloy liner against steel target.The results indicate that the addition of Al leads to the formation of Ce_(3)Al intermetallic compounds in the alloy and reduces the apparent activation energy of the Ce-based alloy by around 53.17%,thereby facilitating energy release.The presence of 5 wt%Al increases the calorific value by approximately 24.5%,and this change allows the oxidation process to be divided into three distinct stages.Compared to an inert copper liner,the average penetration diameter of the CeAl_(5) reactive alloy liner increases by around 42.78%.Furthermore,when compared to the Ce liner,the penetration depth of the CeAl_(5) reactive alloy liner increases by approximately 82.64%.展开更多
The rapid increase in energy demand,the extensive use of fossil fuels and the urgent need to reduce the carbon dioxide emissions have raised concerns in the transportation sector.Alternate renewable and sustainable so...The rapid increase in energy demand,the extensive use of fossil fuels and the urgent need to reduce the carbon dioxide emissions have raised concerns in the transportation sector.Alternate renewable and sustainable sources have become the ultimate solution to overcome the expected depletion of fossil fuels.The conversion of lignocellulosic biomass to liquid(BtL)transportation fuels seems to be a promising path and presents advantages over first generation biofuels and fossil fuels.Therefore,development of BtL systems is critical to increase the potential of this resource in a sustainable and economic way.Conversion of lignocellulosic BtL transportation fuels,such as,gasoline,diesel and jet fuel can be accomplished through various thermochemical processes and processing routes.The major steps for the production of BtL fuels involve feedstock selection,physical pretreatment,production of bio-oil,upgrading of bio-oil to transportation fuels and recovery of value-added products.The present work is aiming to give a comprehensive review of the current process technologies following these major steps and the current scenarios of biomass to liquid facilities for the production of biofuels.展开更多
In this study, the solar thermochemical reactor performance for CO_2 utilization into synthesis gas(H_2+ CO) based on CH_4 reforming process was investigated in the context of carbon capture and utilization(CCU) techn...In this study, the solar thermochemical reactor performance for CO_2 utilization into synthesis gas(H_2+ CO) based on CH_4 reforming process was investigated in the context of carbon capture and utilization(CCU) technologies. The P1 radiation heat transfer model is adopted to establish the heat and mass transfer model coupled with thermochemical reaction kinetics. The reactor thermal behavior with direct heat transfer between gaseous reactant and products evolution and the effects of different structural parameters were evaluated. It was found that the reactor has the potential to utilize by ～60% of CO_2 captured with 40% of CH_4 co-fed into syngas(72.9% of H_2 and 27.1% of CO) at 741.31 k W/mof incident radiation heat flux. However, the solar irradiance heat flux and temperature distribution were found to significantly affect the reactant species conversion efficiency and syngas production. The chemical reaction is mainly driven by the thermal energy and higher species conversion into syngas was observed when the temperature distribution at the inner cavity of the reactor was more uniform. Designed a solar thermochemical reactor able to volumetric store concentrated irradiance could highly improve CCU technologies for producing energy-rich chemicals. Besides, the mixture gas inlet velocity, operating pressure and CO_2/CH_4 feeding ratio were crucial to determining the efficiency of CO_2 utilization to solar fuels. Catalytic CO_2-reforming of CH_4 to chemical energy is a promising strategy for an efficient utilization of CO_2 as a renewable carbon source.展开更多
One of the basic ways to reduce polluting emissions of ship power plants is application of innovative devices for on-board energy generation by means of secondary energy resources.The combined gas turbine and diesel e...One of the basic ways to reduce polluting emissions of ship power plants is application of innovative devices for on-board energy generation by means of secondary energy resources.The combined gas turbine and diesel engine plant with thermochemical recuperation of the heat of secondary energy resources has been considered.It is suggested to conduct the study with the help of mathematical modeling methods.The model takes into account basic physical correlations,material and thermal balances,phase equilibrium,and heat and mass transfer processes.The paper provides the results of mathematical modeling of the processes in a gas turbine and diesel engine power plant with thermochemical recuperation of the gas turbine exhaust gas heat by converting a hydrocarbon fuel.In such a plant,it is possible to reduce the specific fuel consumption of the diesel engine by 20%.The waste heat potential in a gas turbine can provide efficient hydrocarbon fuel conversion at the ratio of powers of the diesel and gas turbine engines being up to 6.When the diesel engine and gas turbine operate simultaneously with the use of the LNG vapor conversion products,the efficiency coefficient of the plant increases by 4%–5%.展开更多
Presents the use of the similar transform and potential theory for calculation of the bypass flow factor and pressure gradient and the analysis of the influence of bypass flow factor and pressure gradient on heat tran...Presents the use of the similar transform and potential theory for calculation of the bypass flow factor and pressure gradient and the analysis of the influence of bypass flow factor and pressure gradient on heat transfer is analyzed, and the distribution of nose cone ablation obtained by combining the controlling equations of boundary layer, the compatible relation of interface and the heat conduction of interior.展开更多
Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin （CUTB） show that gas invasion at the late stage is accompanied by an increase of the contents of HeS a...Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin （CUTB） show that gas invasion at the late stage is accompanied by an increase of the contents of HeS and CO2 in natural gas, by the forming of the high total dissolved solids formation water, by an increase of the content of HCO3^-, relative to Cl^-, by an increase of the 2nd family ions （Ca^2＋, Mg^2＋, Sr^2＋ and Ba^2＋） and by a decrease of the content of SO4^2-, relative to Cl^-. The above phenomena can be explained only by way of thermochemicai sulfate reduction （TSR）. TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula： ∑CH＋CaSO4＋H-2O→H2S＋CO2＋CaCO3. （1） Dissolved SO4^2- in the formation water is consumed in the above reaction, when HeS and CO2 are generated, resulting in a decrease of SO4^2- in the formation water and an increase of both HeS and CO2 in the natural gas. If formation water exists, the generated CO2 will go on reacting with the carbonate to form bicarbonate, which can be dissolved in the formation water, thus resulting in the enrichment of Ca^2＋ and HCO3^-. The above reaction can be described by the following equation： CO2＋HeO＋CaCO3→Ca^2＋＋2HCO3^-. The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃, which is the minimum for TSR to occur. At the same time, dolomitization, which might be a direct result of TSR, has been found in both the Cambrian and the lower Ordovician. The above evidence indicates that TSR is in an active reaction, providing a novel way to reevaluate the exploration potentials of natural gas in this district.展开更多
A theoretical methodology for thermochemical non-equilibrium flow combing with the HLLC(Harten-Lax-van Leer Contact) scheme was applied to study the hypersonic thermochemical non-equilibrium environment of an entry co...A theoretical methodology for thermochemical non-equilibrium flow combing with the HLLC(Harten-Lax-van Leer Contact) scheme was applied to study the hypersonic thermochemical non-equilibrium environment of an entry configuration in ionized flow. A two-temperature controlling model was utilized and the Gupta’s 11 species(N 2, O2, NO, O, N, NO+, N+2, O+2, N+, O+, e)thermochemical non-equilibrium model was taken. Firstly, numerical calculations of hypersonic thermochemical non-equilibrium environments for different aerodynamic shapes were carried out to verify the reliability of the method above. Then, the method was used to research the effects of ionization and wall catalysis on the hypersonic thermochemical non-equilibrium environment of the entry configuration in ionized flow. The shock stand-off distance can be reduced by thermochemical reactions but doesn’t continue to decrease significantly when ionization occurs. The shock stand-off distance calculated by the 11 species model is 4.2% smaller than that calculated by the 5 species(N2, O2, NO, O, N) thermochemical non-equilibrium model without considering ionization.Ionization reduces wall heat flux but increases wall pressure a little. The effect of ionization on aerothermal loads is greater than that of aerodynamic loads. The thermochemical reactions of electrons and ions catalyzed at the wall increase wall heat flux significantly but make a small change in wall pressure. The maximum wall heat flux obtained by only considering the electrons and ions catalyzed at the partially catalytic wall condition is 11.8% less than that calculated at the supercatalytic wall condition.展开更多
This study aimed to establish a closed-cycle operation technology with high thermal efficiency in the thermochemical sulfur-iodine cycle for large-scale hydrogen production.A series of experimental studies were perfor...This study aimed to establish a closed-cycle operation technology with high thermal efficiency in the thermochemical sulfur-iodine cycle for large-scale hydrogen production.A series of experimental studies were performed to investigate the occurrence of side reactions in both the H2SO4 and HI x phases from the H2SO4/HI/I2/H2O quaternary system within a constant temperature range of 323-363 K.The effects of iodine content,water content and reaction temperature on the side reactions were evaluated.The results showed that an increase in the reaction temperature promoted the side reactions.However,they were prevented as the iodine or water content increased.The occurrence of side reactions was faster in kinetics and more intense in the H2SO4 phase than in the HI x phase.The sulfur or hydrogen sulfide formation reaction or the reverse Bunsen reaction was validated under certain conditions.展开更多
A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution e...A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔ θ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle...展开更多
Perovskite material is one of the promising classes of redox catalysts for hydrogen production through two-step ther-mochemical H20 splitting.Herein,an analogue of La1-xCaxMnO3 perovskite was systematically investigat...Perovskite material is one of the promising classes of redox catalysts for hydrogen production through two-step ther-mochemical H20 splitting.Herein,an analogue of La1-xCaxMnO3 perovskite was systematically investigated as a catalyst for thermochemical H2 evolution.The Ca doping level（x = 0.2,0.4,0.6,0.8）and re-oxidation temperature were com-prehensively optimized for the improvement of catalytic performance.According to our experimental results,La0.6-Ca0.4MnO3 perovskite displayed the highest yield of H2 at the re-oxidation temperature of 900℃ and the obtained H2 production was -10 times higher than that of the benchmark ceria catalyst under the same experimental condition.More importantly,Lao.6Ca0.4MnO3 perovskite catalyst exhibited impressive cyclic stability in repetitive O2 and H2 test.展开更多
The dynamic formation,shock-induced inhomogeneous temperature rise and corresponding chemical reaction behaviors of PTFE/Al reactive liner shaped charge jet(RLSCJ)are investigated by the combination of mesoscale simul...The dynamic formation,shock-induced inhomogeneous temperature rise and corresponding chemical reaction behaviors of PTFE/Al reactive liner shaped charge jet(RLSCJ)are investigated by the combination of mesoscale simulation,reaction kinetics and chemical energy release test.A two-dimensional granular model is developed with the randomly normal distribution of aluminum particle sizes and the particle delivery program.Then,the granular model is employed to study the shock-induced thermal behavior during the formation and extension processes of RLSCJ,as well as the temperature history curves of aluminum particles.The simulation results visualize the motion and temperature responses of the RLSCJ at the grain level,and further indicate that the aluminum particles are more likely to gather in the last two-thirds of the jet along its axis.Further analysis shows that the shock,collision,friction and deformation behaviors are all responsible for the steep temperature rise of the reactive jet.In addition,a shock-induced chemical reaction extent model of RLSCJ is built based on the combination of the Arrhenius model and the Avrami-Erofeev kinetic model,by which the chemical reaction growth behavior during the formation and extension stages is described quantitatively.The model indicates the reaction extent highly corresponds to the aluminum particle temperature history at the formation and extension stages.At last,a manometry chamber and the corresponding energy release model are used together to study the macroscopic chemical energy release characteristics of RLSCJ,by which the reaction extent model is verified.展开更多
Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.Howe...Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.However,starch usually suffers from severe foaming and low carbon yield during direct pyrolysis.Herein,we report a simple and eco-friendly dry strategy,by maleic anhydride initiating the esterification of starch,to design carbon microspheres against the starch foaming.Moreover,the infuence of ester grafting on the pyrolytic behavior of starch is also focused.The formation of ester groups in precursor guarantees the structural stability of starch-based intermediate because it can promote the accumulation of unsaturated species and accelerate the water elimination during pyrolysis.Meanwhile,the esterification and dehydration reactions greatly deplete the primary hydroxyl groups in the starch molecules and thus the rapid levoglucosan release is inhibited,which well keeps the spherical morphology of starch and ensures the high carbon yield.In further exploration as anode materials for Lithium-ion batteries,the obtained carbon microspheres exhibit good cyclability and rate performance with a reversible capacity of 444 m Ah g^(-1)at 50 m A g^(-1).This work provides theoretical fundamentals for the controllable thermal transformation of biomass towards wide applications.展开更多
To predict aeroheating performance of hypersonic vehicles accurately in thermochemical nonequilibrium flows accompanied by rarefaction effect,a Nonlinear Coupled Constitutive Relations(NCCR)model coupled with Gupta’s...To predict aeroheating performance of hypersonic vehicles accurately in thermochemical nonequilibrium flows accompanied by rarefaction effect,a Nonlinear Coupled Constitutive Relations(NCCR)model coupled with Gupta’s chemical models and Park’s two-temperature model is firstly proposed in this paper.Three typical cases are intensively investigated for further validation,including hypersonic flows over a two-dimensional cylinder,a RAM-C II flight vehicle and a type HTV-2 flight vehicle.The results predicted by NCCR solution,such as heat flux coefficient and electron number densities,are in better agreement with those of direct simulation Monte Carlo or flight data than Navier-Stokes equations,especially in the extremely nonequilibrium regions,which indicates the potential of the newly-developed solution to capture both thermochemical and rarefied nonequilibrium effects.The comparisons between the present solver and NCCR model without a two-temperature model are also conducted to demonstrate the significance of vibrational energy source term in the accurate simulation of high-Mach flows.展开更多
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 Natural Science Foundation of China(Grant Nos.12090030 and 12002261)National Postdoctoral Program for Innovative Talents,China(Grant No.BX20200267)the Fundamental Research Funds for the Central Universities,China(Grant No.xzy012024019)。
文摘During the re-entry of a hypersonic aircraft into the earth’s atmosphere,the surrounding air experiences dissociation,ionization,and other complex chemical phenomena due to extreme temperature by shock wave.To ensure thermal safety,the thermochemical non-equilibrium effects resulting from real-gas behavior should be taken into account.In this paper,the characteristics of a double-cone hypersonic laminar flow,including distributions of wall pressure,heat flux,and species dissociation are numerically analyzed with incoming enthalpy of 9.65-21.77 MJ/kg.The thermochemical non-equilibrium flow at different enthalpy and wall temperatures is performed with two-temperature model and Park’s seven chemical reaction model.It is found that the doublecone flow features complex shock-shock interactions to form triple points.The flow topology is further brought out from the analysis of streamlines.At the lowest incoming enthalpy with isothermal wall conditions,two foci points appear.While others highlight only one focal point.As the increment of incoming enthalpy,the heat flux and dissociation of nitrogen and oxygen also increase.An increasing wall temperature leads to a larger separation bubble and a lower value of heat flux and pressure peak,while massive dissociation occurs without obvious ionization under considered cases.
文摘The increasing need for sustainable energy and the environmental impacts of reliance on fossil fuels have sparked greater interest in biomass as a renewable energy source.This review provides an in-depth assessment of biooil and biochar generation through the pyrolysis of sawdust,a significant variety of lignocellulosic biomass.The paper investigates different thermochemical conversion methods,including fast,slow,catalytic,flash,and co-pyrolysis,while emphasizing their operational parameters,reactor designs,and effects on product yields.The influence of temperature,heating rate,and catalysts on enhancing the quality and quantity of bio-oil and biochar is thoroughly analyzed.Additionally,the review examines advanced reactor technologies such as fluidized beds,fixed beds,auger reactors,and plasma pyrolysis systems.It also discusses recent progress in catalyst innovation and product enhancement techniques to overcome the challenges posed by bio-oil,including its high oxygen content and low stability.By synthesizing experimental results and conducting comparative analyses,the paper identifies existing research gaps and provides insights into future paths for effective biomass utilization,thereby aiding in the creation of economically viable and environmentally responsible bioenergy systems.
基金Supported by the National Natural Science Foundation of China(Nos.91858213,41776057,41761134051)part of the PhD work of O J AKINRINADE and the National Key Research and Development Program of China(Nos.2023 YFF 0803400,2023 YFF 0803404)。
文摘Based on Moho and Curie depth,heat flow,and upper mantle S-wave velocity anomaly,we infer the thermo-chemical structure of the lithospheres in Africa and surrounding oceans.The Moho depth is derived from gravity anomaly using the Parker-Oldenburg method,with constraints from seismic Moho.Crustal stratification defined by Curie-Moho depth difference shows that thermal and strong compositional processes may have shaped the lithospheric architecture of the African continental plate.Moho and Curie depths indicate the southern and eastern African cratons have thermochemical structures different from the West African Craton.Large Curie-Moho depth difference in southern and eastern Africa aligns with the low velocity anomaly originated from the core-mantle boundary.Mantle upwelling from the African low-velocity anomaly presumably induced partial melting at great depth,and the release of mineral-rich fluid and large amounts of volatile components facilitates a regional metasomatism,and results in a depleted,predominantly felsic,low-density paramagnetic crust.Mantle xenolith in kimberlites and volcanic rocks supports metasomatism by melts transmitted through narrow conduits as an intermittent or continuous upward flux of mineral-rich fluid.Alignment of the Curie-Moho depth difference at the intra-plate volcanic province correlates with weak lithospheric strength along the corridor connecting the intra-plate volcanic province with the Ethiopian plateau,suggesting a pathway for thermochemical asthenospheric flow.Crustal stratification and compositional-driven density layering support crustal buoyancy and uplift in the Hoggar,and southern and eastern Africa.A magnetized uppermost mantle is prevalent in the entire oceanic region,except at large igneous provinces(LIPs),volcanic seamounts,and oceanic plateaus,which have partial paramagnetic crusts.Our results support thermochemical upwelling related to the low velocity anomaly beneath the African plate.
文摘Hydrogen is recognized as a clean energy carrier that can decarbonize heavy industry and the aviation system.However,the infrastructure is not yet ready for a hydrogen economy and large-scale hydrogen storage is needed to balance the mismatch between supply and demand.Therefore,depleted gas fields have been proposed as suitable storage sites,given the presence of infrastructure and pipeline network for distribution and utilization.Attempts have been made to analyze the suitability of these reservoirs for hydrogen storage,with a focus on choosing higher temperature and salinity conditions to neutralize the effects of microbial activities as one of the main sources of hydrogen loss in the depleted gas reservoirs.However,thermochemical sulfate reduction(TSR)is activated at high temperatures and has a huge potential not only to consume hydrogen through abiotic reactions but also to generate a huge amount of H_(2)S.In this study,a onedimensional diffusion-based mass transport model was built using PHREEQC to highlight the potential challenges posed by the TSR in depleted gas fields.The results obtained indicated that the presence of iron minerals(pyrite and hematite)is crucial for H_(2)S generation through TSR reactions.An increase in temperature also leads to an increase in H_(2)S concentration in the brine and gas phase.However,since most of the H_(2)S formation comes from pyrite dissolution and pyrite dissolution is still strong at lower temperatures,a low temperature is not necessarily the best selection criterion to avoid H_(2)S formation.Thus,precautions must be taken to ensure that activation of TSR does not pose significant environmental problems.
基金funded by the Natural Science Foundation of China(Grants Nos.42272167,U24B6001,and 41772153)Science&Technology Project of Sinopec(Grant Nos.P23167 and P24173).
文摘Thiadiamondoids(TDs)have recently attracted increasing attention as molecular proxies for thermochemical sulfate reduction(TSR)reactions in reservoirs.However,their formation mechanisms,as well as the generation and evolution processes,remain poorly understood.In this study,simulation experiments with a duration of 160 h were conducted on the model compound 1,3-dimethyladamantane(1,3-DMA)using the CaSO_(4),MgSO_(4),and elemental S systems,with measurements at the 10th,20th,40th,80th and 160th hours during the simulation process being presented.The results indicate that at the end of simulation,the MgSO_(4) system exhibited the lowest residual amounts of 1,3-DMA,suggesting the highest degree of TSR.Four types of non-hydrocarbon compounds with adamantane structures were detected in the liquid products in the three experiment systems:adamantanones,adamantanols,adamantanethiols(ATs),and thiaadamantanes(TAs).Among these,adamantanones exhibited the highest concentrations in the three simulation systems.In addition,TAs were dominated by C_(3)-TAs in the CaSO_(4) and MgSO_(4) systems and by C_(2)-TAs in the elemental S system.The simulation experiments revealed a strong correlation between the concentrations of TAs and adamantanones,suggesting that adamantanones might be the intermediates for TAs.Combined with the synthesis mechanism of TAs from thiaadamamantane-4,8-dione,TDs might have two different genetic mechanisms:(a)low temperature cationic carbon ion rearrangement from diagenesis to early catagenesis stage,and(b)a free sulfur radical mechanism in high-temperature TSR process during middle-late catagenesis.TAs exhibited different generation and evolution processes across different experiment systems.Notably,the MgSO_(4) system revealed that TAs undergo generation,accumulation,and destruction process,corresponding to Easy%Ro values of 0.89%-0.98%,0.98%-1.21%,and>1.21%,respectively.Among these three simulation systems,dibenzothiophenes(DBTs)concentrations consistently trended upwards,indicating TAs have lower thermal stability than DBTs.
文摘Cerium-aluminum(CeAl)alloy is promising reactive structural materials(RSMs)with significant potential for liner applications.To investigate the thermochemical characteristics of CeAl alloy and the perforation behavior of its liner impacting steel targets,a CeAl alloy liner with 5 wt%Al content was fabricated,with a cerium(Ce)liner and a copper(Cu)liner used as control.The microstructure and elemental distribution of the CeAl alloy were analyzed using SEM,EDS,and XRD.The thermochemical reaction mechanism of the CeAl alloy was examined through TG-DSC.Penetration experiments were conducted to explore the combined effects of invasion and implosion of CeAl alloy liner against steel target.The results indicate that the addition of Al leads to the formation of Ce_(3)Al intermetallic compounds in the alloy and reduces the apparent activation energy of the Ce-based alloy by around 53.17%,thereby facilitating energy release.The presence of 5 wt%Al increases the calorific value by approximately 24.5%,and this change allows the oxidation process to be divided into three distinct stages.Compared to an inert copper liner,the average penetration diameter of the CeAl_(5) reactive alloy liner increases by around 42.78%.Furthermore,when compared to the Ce liner,the penetration depth of the CeAl_(5) reactive alloy liner increases by approximately 82.64%.
基金financial support from CONACYT-The Mexican National Council for Science and Technology (REFERENCE: 326204/439098)the University of Southern Denmark
文摘The rapid increase in energy demand,the extensive use of fossil fuels and the urgent need to reduce the carbon dioxide emissions have raised concerns in the transportation sector.Alternate renewable and sustainable sources have become the ultimate solution to overcome the expected depletion of fossil fuels.The conversion of lignocellulosic biomass to liquid(BtL)transportation fuels seems to be a promising path and presents advantages over first generation biofuels and fossil fuels.Therefore,development of BtL systems is critical to increase the potential of this resource in a sustainable and economic way.Conversion of lignocellulosic BtL transportation fuels,such as,gasoline,diesel and jet fuel can be accomplished through various thermochemical processes and processing routes.The major steps for the production of BtL fuels involve feedstock selection,physical pretreatment,production of bio-oil,upgrading of bio-oil to transportation fuels and recovery of value-added products.The present work is aiming to give a comprehensive review of the current process technologies following these major steps and the current scenarios of biomass to liquid facilities for the production of biofuels.
基金supported by the National Natural Science Foundation of China (No. 51522601)Chang Jiang Young Scholars Program of China (Q2016186)the Fok Ying Tong Education Foundation of China (No. 141055)
文摘In this study, the solar thermochemical reactor performance for CO_2 utilization into synthesis gas(H_2+ CO) based on CH_4 reforming process was investigated in the context of carbon capture and utilization(CCU) technologies. The P1 radiation heat transfer model is adopted to establish the heat and mass transfer model coupled with thermochemical reaction kinetics. The reactor thermal behavior with direct heat transfer between gaseous reactant and products evolution and the effects of different structural parameters were evaluated. It was found that the reactor has the potential to utilize by ～60% of CO_2 captured with 40% of CH_4 co-fed into syngas(72.9% of H_2 and 27.1% of CO) at 741.31 k W/mof incident radiation heat flux. However, the solar irradiance heat flux and temperature distribution were found to significantly affect the reactant species conversion efficiency and syngas production. The chemical reaction is mainly driven by the thermal energy and higher species conversion into syngas was observed when the temperature distribution at the inner cavity of the reactor was more uniform. Designed a solar thermochemical reactor able to volumetric store concentrated irradiance could highly improve CCU technologies for producing energy-rich chemicals. Besides, the mixture gas inlet velocity, operating pressure and CO_2/CH_4 feeding ratio were crucial to determining the efficiency of CO_2 utilization to solar fuels. Catalytic CO_2-reforming of CH_4 to chemical energy is a promising strategy for an efficient utilization of CO_2 as a renewable carbon source.
文摘One of the basic ways to reduce polluting emissions of ship power plants is application of innovative devices for on-board energy generation by means of secondary energy resources.The combined gas turbine and diesel engine plant with thermochemical recuperation of the heat of secondary energy resources has been considered.It is suggested to conduct the study with the help of mathematical modeling methods.The model takes into account basic physical correlations,material and thermal balances,phase equilibrium,and heat and mass transfer processes.The paper provides the results of mathematical modeling of the processes in a gas turbine and diesel engine power plant with thermochemical recuperation of the gas turbine exhaust gas heat by converting a hydrocarbon fuel.In such a plant,it is possible to reduce the specific fuel consumption of the diesel engine by 20%.The waste heat potential in a gas turbine can provide efficient hydrocarbon fuel conversion at the ratio of powers of the diesel and gas turbine engines being up to 6.When the diesel engine and gas turbine operate simultaneously with the use of the LNG vapor conversion products,the efficiency coefficient of the plant increases by 4%–5%.
文摘Presents the use of the similar transform and potential theory for calculation of the bypass flow factor and pressure gradient and the analysis of the influence of bypass flow factor and pressure gradient on heat transfer is analyzed, and the distribution of nose cone ablation obtained by combining the controlling equations of boundary layer, the compatible relation of interface and the heat conduction of interior.
基金supported by the State 973 Project(Grant No.2006CB202308)the National Natural Science Foundation of China(Grant No.40872097)
文摘Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin （CUTB） show that gas invasion at the late stage is accompanied by an increase of the contents of HeS and CO2 in natural gas, by the forming of the high total dissolved solids formation water, by an increase of the content of HCO3^-, relative to Cl^-, by an increase of the 2nd family ions （Ca^2＋, Mg^2＋, Sr^2＋ and Ba^2＋） and by a decrease of the content of SO4^2-, relative to Cl^-. The above phenomena can be explained only by way of thermochemicai sulfate reduction （TSR）. TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula： ∑CH＋CaSO4＋H-2O→H2S＋CO2＋CaCO3. （1） Dissolved SO4^2- in the formation water is consumed in the above reaction, when HeS and CO2 are generated, resulting in a decrease of SO4^2- in the formation water and an increase of both HeS and CO2 in the natural gas. If formation water exists, the generated CO2 will go on reacting with the carbonate to form bicarbonate, which can be dissolved in the formation water, thus resulting in the enrichment of Ca^2＋ and HCO3^-. The above reaction can be described by the following equation： CO2＋HeO＋CaCO3→Ca^2＋＋2HCO3^-. The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃, which is the minimum for TSR to occur. At the same time, dolomitization, which might be a direct result of TSR, has been found in both the Cambrian and the lower Ordovician. The above evidence indicates that TSR is in an active reaction, providing a novel way to reevaluate the exploration potentials of natural gas in this district.
文摘A theoretical methodology for thermochemical non-equilibrium flow combing with the HLLC(Harten-Lax-van Leer Contact) scheme was applied to study the hypersonic thermochemical non-equilibrium environment of an entry configuration in ionized flow. A two-temperature controlling model was utilized and the Gupta’s 11 species(N 2, O2, NO, O, N, NO+, N+2, O+2, N+, O+, e)thermochemical non-equilibrium model was taken. Firstly, numerical calculations of hypersonic thermochemical non-equilibrium environments for different aerodynamic shapes were carried out to verify the reliability of the method above. Then, the method was used to research the effects of ionization and wall catalysis on the hypersonic thermochemical non-equilibrium environment of the entry configuration in ionized flow. The shock stand-off distance can be reduced by thermochemical reactions but doesn’t continue to decrease significantly when ionization occurs. The shock stand-off distance calculated by the 11 species model is 4.2% smaller than that calculated by the 5 species(N2, O2, NO, O, N) thermochemical non-equilibrium model without considering ionization.Ionization reduces wall heat flux but increases wall pressure a little. The effect of ionization on aerothermal loads is greater than that of aerodynamic loads. The thermochemical reactions of electrons and ions catalyzed at the wall increase wall heat flux significantly but make a small change in wall pressure. The maximum wall heat flux obtained by only considering the electrons and ions catalyzed at the partially catalytic wall condition is 11.8% less than that calculated at the supercatalytic wall condition.
基金Project (No. 51006088) supported by the National Natural Science Foundation of China
文摘This study aimed to establish a closed-cycle operation technology with high thermal efficiency in the thermochemical sulfur-iodine cycle for large-scale hydrogen production.A series of experimental studies were performed to investigate the occurrence of side reactions in both the H2SO4 and HI x phases from the H2SO4/HI/I2/H2O quaternary system within a constant temperature range of 323-363 K.The effects of iodine content,water content and reaction temperature on the side reactions were evaluated.The results showed that an increase in the reaction temperature promoted the side reactions.However,they were prevented as the iodine or water content increased.The occurrence of side reactions was faster in kinetics and more intense in the H2SO4 phase than in the HI x phase.The sulfur or hydrogen sulfide formation reaction or the reverse Bunsen reaction was validated under certain conditions.
基金supported by the National Natural Sciences Foundation of China (20773034)the Natural Science Foundation of Hebei Province (B2007000237)
文摘A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔ θ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle...
基金financially supported by Australian Research Council(ARC)the National Natural Science Foundation of China(Grant Nos.51372248 and 51432009)
文摘Perovskite material is one of the promising classes of redox catalysts for hydrogen production through two-step ther-mochemical H20 splitting.Herein,an analogue of La1-xCaxMnO3 perovskite was systematically investigated as a catalyst for thermochemical H2 evolution.The Ca doping level（x = 0.2,0.4,0.6,0.8）and re-oxidation temperature were com-prehensively optimized for the improvement of catalytic performance.According to our experimental results,La0.6-Ca0.4MnO3 perovskite displayed the highest yield of H2 at the re-oxidation temperature of 900℃ and the obtained H2 production was -10 times higher than that of the benchmark ceria catalyst under the same experimental condition.More importantly,Lao.6Ca0.4MnO3 perovskite catalyst exhibited impressive cyclic stability in repetitive O2 and H2 test.
基金supported by the National Natural Science Foundation of China (No. 12172052)the China Postdoctoral Science Foundation (No. 3020036722021)
文摘The dynamic formation,shock-induced inhomogeneous temperature rise and corresponding chemical reaction behaviors of PTFE/Al reactive liner shaped charge jet(RLSCJ)are investigated by the combination of mesoscale simulation,reaction kinetics and chemical energy release test.A two-dimensional granular model is developed with the randomly normal distribution of aluminum particle sizes and the particle delivery program.Then,the granular model is employed to study the shock-induced thermal behavior during the formation and extension processes of RLSCJ,as well as the temperature history curves of aluminum particles.The simulation results visualize the motion and temperature responses of the RLSCJ at the grain level,and further indicate that the aluminum particles are more likely to gather in the last two-thirds of the jet along its axis.Further analysis shows that the shock,collision,friction and deformation behaviors are all responsible for the steep temperature rise of the reactive jet.In addition,a shock-induced chemical reaction extent model of RLSCJ is built based on the combination of the Arrhenius model and the Avrami-Erofeev kinetic model,by which the chemical reaction growth behavior during the formation and extension stages is described quantitatively.The model indicates the reaction extent highly corresponds to the aluminum particle temperature history at the formation and extension stages.At last,a manometry chamber and the corresponding energy release model are used together to study the macroscopic chemical energy release characteristics of RLSCJ,by which the reaction extent model is verified.
基金supported by the National Science Foundation for Excellent Young Scholars of China(21922815)the Key Research and Development(R&D)Projects of Shanxi Province(201903D121180)the National Key Research and Development(R&D)Program of China。
文摘Starch,as a typical polysaccharide with natural spherical morphology,is not only a preferred precursor for preparing carbon materials but also a model polymer for investigating thermochemical evolution mechanisms.However,starch usually suffers from severe foaming and low carbon yield during direct pyrolysis.Herein,we report a simple and eco-friendly dry strategy,by maleic anhydride initiating the esterification of starch,to design carbon microspheres against the starch foaming.Moreover,the infuence of ester grafting on the pyrolytic behavior of starch is also focused.The formation of ester groups in precursor guarantees the structural stability of starch-based intermediate because it can promote the accumulation of unsaturated species and accelerate the water elimination during pyrolysis.Meanwhile,the esterification and dehydration reactions greatly deplete the primary hydroxyl groups in the starch molecules and thus the rapid levoglucosan release is inhibited,which well keeps the spherical morphology of starch and ensures the high carbon yield.In further exploration as anode materials for Lithium-ion batteries,the obtained carbon microspheres exhibit good cyclability and rate performance with a reversible capacity of 444 m Ah g^(-1)at 50 m A g^(-1).This work provides theoretical fundamentals for the controllable thermal transformation of biomass towards wide applications.
基金financially co-supported by the National Natural Science Foundation of China(Nos.12002306,U20B2007,11572284 and 6162790014)National Numerical Wind Tunnel Project,China(No.NNW2019ZT3-A08)。
文摘To predict aeroheating performance of hypersonic vehicles accurately in thermochemical nonequilibrium flows accompanied by rarefaction effect,a Nonlinear Coupled Constitutive Relations(NCCR)model coupled with Gupta’s chemical models and Park’s two-temperature model is firstly proposed in this paper.Three typical cases are intensively investigated for further validation,including hypersonic flows over a two-dimensional cylinder,a RAM-C II flight vehicle and a type HTV-2 flight vehicle.The results predicted by NCCR solution,such as heat flux coefficient and electron number densities,are in better agreement with those of direct simulation Monte Carlo or flight data than Navier-Stokes equations,especially in the extremely nonequilibrium regions,which indicates the potential of the newly-developed solution to capture both thermochemical and rarefied nonequilibrium effects.The comparisons between the present solver and NCCR model without a two-temperature model are also conducted to demonstrate the significance of vibrational energy source term in the accurate simulation of high-Mach flows.
