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

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

Novel sandwich structured glass fiber Cloth/Poly(ethylene oxide)-MXene composite electrolyte

Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.

Heterogeneous dynamic modeling and simulation of an industrial ethylene oxide reactor experiencing catalyst deactivation

This paper investigates steady-state and dynamic simulation of an industrial fixed-bed ethylene oxide reactor. A mathematical heterogeneous one-dimensional model is developed for simulation of reactor performance in the presence of long term deactivation of silver/a-alumina catalyst. In this paper, steady-state model of the reactor is solved and results of steady state simulation are fed to dynamic simulator as initial condition. When results of dynamic simulation are compared with industrial reactor data, it is found that there were good agreements between simulation results and industrial data. The proposed model is also validated by industrial process data for a period of 1100 operating days.

Synthesis and Characterization of Multi-block(β)±butyrolactone(BL)-ethylene Oxide(EO) Copolymer

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Effects of Hydrophobicity of Ethylene Oxide-Propylene Oxide Copolymers on Phase Diagrams of Aqueous Two-Phase Systems and Partition Behaviors of Cephalexin and 7-Aminodeacetoxicephalos-poranic Acid

A series of ethylene oxide (EO)-propylene oxide (PO) randomco-polymers (EOPO) were used to form aqueous two-phase systems (ATPS)with ammonium sulfate. Effects of EOPO's properties on the phaseseparation behaviors and on the partition of cephalexin and7-aminodesacetoxicephalosporanic acid (7-ADCA) in ATPS wereinvestigated. Both the molar mass and molar ratio of EO to PO of EOPOcould greatly influence partition behaviors of cephalexin and 7-ADCAas well as the binodal curve of ATPS.

Formation mechanism of micro-flows in aqueous poly(ethylene oxide) droplets on a substrate at different temperatures

The drying of aqueous poly（ethylene oxide） （PEO） droplet on a substrate at different temperatures was studied. It was found that the contact line receded when the substrate was at a temperature above 60 ℃. Different nucleation behavior and surface profiles of PEO films were found in different droplets drying processes. The rheological properties of aqueous PEO solutions were studied to understand the mechanism of contact line recession and micro-flow in drying aqueous PEO droplets. It was found that at low temperature, the contact line was static because of great viscous stress; while at high temperature, it receded because of great Marangoni force and the decrease of viscous stress. It was indicated that Marangoni convection was inhibited by the outward capillary flow and viscous stress at low temperature, whereas it became dominant at high temperature. Two types of mechanism for surface profiles and nucleation of PEO film from drying droplets are proposed, providing a theoretical guide for polymer solution application in oil and gas foam flooding technology.

Simultaneous generation of electricity, ethylene and decomposition of nitrous oxide via protonic ceramic fuel cell membrane reactor

Ethylene,one of the most widely produced building blocks in the petrochemical industry,has received intense attention.Ethylene production,using electrochemical hydrogen pump-facilitated nonoxidative dehydrogenation of ethane(NDE)to ethylene,is an emerging and promising route,promoting the transformation of the ethylene industry from energy-intensive steam cracking process to new electrochemical membrane reactor technology.In this work,the NDE reaction is incorporated into a BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)electrolyte-supported protonic ceramic fuel cell membrane reactor to co-generate electricity and ethylene,utilizing the Nb and Cu doped perovskite oxide Pr_(0.6)Sr_(0.4)Fe_(0.8)Nb_(0.1)Cu_(0.1)O_(3-δ)(PSFNCu)as anode catalytic layer.Due to the doping of Nb and Cu,PSFNCu was endowed with high reduction tolerance and rich oxygen vacancies,showing excellent NDE catalytic performance.The maximum power density of the assembled reactor reaches 200 mW cm^(-2)at 750℃,with high ethane conversion(44.9%)and ethylene selectivity(92.7%).Moreover,the nitrous oxide decomposition was first coupled in the protonic ceramic fuel cell membrane reactor to consume the permeated protons.As a result,the generation of electricity,ethylene and decomposition of nitrous oxide can be simultaneously obtained by a single reactor.Specifically,the maximum power density of the cell reaches 208 mW cm^(-2)at 750℃,with high ethane conversion(45.2%),ethylene selectivity(92.5%),and nitrous oxide conversion(19,0%).This multi-win technology is promising for not only the production of chemicals and energy but also greenhouse gas reduction.

DFT Study of Mechanism of Extraction Reaction Between Germylene Carbene （H2Ge=C：） and Its Derivatives and Ethylene Oxide

The mechanism of the oxide extraction reaction between singlet germylene carbene and its derivatives X2Ge=C： （X=H, F, Cl, CH3） and ethylene oxide has been investigated with B3LYP/6-311G（d,p） method. The results show that this kind of reaction has similar mechanism, the shift of 2p lone electron pair of O in ethylene oxide to the 2p unoccupied orbital of C in X2Ge=C： gives a p→p donor-acceptor bond, thereby leading to the formation of intermediate. As the p→p donor-acceptor bond continues to strengthen, that is the C-O bond continues to shorten, the intermediate generates product （P＋C2H4） via transition state. It is the substituent electronegativity that mainly affect the extraction reactions. When the substituent electronegativity is greater, the energy barrier is lower, and the reaction rate is greater.

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

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

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

Hydrogen Sulfide May Function Downstream of Nitric Oxide in Ethylene-Induced Stomatal Closure in Vicia faba L.

Pharmacological, laser scanning confocal microscopic （LSCM）, and spectrophotographic approaches were used to study the roles of hydrogen sulfide （H2S） and nitric oxide （NO） in signaling transduction of stomatal movement in response to ethylene in Viciafaba L. Ethylene treatment resulted in the dose-dependent stomatal closure under light, and this effect was blocked by the inhibitors of H2S biosynthesis in V. faba L. Additionally, ethylene induces H2S generation and increases L-/D-cysteine desulfhydrase （pyridoxalphosphate-dependent enzyme） activity in leaves of V. faba L. Inhibitors of H2S biosynthesis have no effect on the ethylene-induced stomatal closure, NO accumulation, and nitrate reductase （NR） activity in guard cells or leaves of II. faba L. Moreover, the ethylene-induced increase of H2S levels and L-/D- cysteine desulfhydrase activity declined when NO generation was inhibited. Therefore, we conclude that H2S and NO probably are involved in the signal transduction pathway of ethylene-induced stomatal closure. H2S may represent a novel component downstream of NO in the ethylene-induced stomatal movement in V. faba L.

RANDOM COPOLYMER OF PROPYLENE OXIDE AND ETHYLENE OXIDE PREPARED BY DOUBLE METAL CYANIDE COMPLEX CATALYST

Copolymerization of propylene oxide (PO) and ethylene oxide (EO) using double metal cyanide (DMC) complex as the catalyst was carried out. The structure of random copolymers was confirmed by C-13-NMR and IR spectra. H-1-NMR analysis shows that the EO content in the copolymer is the same as that in the initial monomer feed. Moderate molecular weight copolymers with various EO content were obtained and their values of molecular weight distribution (MWD) fell in the range of 1.21-1.55. It was found that the molecular weight of copolymers is controlled by the mass ratio of EO+PO to initiator moles used, The reaction rate as well as polymer yield decrease with increasing EO content in the feed composition.

RING OPENING COPOLYMERIZATION OF SUCCINIC ANHYDRIDE-ETHYLENE OXIDE BY Al(Ⅲ) ORGANOMETALLIC CATALYSTS

Ring opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO)was successfully carried out by using a series of aluminum-based catalyst in 1,4-dioxane at62±2℃. The results showed that in-situ AlR_3-H_2O (R=ethyl, iso-butyl) catalysts gavehigher molecular weight (M_w～10~4), while Al(OR)_3 catalysts gave the higher alternatingcopolymer structure with slightly lower molecular weight. The in-situ AlR_3-H_2O systemshave been evaluated in more detail for the reaction which showed the optimum H_2O/Almolar ratio to be 0.5. The copolymers with different composition (F_(SA)/F_(EO)= 36/64to 45/55 mol/mol) were synthesized by using different monomer feed ratio. The melt-ing point (T_m), glass transition temperature (T_g) and enthalpy of fusion (ΔH_f) of thesecopolymers are depended on the copolymer composition and in the range of 87～102℃,-12～-18℃, and 37～66J/g, respectively. The second heating scan of DSC also in-dicated that the higher alternating copolymer was more easily recrystallized. The onsetdecomposition temperature was more than 300℃ under nitrogen and influenced by thecopolymer composition.

Effects of Nitric Oxide and Exogenous Ethylene Treatments on Ethylene Biosynthesis in Feicheng Peach

The effects of nitric oxide （NO） and exogenous ethylene on ethylene biosynthesis in harvested Feicheng peaches were studied. The antagonistic actions between NO and exogenous ethylene was also investigated. The Feicheng peaches were fumigated with 10μL L^-1 NO, 1 000 μL L^-1 ethylene, or 10 μL L^-1 NO plus 1 000 μL L^-1 ethylene for 3 h. The results suggested that application of exogenous ethylene promoted the biosynthesis of endogenous ethylene in peach fruit. The treatment with NO remarkably inhibited the biosynthesis of ethylene by significantly reducing the activities of ACC synthase （ACS） and ACC oxidase （ACO）. Ethylene biosynthesis in the fruits treated with both NO and exogenous ethylene was lower than that in fruits treated with exogenous ethylene alone but higher than that in fruits treated with NO alone, suggesting that there were antagonistic actions between NO and exogenous ethylene. NO could inhibit the biosynthesis of ethylene and the catalysis of exogenous ethylene during ethylene biosynthesis in peach fruits.

SYNTHESIS AND CHARACTERIZATION OF AMPHIPHILIC GRAFT COPOLYMER CONTAINING MICROPHASE SEPARATED AND LONG POLY(ETHYLENE OXIDE) SIDE CHAIN STRUCTURES

Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.

Enhanced Electrochemical Performance of Poly(ethylene oxide)Composite Polymer Electrolyte via Incorporating Lithiated Covalent Organic Framework

The lithiated covalent organic framework(named TpPa-SO_(3) Li),which was prepared by a mild chemical lithiation strategy,was introduced in poly(ethylene oxide)(PEO)to produce the composite polymer electrolytes(CPEs).Li-ion can transfer along the PEO chain or across the layer of TpPa-SO_(3) Li within the nanochannels,resulting in a high Li-ion conductivity of3.01×10^(-4)S/cm at 60℃.When the CPE with 0.75 wt.%TpPa-SO_(3) Li was used in the LiFePO_(4)‖Li solid-state battery,the cell delivered a stable capacity of 125 mA·h/g after 250 cycles at 0.5 C,60℃.In comparison,the cell using the CPE without TpPa-SO_(3) Li exhibited a capacity of only 118 mA·h/g.

Analysis of residual crosslinking agent content in UV cross-linked poly(ethylene oxide) hydrogels for dermatological application by gas chromatography

Acrylates have been widely used in the synthesis of pharmaceutical polymers. The quantitation of residual acrylate monomers is vital as they are strong irritants and allergens, but after polymerization, are relatively inert, causing no irritation and allergies. Poly(ethylene oxide)(PEO) hydrogels were prepared using pentaerythritol tetra-acrylate(PETRA) as UV crosslinking agent. A simple, accurate, and robust quantitation method was developed based on gas chromatographic techniques(GC), which is suitable for routine analysis of residual PETRA monomers in these hydrogels. Unreacted PETRA was initially identified using gas chromatography–mass spectrometry(GC–MS). The quantitation of analyte was performed and validated using gas chromatography equipped with a flame ionization detector(GC–FID). A linear relationship was obtained over the range of 0.0002%–0.0450%(m/m) with a correlation coefficient(r2)greater than 0.99. The recovery( 4 90%), intra-day precision(%RSD o 0.67), inter-day precision(%RSD o2.5%), and robustness(%RSD o1.62%) of the method were within the acceptable values. The limit of detection(LOD) and limit of quantitation(LOQ) were 0.0001%(m/m) and 0.0002%(m/m), respectively.This assay provides a simple and quick way of screening for residual acrylate monomer in hydrogels.

Laminar Composite Solid Electrolyte with Poly(Ethylene Oxide)-Threaded Metal-Organic Framework Nanosheets for High-Performance All-Solid-State Lithium Battery

Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.

Advances in high carbon dioxide separation performance of poly(ethylene oxide)-based membranes

Poly(ethylene-oxide)(PEO)-based membranes have attracted much attention recently for CO2 separation because CO2 is highly soluble into PEO and shows high selectivity over other gases such as CH4 and N2.Unfortunately,those membranes are not strong enough mechanically and highly crystalline,which hinders their broader applications for separation membranes.In this review discussions are made,as much in detail as possible,on the strategies to improve gas separation performance of PEO-based membranes.Some of techniques such as synthesis of graft copolymers that contain PEO,cross-linking of polymers and blending with long chains polymers contributed significantly to improvement of membrane.Incorporation of ionic liquids/nanoparticles has also been found effective.However,surface modification of nanoparticles has been done chemically or physically to enhance their compatibility with polymer matrix.As a result of all such efforts,an excellent performance,i.e.,CO2 permeability up to 200 Barrer,CO2/N2 selectivity up to 200 and CO2/CH4 selectivity up to 70,could be achieved.Another method is to introduce functional groups into PEO-based polymers which boosted CO2 permeability up to 200 Barrer with CO2/CH4 selectivity between 40 and 50.The CO2 permeability of PEO-based membranes increases,without much change in selectivity,when the length of ethylene oxide is increased.

Synthesis and cost estimation of ethylene oxide process using PRO/Ⅱ

Ethylene oxide （EO） is a sold-out intermediate material for producing various chemicals.Major chemical companies are interested in whether new EO plant can create profit.This research is undertaken to investigate the economic feasibility of EO production.Direct oxidation of ethylene using silver on alpha-A12O3 catalyst type is adapted to produce EO of 60 000 t/year.We conduct the conceptual design.Firstly,we synthesize the optimal structure and then determine optimal conditions and the size of the equipments.Feasibility study shows that profit and loss turning point turns out to be 3.2 years based on the present market price.In addition,we conducts the economic analysis to prepare the risk of raw material market price variation ranging from 70％ to 130％.