Insight into the topology effect on the diffusion of ethene and propene in zeolites: A molecular dynamics simulation study

Selectivity control is a difficult scientific and industrial challenge in methanol-to-olefins(MTO)conversion.It has been experimentally established that the topology of zeolite catalysts influenced the distribution of products.Besides the topology effect on reaction kinetics,the topology influences the diffusion of reactants and products in catalysts as well.In this work,by using COMPASS force-field molecular dynamics method,we investigated the intracrystalline diffusion of ethene and propene in four different zeolites,CHA,MFI,BEA and FAU,at different temperatures.The self-diffusion coefficients and diffusion activation barriers were calculated.A strong restriction on the diffusion of propene in CHA was observed because the self-diffusion coefficient ratio of ethene to propene is larger than 18 and the diffusion activation barrier of propene is more than 20 kJ/mol in CHA.This ratio decreases with the increase of temperature in the four investigated zeolites.The shape selectivity on products from diffusion perspective can provide some implications on the understanding of the selectivity difference between HSAPO-34 and HZSM-5 catalysts for the MTO conversion.

Effect of Reaction Temperature and Pressure on the Metathesis Reaction between Ethene and 2-Butene to Propene on the WO_3/Al_2O_3-HY Catalyst

Effect of reaction temperature and pressure on the metathesis reaction between ethene and 2-butene to propene was studied on the WO3/γ-Al2O3-HY catalyst. The activity is found to increase with elevated temperature and reaches a plateau at 150-240 ℃. After that, the activity undergoes a remarkable decrement at too high temperature. The effect of temperature is elucidated by the oxidation state of tungsten species. The evaluation results also indicate that the stability is dependent on this reaction parameter. Medium pressure （0.5-0.8 MPa） is favorable for stability, while atmospheric pressure or too high pressure （〉1.0 MPa） deteriorates the stability. For explanation, UV Vis, FT-IR, O2-TPO, and TG techniques are used to characterize the spent catalysts.

Cross metathesis of butene-2 and ethene to propene overMo/MCM-22-Al_2O_3 catalysts with different Al_2O_3 contents

A series of 3.0Mo/MCM-22-Al2O3 catalysts with γ-Al2O3 contents in the range of 0-100 wt% were prepared and applied in the metathesis reaction of ethene and butene-2. Addition of γ-Al2O3did not affect the structure of MCM-22 zeolite as evidenced by XRD and N2 adsorption measurements. It was deduced from TPR experiments that γ-Al2O3 phase favored the formation of polymolybdate or multilayered Mo oxide, while more Al2（MoO4）3 species were generated over MCM-22 zeolites. Alumina content in the support was directly related to the metathesis activity of ethene and butene-2 to propene. Mo species with higher valence （Mo6＋or Mo5＋） contributed more to the excellent performance of catalyst than metallic Mo. The best catalyst activity and stability was obtained over 3.0Mo/（MCM-22-30%Al2O3） under the reaction condition of 1.0 MPa and 125℃ using N2 as the pretreatment gas.

Oxidative dehydrogenation of ethane to ethene over a superbase supported LiCl system

LiCl-promoted superbase catalysts were found to be stable and highly selective to ethene for oxidative dehydrogenation of ethane,giving 84%ethane conversion and 74%ethene yield at 923 K.Results indicated that the stronger the basicity of LiC1-based catalysts,the better the catalytic performance.

The Influence of Temperature on Ethene Diffusion in HZSM-5 Studied by Molecular Dynamics

Molecular dynamics(MD) simulation of ethene diffusion in the lattice of HZSM 5 was performed at the temperature ranging from 300 K to 700 K. The calculated diffusion coefficients increase with the temperature from 2.60×10 -9 m 2/s at 300 K to 12.78×10 -9 m 2/s at 700 K. The Arrhenius plot gives an activation energy of 6.31 kJ/mol . The anisotropy of the diffusion process was examined.

ON NONEQUILIBRIUM OF PYROLYSIS PROCESS IN THE MANUFACTURE OF ETHENE

Nonequilibrium process for cracking ethane and n-buthane in the manufacture of ethene has been analytically and numerically investigated in a Heaviside function temperature field and through a normal shock wave. The results demonstrate that, while the reaction temperature increases, the maximum value of ethene yield is increased, and the optimal reaction duration is sharply shortened. For the identical initial reaction temperature, the maximum value of ethene yield through a stationary normal shock wave is less than that in a Heaviside function temperature field. However, the ethene consumption after the maximum value in the former case is less than that in the latter. Higher ethene yield will be obtained by using the gasdynamic heating method than by using the current methods. (Edited author abstract) 5 Refs.

Solid-Phase Stereoselective Synthesis of(E)-1,2-Disubstituted Ethenes from Polymer-Sopportedα-Selenoaldehydes

Reaction of polymer-supported a-selenoaldehydes with Grignard reagents afforded polymer-bound B-hydroxyalkyl selenides, which treated with thionyl chloride and triethylamine leading to (E)-1, 2-disubstituted ethenes in good yield.

Direct Oxidation of Ethene to Acetic Acid

Direct oxidation of ethene to acetic acid over Pd-SiW12/SiO2 catalysts prepared by several methods was studied. A better method for reducing palladium composition of the catalysts was found. Acetic acid was obtained with selectivity of 82.7% and once-through space time yield (STY) of 257.4 g/h .L.

Qilu Petrochem Ethene Installation Hits Target Ahead of Schedule

TheetheneinstallationofQiluPetrochemCorp.,akeyStateproject,hasproduced450,000tonsofethylenethisyear,achievingtheafter-transformationannualproductioncapacity30daysaheadofschedulewithallthemajortechnicalindicessettinghistoricalrecords.Thustheinstallati...

Experimental Investigation on Hydrothermal Reduction of Sulfates to H₂S and Organic Sulfides by Ethene

The kinetic characteristics of alkenes involved in thermochemical sulfate reduction (TSR) have been never reported in geological literature. In this study, TSR by ethene under hydrothermal conditions was performed in the constrained simulation experiments. Typical TSR products consisted of H2S, CO2, mercaptans, sulfides, thiophenes derivatives and benzothiophene. The apparent activation energy E and apparent frequency factor A for TSR by ethene were determined as 76.370 kJ/mol and 4.579 s-1, respectively. The lower activation energy for ethene involved in TSR relative to ethane suggested that the reactivity of ethene is much higher than that of ethane, in accordance with the thermodynamic analysis. Rate constants were determined experimentally using first-order kinetics extrapolate to MgSO4 half-lives of 67.329 years - 3.053 years in deep burial diagenetic settings (120°C - 180°C). These values demonstrate that the reaction rate for TSR by ethene is extraordinarily fast in high-temperature gas reservoirs (120°C - 180°C). Consequently, the newly formed ethene from thermal cracking and TSR alteration of natural gas and/or petroleum could not survive after TSR process and were rarely detected in natural TSR reservoirs.

Influences of Brnsted Acidic Sites in HZSM-5 on Polarization and Electronegativity of Ethene Studied by Molecular Dynamics

Molecular dynamics simulation has been performed for studying thepolarization and electronegativity of ethene molecules near Broensted acidic sites in H[Al] ZSM-5.The result shows that the molecules are polarized most at the edges of intersections and least atthe segments of channels. On the contrary, the highest global molecular electronegativity is foundat the centers of channel segments. Al substitution slightly increases the molecular dipole moment,but hardly affects the molecular electronegativity. Broensted acidic proton decreases the dipolemoment of guest molecule, but increases the molecular elec-tronegativity.

Molecular dynamics simulation of ethene adsorption,polarization and diffusion in three kinds of zeolites

Molecular dynamics （MD） simulation was performed to study ethene adsorption, polarization and diffusion in orthorhombic and monoclinic MFI and H[Al] ZSM-5 at 300 K. The resuits show that the interaction between ethene molecule and orthorhombic MFI is the strongest.Ethene molecules possess relatively low energy in the lattice of orthorhombic MFI. The existence of Al and Brnsted H atoms in the framework of H[AI]ZSM-5 can lower the energy of adsorbed ethene molecules. At the edges of intersections of channels, especially those near Al sites,ethene molecules are polarized most. Ethene molecules prefer the locations at the centers of channel intersections. The diffusion coefficients of ethene in the lattices of orthorhombic, monoclinic MFI and H[AI]ZSM-5 are 2.7 x 10-9, 2.1 x l0-9, 1.6 x 10-9 m2·s-1, respectively. The infrared spectrum of ethene in the framework of H[Al] ZSM-5 shows five vibration peaks (v10,v7, v12, v11 and V9), which is consistent with the experimental result.

Photochromism of cis(z)-1,2-bispyrryl-substituted ethene derivatives

Photochromism of two bispyrryl-substituted ethenes, 2, 3-bis-(1-p-methoxyphenyl-5-phenyl-2-methyl-3-pyrryl)-2-butene (BPE1) and 2,3-bis(1-p-bromophenyl-4-phenyl-2-methyl-3-pyrryl)-2-butene (BPE2), was studied by laser flash photolysis technique. The results indicate that photocyclization of these compounds proceeds mainly via the excited triplet state, and the cis-trans isomerization proceeds mainly via the excited singlet state. After UV laser pulse irradiation, both photocylization and cis-trans isomerization of BPEl occur, but photocydization is the main reaction. On the other hand, laser photolysis of BPE2 leads mainly to photocydization. The effects of the substituents on the photochromic mechanism are also discussed.

A Flow-Tube and PERCA Study of Radical Yields in the Ozonolysis of Ethene

The production of radicals in the ozonolysis of ethene in air in a flow tube was monitored directly by a chemical amplification instrument at room temperature （298±2） K and 1 × 10^5 Pa. The radical yield is 0.50± 0.08 （σ） and found to be independent of CO. The result shows that the indirectly measured radical yields for the ozonolysis of ethene may be underestimated by a factor of 2.

A pilot scale test of ozonization treatment of ethene wastewater for reuse

Apilot scale test of advanced treatment of ethene wastewater by ozonization was carried out for industrial water reuse.Effects of different operating conditions on COD degradation,such as wastewater flow rate,ozonized gas flow rate,operating voltage of ozonizer and two ozone generation means,using pure oxygen or air,was investigated.The results show that the increase of ozonizer operating voltage,the decrease of wastewater flow rate and the suitable ozonized gas flowrate improve the removal ofCOD inwastewater and thatozone generatedrespectively fromair and pure oxygen can effectively remove COD of ethene wastewater to meet the industrial water reuse criterion.

Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

Absolute rate constants for the reaction of ozone with dimethyl sulfide （DMS） were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range, the data could be fit to the simple Arrhenius expression as kDMS = （9.96 ± 3.61） × 10^-11 exp （-（7309.7 ± 1098.2）/T） cm^3/（molecule.s）. A compared investigation of the reaction between ozone and ethene had a kC2H4 value of （1.35 ± 0.11） × 10^-18 cm^3/（molecule.s） at room temperature.

Effect of Metallic Additives on Structure and Catalytic Properties of Supported NiPB/SiO_2 Catalyst

A new preparation method was proposed to deposit amorphous alloys alloys containing NiPand metallic metallic additives such as Fe.Co. and Cu.The different effects of metallic additive onstructure and catalytic properties of supported amorphous NiMPB/SiO2 (M=Fe, Co. Cu) cafalysts were observed,and the improvement of catalytic activity due to heating pretreatment in hydrogenwas found.

Reaction of Polymer-supported Selenovinyl Bromide with Grignard Reagents: A Facile Route to the Synthesis of (E)-1, 2-Disubstituted Olefins

Polymer-supported selenovinyl bromide, easily prepared from polymer-supported selenenyl bromide with acetylene, reacts with different Grignard reagents using a step-by-step strategy to obtain （E）-1, 2-disubstituted ethenes in good yields.

Dynamic cooperations between lattice oxygen and oxygen vacancies for photocatalytic ethane dehydrogenation by a self-restoring LaVO_(4)catalyst

Thermocatalytic nonoxidative ethane dehydrogenation(EDH)is a promising strategy for ethene production but suffers from intense energy consumption and poor catalyst durability;exploring technology that permits efficient EDH by solar energy remains a giant challenge.Herein,we present that an oxygen vacancy(O_v)-rich LaVO_(4)(LaVO_(4)-O_v)catalyst is highly active and stable for photocatalytic EDH,through a dynamic lattice oxygen(O_(latt.))and O_(v)co-mediated mechanism.Irradiated by simulated sunlight at mild conditions,LaVO_(4)-O_(v)effectively dehydrogenates undiluted ethane to produce C_(2)H_(4)and CO with a conversion of 2.3%.By loading a small amount of Pt cocatalyst,the evolution and selectivity of C_(2)H_(4)are enhanced to 275μmol h^(-1)g^(-1)and 96.8%.Of note,LaVO_(4)-O_(v)appears nearly no carbon deposition after the reaction.The isotope tracked reactions reveal that the consumed O_(latt.)recuperates by exposing the used catalyst with O_(2),thus establishing a dynamic cycle of O_(latt.)and achieving a facile catalyst regeneration to preserve its intrinsic activity.The refreshed LaVO_(4)-O_(v)exhibits superior reusability and delivers a turnover number of about 305.The O_(v)promotes photo absorption,boosts ethane adsorption/activation,and accelerates charge separation/transfer,thus improving the photocatalytic efficiency.The possible photocatalytic EDH mechanism is proposed,considering the key intermediates predicted by density functional theory(DFT)and monitored by in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).