Effect of long reaction distance on gas composition from organic-rich shale pyrolysis under high-temperature steam environment

When high-temperature steam is used as a medium to pyrolyze organic-rich shale,water steam not only acts as heat transfer but also participates in the chemical reaction of organic matter pyrolysis,thus affecting the generation law and release characteristics of gas products.In this study,based on a long-distance reaction system of organic-rich shale pyrolysis via steam injection,the effects of steam temperature and reaction distance on gas product composition are analyzed in depth and compared with other pyrolysis processes.The advantages of organic-rich shale pyrolysis via steam injection are then evaluated.The volume concentration of hydrogen in the gas product obtained via the steam injection pyrolysis of organic-rich shale is the highest,which is more than 60%.The hydrogen content increases as the reaction distance is extended;however,the rate of increase changes gradually.Increasing the reaction distance from 800 to 4000 mm increases the hydrogen content from 34.91%to 69.68%and from 63.13%to 78.61%when the steam temperature is 500℃ and 555℃,respectively.However,the higher the heat injection temperature,the smaller the reaction distance required to form a high concentration hydrogen pyrolysis environment(hydrogen concentration>60%).When the steam pyrolysis temperature is increased from 500℃ to 555℃,the reaction distance required to form a high concentration of hydrogen is reduced from 3800 to 800 mm.Compared with the direct retorting process,the volume concentration of hydrogen obtained from high-temperature steam pyrolysis of organic-rich shale is 8.82 and 10.72 times that of the commonly used Fushun and Kivite furnaces,respectively.The pyrolysis of organic-rich shale via steam injection is a pyrolysis process in a hydrogen-rich environment.

Effects of acid-rock reaction on physical properties during CO_(2)-rich industrial waste gas(CO_(2)-rich IWG)injection in shale reservoirs

"Carbon peaking and carbon neutrality"is an essential national strategy,and the geological storage and utilization of CO_(2)is a hot issue today.However,due to the scarcity of pure CO_(2)gas sources in China and the high cost of CO_(2)capture,CO_(2)-rich industrial waste gas(CO_(2)-rich IWG)is gradually emerging into the public's gaze.CO_(2)has good adsorption properties on shale surfaces,but acidic gases can react with shale,so the mechanism of the CO_(2)-rich IWG-water-shale reaction and the change in reservoir properties will determine the stability of geological storage.Therefore,based on the mineral composition of the Longmaxi Formation shale,this study constructs a thermodynamic equilibrium model of water-rock reactions and simulates the regularity of reactions between CO_(2)-rich IWG and shale minerals.The results indicate that CO_(2)consumed 12%after reaction,and impurity gases in the CO_(2)-rich IWG can be dissolved entirely,thus demonstrating the feasibility of treating IWG through water-rock reactions.Since IWG inhibits the dissolution of CO_(2),the optimal composition of CO_(2)-rich IWG is 95%CO_(2)and 5%IWG when CO_(2)geological storage is the main goal.In contrast,when the main goal is the geological storage of total CO_(2)-rich IWG or impurity gas,the optimal CO_(2)-rich IWG composition is 50%CO_(2)and 50%IWG.In the CO_(2)-rich IWG-water-shale reaction,temperature has less influence on the water-rock reaction,while pressure is the most important parameter.SO2 has the greatest impact on water-rock reaction in gas.For minerals,clay minerals such as illite and montmorillonite had a significant effect on water-rock reaction.The overall reaction is dominated by precipitation and the volume of the rock skeleton has increased by 0.74 cm3,resulting in a decrease in shale porosity,which enhances the stability of CO_(2)geological storage to some extent.During the reaction between CO_(2)-rich IWG-water-shale at simulated temperatures and pressures,precipitation is the main reaction,and shale porosity decreases.However,as the reservoir water content increases,the reaction will first dissolve and then precipitate before dissolving again.When the water content is less than 0.0005 kg or greater than 0.4 kg,it will lead to an increase in reservoir porosity,which ultimately reduces the long-term geological storage stability of CO_(2)-rich IWG.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Model Prediction and Optimal Control of Gas Oxygen Content for A Municipal Solid Waste Incineration Process

In the municipal solid waste incineration process,it is difficult to effectively control the gas oxygen content by setting the air flow according to artificial experience.To address this problem,this paper proposes an optimization control method of gas oxygen content based on model predictive control.First,a stochastic configuration network is utilized to establish a prediction model of gas oxygen content.Second,an improved differential evolution algorithm that is based on parameter adaptive and t-distribution strategy is employed to address the set value of air flow.Finally,model predictive control is combined with the event triggering strategy to reduce the amount of computation and the controller's frequent actions.The experimental results show that the optimization control method proposed in this paper obtains a smaller degree of fluctuation in the air flow set value,which can ensure the tracking control performance of the gas oxygen content while reducing the amount of calculation.

For more and purer hydrogen-the progress and challenges in water gas shift reaction

The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.

Experimental study on solid particle migration and production behaviors during marine natural gas hydrate dissociation by depressurization

Sand production is one of the main obstacles restricting gas extraction efficiency and safety from marine natural gas hydrate(NGH)reservoirs.Particle migration within the NGH reservoir dominates sand production behaviors,while their relationships were rarely reported,severely constrains quantitative evaluation of sand production risks.This paper reports the optical observations of solid particle migration and production from micrometer to mesoscopic scales conditioned to gravel packing during depressurization-induced NGH dissociation for the first time.Theoretical evolutionary modes of sand migration are established based on experimental observations,and its implications on field NGH are comprehensively discussed.Five particle migration regimes of local borehole failure,continuous collapse,wormhole expansion,extensive slow deformation,and pore-wall fluidization are proved to occur during depressurization.The types of particle migration regimes and their transmission modes during depressurization are predominantly determined by initial hydrate saturation.In contrast,the depressurization mainly dominates the transmission rate of the particle migration regimes.Furthermore,both the cumulative mass and the medium grain size of the produced sand decrease linearly with increasing initial methane hydrate(MH)saturation.Discontinuous gas bubble emission,expansion,and explosion during MH dissociation delay sand migration into the wellbore.At the same time,continuous water flow is a requirement for sand production during hydrate dissociation by depressurization.The experiments enlighten us that a constitutive model that can illustrate visible particle migration regimes and their transmission modes is urgently needed to bridge numerical simulation and field applications.Optimizing wellbore layout positions or special reservoir treatment shall be important for mitigating sand production tendency during NGH exploitation.

A COMPUTERIZED SYSTEM ON KINETIC ANALYSIS AND EVALUATION OF GAS/SOLID REACTIONS

The present paper presents the structure, features and functions of a computerized system on kinetic analysis and evaluation of gas/solid reactions, KinPreGSR. Kin-PreGSR is a menu driven system, can be operated with MS Windows as workbench in a PC computer. It has been developed using visual C++ with FoxPro hybrid coding technique.KinPreGSR combines the characteristics of gas/solid reactions with the kinetic models as well as mass and heat transfer equations. The database files were established for the apparent activation energies of some reduction and decomposition reactions to allow the prediction of the reaction kinetics to some extents. Outputs can be displayed using graphical or numerical forms. Examples regarding the oxide reduction and carbonate decomposition under isothermal conditions are given to show those functions.

Process intensification in gas/liquid/solid reaction in trickle bed reactors: A review

As an important form of reactors for gas/liquid/solid catalytic reaction,trickle bed reactors (TBRs) are widely applied in petroleum industry,biochemical,fine chemical and pharmaceutical industries because of their flexibility,simplicity of operation and high throughput.However,TBRs also show inefficient production and hot pots caused by non-uniform fluid distribution and incomplete wetting of the catalyst,which limit their further application in chemical industry.Also,process intensification in TBRs is necessary as the decrease in quality of processed crude oil,caused by increased exploitation depths,and more restrictive environmental regulations and emission standards for industry,caused by increased environment protection consciousness.In recent years,lots of strategies for process intensification in TBRs have been proposed to improve reaction performance to meet the current and future demands of chemical industry from the environmental and economic perspective.This article summarizes the recent progress in techniques for intensifying gas/liquid/solid reaction in TBRs and application of intensified TBRs in petroleum industry.

Understanding fundamentals of electrochemical reactions with tender X-rays:A new lab-based operando X-ray photoelectron spectroscopy method for probing liquid/solid and gas/solid interfaces across a variety of electrochemical systems

Electrocatalysis is key to improving energy efficiency,reducing carbon emissions,and providing a sustainable way of meeting global energy needs.Therefore,elucidating electrochemical reaction mechanisms at the electrolyte/electrode interfaces is essential for developing advanced renewable energy technologies.However,the direct probing of real-time interfacial changes,i.e.,the surface intermediates,chemical environment,and electronic structure,under operating conditions is challenging and necessitates the use of in situ methods.Herein,we present a new lab-based instrument commissioned to perform in situ chemical analysis at liquid/solid interfaces using ambient pressure X-ray photoelectron spectroscopy(APXPS).This setup takes advantage of a chromium source of tender X-rays and is designed to study liquid/solid interfaces by the“dip and pull”method.Each of the main components was carefully described,and the results of performance tests are presented.Using a three-electrode setup,the system can probe the intermediate species and potential shifts across the liquid electrolyte/solid electrode interface.In addition,we demonstrate how this system allows the study of interfacial changes at gas/solid interfaces using a case study:a sodium–oxygen model battery.However,the use of APXPS in electrochemical studies is still in the early stages,so we summarize the current challenges and some developmental frontiers.Despite the challenges,we expect that joint efforts to improve instruments and the electrochemical setup will enable us to obtain a better understanding of the composition–reactivity relationship at electrochemical interfaces under realistic reaction conditions.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.

Numerical Simulation on Gas-Solid Two-Phase Turbulent Flow in FCC Riser Reactors(Ⅰ) Turbulent Gas-Solid Flow-Reaction Model

Gas-solid two-phase turbulent flows,mass transfer,heat transfer and catalytic cracking reactions areknown to exert interrelated influences in commercial fluid catalytic cracking(FCC)riser reactors.In the presentpaper,a three-dimensional turbulent gas-solid two-phase flow-reaction model for FCC riser reactors was devel-oped.The model took into account the gas-solid two-phase turbulent flows,inter-phase heat transfer,masstransfer,catalytic cracking reactions and their interrelated influence.The k-V-k_P two-phase turbulence modelwas employed and modified for the two-phase turbulent flow patterns with relatively high particle concentration.Boundary conditions for the flow-reaction model were given.Related numerical algorithm was formed and a nu-merical code was drawn up.Numerical modeling for commercial FCC riser reactors could be carried out with thepresented model.

Decouple charge transfer reactions in the Li-ion battery

In the development of Li-ion batteries(LIBs)with high energy/power density,long cycle-life,fast charging,and high safety,an insight into charge transfer reactions is required.Although electrochemical impedance spectroscopy(EIS)is regarded as a powerful diagnosis tool,it is not a direct but an indirect measurement.With respect to this,some critical questions need to be answered:(i)why EIS can reflect the kinetics of charge transfer reactions;(ii)what the inherent logical relationship between impedance models under different physical scenes is;(iii)how charge transfer reactions compete with each other at multiple scales.This work aims at answering these questions via developing a theory framework so as to mitigate the blindness and uncertainty in unveiling charge transfer reactions in LIBs.To systematically answer the above questions,this article is organized into a three-in-one(review,tutorial,and research)type and the following contributions are made:(i)a brief review is given for impedance model development of the LIBs over the past half century;(ii)an open source code toolbox is developed based on the unified impedance model;(iii)the competive mechanisms of charge transfer reactions are unveiled based on the developed EIS-Toolbox@LIB.This work not only clarifies theoretical fundamentals,but also provides an easy-to-use open source code for EIS-Toolbox@LIB to optimize fast charge/discharge,mitigate cycle aging,and improve energy/power density.

Insights into the hydrogen evolution reaction in vanadium redox flow batteries:A synchrotron radiation based X-ray imaging study

The parasitic hydrogen evolution reaction(HER)in the negative half-cell of vanadium redox flow batteries(VRFBs)causes severe efficiency losses.Thus,a deeper understanding of this process and the accompanying bubble formation is crucial.This benchmarking study locally analyzes the bubble distribution in thick,porous electrodes for the first time using deep learning-based image segmentation of synchrotron X-ray micro-tomograms.Each large three-dimensional data set was processed precisely in less than one minute while minimizing human errors and pointing out areas of increased HER activity in VRFBs.The study systematically varies the electrode potential and material,concluding that more negative electrode potentials of-200 m V vs.reversible hydrogen electrode(RHE)and lower cause more substantial bubble formation,resulting in bubble fractions of around 15%–20%in carbon felt electrodes.Contrarily,the bubble fractions stay only around 2%in an electrode combining carbon felt and carbon paper.The detected areas with high HER activity,such as the border subregion with more than 30%bubble fraction in carbon felt electrodes,the cutting edges,and preferential spots in the electrode bulk,are potential-independent and suggest that larger electrodes with a higher bulk-to-border ratio might reduce HER-related performance losses.The described combination of electrochemical measurements,local X-ray microtomography,AI-based segmentation,and 3D morphometric analysis is a powerful and novel approach for local bubble analysis in three-dimensional porous electrodes,providing an essential toolkit for a broad community working on bubble-generating electrochemical systems.

Nitriding of Medium Carbon Ferromanganese Alloy in Gas Solid Reaction

Nitriding process of medium carbon ferromanganese was carried out in the solid state, on lab and bench scale at temperature range 1023-1323 K using different nitrogen and hydrogen pressures. The influence of H2/N2 gas ratio, temperature and time on nitriding process of fine (-2 mm) medium carbon ferromanganese were investigated. Nitrogen content, in weight percent ranging from 2.1 to 9.7 could be obtained. The optimum temperature and time of nitriding process was found to be 1223 K and 21.6 ks respectively. The results showed that nitrogen content is mainly depending on time and temperature of nitriding process. The comparison between results of lab and bench scale, at optimum conditions, showed good coincidence. At optimum conditions;1223 K, 21.6 ks and at 2/8 of H2/N2, nitrogen content of fine medium carbon ferromanganese was 9.5%.

Thermochemical Heat Storage Performance in the Gas/Liquid-Solid Reactions of SrCl2 with NH3

Thermochemical heat storage is a promising technology for improving energy efficiency through the utilization of low-grade waste heat. The formation of a SrCl2 ammine complex was selected as the reaction system for the purpose of this study. Discharge characteristics were evaluated in a packed bed reactor for both the gas-solid reaction and the liquid-solid reaction. The average power of the gas-solid reaction was influenced by the pressure of the supplied ammonia gas, with greater powers being recorded at higher ammonia pressure. For the liquid-solid reaction, the obtained average power was comparable to that obtained for the gas-solid reaction at 0.2 MPa. Moreover, the lower heat transfer resistance in the reactor was observed, which was likely caused by the presence of liquid ammonia in the system. Finally, the short-term durability of the liquid-solid reaction system was demonstrated over 10 stable charge/discharge cycles.

Criterion of gas and solid dual-phase flow atomization crash in molten metal

A self-invented atomization process, in which molten metal is atomized into powder by a high-velocity gas stream carrying solid particles as the atomization medium, was introduced. The characteristics of powders prepared by common gas atomization and dual-phase flow atomization under similar conditions were compared. The experimental results show that the dual-phase flow-atomized powders have average particle sizes that are one-half that of the common gas-atomized particles;additionally, they possess a finer microstructure and higher cooling rate under the same atomization gas pressure and the same gas flow. The Weber number in the crash criteria of liquid atomization is adopted to measure the crash ability of the atomization media. The Weber number of the dual-phase flow atomization medium is the sum of that of the gas and the solid particles. Furthermore, the critical equation of the crash model in dual-phase flow atomization is established, and the main regularities associated with this process were analyzed.

Microwave direct synthesis and thermoelectric properties of Mg_(2)Si by solid-state reaction

In order to reduce the oxidation and volatilization caused by Mg element in the traditional methods for synthesizing Mg2Si compounds,Mg2Si thermoelectric materials were prepared by solid state reaction and microwave radiation techniques.Structure and phase composition of the materials were investigated by X-ray diffraction.The electrical conductivity,Seebeck coefficient and thermal conductivity were measured as a function of temperature from 300 to 700 K.It is found that high purity Mg2Si powders can be obtained with excessive content of 8% Mg from the stoichiometric Mg2Si at 853 K and 2.5 kW for 30 min.A maximum dimensionless figure of merit,ZT,of about 0.13 was obtained for Mg2Si at 600 K.

Amine-grafted on lanthanide metal-organic frameworks:Three solid base catalysts for Knoevenagel condensation reaction

A post-synthetic modification strategy has been used to prepare three solid base catalysts, including Er（btc）（ED）075（H2O）0.25 （2, btc = 1,3,5-benzenetricarboxylates, ED = 1,2-ethanediamine）, Er（btc）（PP）0.55（H20）0.45 （3, PP = piperazine）, and Er（btc）（DABCO）0.15（H2O）0.85 （4, DABCO = 1,4- diazabicyclo[2.2.2]octane）, by grafting three different diamines onto the coordinatively unsaturated Er（III） ions into the channels of the desolvated lanthanide metal-organic framework （Er（otc））. The resulting metal-organic frameworks were characterized by elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and N2 adsorption. Based on its higher loading ratio of the diamine, as well as its greater stability and porosity, catalyst 2 exhibited higher catalytic activity and reusability than catalysts 3 and 4- for the Knoevenagel condensation reaction. The catalytic mechanism of 2 has also been investigated using size-selective catalysis tests.

Supercritical-hydrothermal accelerated solid state reaction route for synthesis of LiMn_2O_4 cathode material for high-power Li-ion batteries

Synthesis of the spinel structure lithium manganese oxide （LiMn2O4） by supercritical hydrothermal （SH） accelerated solid state reaction （SSR） route was studied. The impacts of the reaction pressure, reaction temperature and reaction time of SH route, and the calcination temperature of SSR route on the purity, particle morphology and electrochemical properties of the prepared LiMn2O4 materials were studied. The experimental results show that after 15 min reaction in SH route at 400 ℃ and 30 MPa, the reaction time of SSR could be significantly decreased, e.g. down to 3 h with the formation temperature of 800 ℃, compared with the conventional solid state reaction method. The prepared LiMn2O4 material exhibits good crystallinity, uniform size distribution and good electrochemical performance, and has an initial specific capacity of 120 mA.h/g at a rate of 0.1C （1C=148 mA/g） and a good rate capability at high rates, even up to 50C.

Preparation of Nitrogen-Doped Carbon Catalyst to Oxygen Reduction Reaction and Influence of Protective Gas Flowing on Its Activity

A non-precious metal catalyst MnHMTA/C to oxygen reduction reaction was prepared by py- rolyzing a precursor from manganese chloride, hexamethylenetetramine and acetylene black in nitrogen gas atmosphere. The effect of heat treatment temperature and flowing of nitrogen gas were investigated. A catalyst with the highest activity can be obtained at 700 ℃. Mn（Ⅱ） ion was changed to MnO in heat treatment, which improved the catalytic activity of the catalyst. Hexamethylenetetramine takes part in the formation of active site of the catalyst as its decomposed gases. The flowing of protective gas takes the decomposed gases out of the tube furnace and brings negative effect on the catalytic activity of the MnHMTA/C catalyst.