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Here we demonstrate that Ga,Al-*BEA zeolites are effective bifunctional catalysts for para -xylene ( p -xylene) production from bio-derived 2,5-dimethylfuran (DMF) through tandem Diels–Alder/dehydration reactions.
The rotational constants and quartic centrifugal distortion coefficients of hexafluoro-o-xylene were precisely derived from the 8 GHz to 18 GHz gas phase microwave spectrum. In addition, the rotational constants of all singly substituted 13 C isotopologues were determined. Instead of the intuitively expected symmetry of C 2v , as in o-xylene, calculations with a variety of methods (B3LYP, CAM-B3LYP, ωB97XD, MP2, and coupled-cluster singles, doubles, and perturbative triples) predict a C 2 symmetry structure in which the two CF 3 groups rotate in opposite directions by about 16°. While the experimental results in this study are not capable of proving this unusual symmetry, they can support future microwave, gas phase electron diffraction or nuclear magnetic resonance studies. From the presented data, a preliminary r 0 structure was determined, reproducing the experimental rotational constants with deviations of no more than 15 kHz. Analysis of the interactions between the two CF 3 groups using an effective fragment potential approach identifies two major contributions to their interaction, due to exchange-repulsion and electrostatic repulsion, with electrostatic repulsion responsible for the barrier at the C 2v geometry.
Neutron time-of-flight (nTOF) spectrometers are essential instruments for measuring and evaluating the performance of inertial confinement fusion implosions. The neutron spectrometers utilized for the OMEGA laser include two liquid-based scintillators, each consisting of a large volume filled with xylene that is coupled to four photomultiplier tubes. Analysis of the signal from these detectors requires detailed knowledge of the scintillator’s light output, which is needed to fit the nTOF spectrum, from which the neutron energy spectrum is informed. The light output is nonlinearly proportional to the neutron energy, which, in turn, affects the interpretation of the neutron energy spectrum from a TOF signal. A recent campaign on OMEGA was performed to calibrate the xylene detectors and infer the shape of the light-output curve. The campaign utilized materials with increasing Z placed in the OMEGA target chamber to initiate scattering events with the 14 MeV fusion neutrons. This process leads to the production of backscatter neutrons of varying energies that appear as peaks in the nTOF data. Simulations using a neutron transport code were combined with the measured deuterium–tritium neutron yields to calculate the expected backscattered neutron yields from the well-known scattering cross sections of each material. Furthermore, the neutron-energy dependent light output of the scintillator inferred from the experiment is compared to the light-output curve simulated with a neutron transport code for the following neutron energies: 1.5, 2.5, 6, and 14 MeV.
We have experimentally characterized the neutron light output response functions of a deuterated-xylene scintillator for neutron energies lower than 10 MeV. We then used the response matrix to unfold the energy distribution of neutrons produced via several reactions, i.e. spontaneous fission, d(d,n)3He, 27Al(d,n)28Si, and 9Be(alpha,n)12C. Organic scintillators based on deuterated compounds show a fast response and good gamma-neutron discrimination capability, similar to proton-based scintillators. Deuterated scintillators can also effectively provide neutron spectra by unfolding measured data with the detector response matrix, without the need of time-of-flight. Deuteron recoils, produced by elastic collisions between deuterium and impinging neutrons, are preferentially forward-scattered. This non-isotropic reaction results in distinct peaks in the response functions to monoenergetic neutrons. In this work, we evaluated a custom-fabricated 7.62 cm x 7.62 cm deuterated-xylene (EJ301D) liquid scintillator. This liquid has a low volatility and higher flash point, compared to benzene-based deuterated detectors, e.g. EJ315 and NE230. We measured the EJ301D detector neutron response matrix (up to 6 MeV neutron energy) using an intense Cf252 source and the time-of-flight technique. The number of response functions obtained using our method is only limited by counting statistics and by the experimentally achievable energy resolution. Multi-channel unfolding was performed successfully for neutron spectra with different energy spectra.
Para-xylene is an intermediate compound to several valuable commodity chemicals including polyethylene terephthalate (PET) and currently produced from fossil feedstock through a complex sequence of steps utilizing energy intensive process. Recent work from PNNL has demonstrated the conversion of ethanol produced from waste feedstocks such as municipal solid waste to para-xylene via simple three step process.
Here, we investigated the photodissociation dynamics of three xylene isomers C 6 H 4 (CH 3 ) 2 at 157nm. The center-of-mass translational energy distributions of C 7 H 7 radicals were found to peak at 26kJmol −1 . Although the ionization energy of the C 7 H 7 tolyl fragment exceeds the energy of a 157nm photon, C 7 H 7 + was observed as a result of the photoionization of vibrationally ‘hot’ tolyl (C 7 H 7 ) radicals and/or two-photon ionization. The formation of rovibrationally excited tolyl fragments was discussed. Our experiments suggest the presence of tolyl radicals in the interstellar medium as a precursor to methylated polycyclic aromatic hydrocarbons upon reaction with vinylacetylene (C 4 H 4 ).
Results are reported of knock-limited tests of five aromatics, each individually blended with selected base fuels and tested with and without TEL, using 17.6, F-4, and F-3 small-scale engines. The five aromatics rated in the following order of decreasing antiknock effectiveness at fuel/air ratio 0.10: m-xylene, 1-isopropyl-4-methylbenzene, n-propylbenzene, isobutylbenzene, and n-butylbenzene.
Abstract The control of membrane morphology and microstructure is crucial to improve the separation performance of molecular‐sieve membranes. This can be enabled by making thin, dense, and uniform seed‐crystal coatings, which are then intergrown into continuous membranes. Herein, we show a novel and simple floating particle coating method can give closely packed monolayers of zeolite nanosheets on nonporous or porous supports. The zeolite nanosheet monolayer is formed at the air–water interface in a conical Teflon trough. As the water in the trough is drained, the monolayer is deposited on a support placed below. Membranes prepared by gel‐free secondary growth of the nanosheets deposited by this method show unprecedented ultra‐selective performance for separation of para‐ from ortho‐xylene (separation factor >10 000).
The control of membrane morphology and microstructure is crucial to improve the separation performance of molecular-sieve membranes. This can be enabled by making thin, dense, and uniform seed-crystal coatings, which are then intergrown into continuous membranes. Herein, we show a novel and simple floating particle coating method can give closely packed monolayers of zeolite nanosheets on nonporous or porous supports. The zeolite nanosheet monolayer is formed at the air–water interface in a conical Teflon trough. As the water in the trough is drained, the monolayer is deposited on a support placed below. Membranes prepared by gel-free secondary growth of the nanosheets deposited by this method show unprecedented ultra-selective performance for separation of para- from ortho-xylene (separation factor >10,000).
In this work, we use molecular dynamics simulations to evaluate the behavior of toluene (TOL) and p-xylene (XYL) within three different solvents: n -hexane (HEX), n -heptane (HEP), and a thermally-robust ionic liquid (triphenyl-p-phenyl sulfonyl phenyl phosphonium + bis(trifluoromethylsulfonyl)imide (TPSP + Tf 2 N)). Several different temperatures are explored, while the solvation structures, energetics, and dynamics of TOL and XYL are evaluated. The solvation free energy (ΔG solv ) and transfer free energy (ΔG transfer ) of TOL and XYL are calculated using thermodynamic integration (TI). The transfer free energy of XYL from HEP/HEX to TPSP + Tf 2 N is more favorable than that of TOL over the entire temperature range, while the transfer of both TOL and XYL becomes less favorable as the temperature increases. The diffusion rates of TOL and XYL are lower in the ionic liquid when compared to HEP and HEX, but the thermal stability of TPSP + Tf 2 N may allow for higher operating temperatures and accelerated mass transport rates.
The adsorption and reaction properties of H-BEA, SnBEA, ZrBEA and siliceous BEA were examined to understand the reaction of 2,5-dimethylfuran (DMF) with ethylene to form p -xylene.
Adsorptive separation of physically and chemically similar molecules and understanding the underlying host–guest interactions at the molecular level are of significant scientific and practical importance. Here we report the development of a novel calcium-based metal–organic framework, formulated as Ca 3 (Htcpp) 2 (H 4 tcpp = 2,3,5,6-tetrakis(4-carboxyphenyl)-pyrazine) featuring microporosity and high stability. This compound shows distinct adsorption behavior toward xylene isomers and is capable of separating them efficiently at an industrially relevant temperature. The selective adsorption is attributed to a synergetic thermodynamic and kinetic effect. Here, the host–guest interactions were probed directly by single-crystal X-ray diffraction analysis and the adsorption affinity was evaluated through computational molecular simulations.
Our research aims to tackle the challenge in recycling end-of-life plastics, the accumulation of which has become a grand challenge to our society, sustainability and economy. Guided by life-cycle assessment (LCA) and tech-economic analysis (TEA), we specifically target the catalytic conversion of low-cost #3-7 plastic mixtures ($\$$5/ton) into p-xylene (>$\$$1000/ton), one of the most valuable hydrocarbon products. This goal is achieved by carrying out integrated research including catalysis, process engineering, and reactor design. The ultimate goal of this project is to enable energy-efficient and economically viable depolymerization of end-of-life plastic mixtures into value-added commodity chemicals.
Photolysis of 2,5-dibenzoyl-p-xylene produces two discrete o-xylenols which undergo Diels-Alder cycloadditions with standard dienophiles, such as methyl acrylate, to produce 1,5-dihydroxy-1,5-diphenyl-l,2,3,4,5,6,7,8-octahydroanthracenes, 2a, in good yield (greater than 80%). The anti bisadduct crystallizes into hydrogen bonded stacks. Conversion of both syn- and anti-bisadducts to the corresponding anthracenes was achieved through the use of standard dehydration and aromatization chemistry.
Methods and phosphorus-containing solid catalysts for catalyzing dehydration of cyclic ethers (e.g., furans, such as 2,5-dimethylfuran) and alcohols (e.g., ethanol and isopropanol). The alcohols and cyclic ethers may be derived from biomass. One example includes a tandem Diels-Alder cycloaddition and dehydration of biomass-derived 2,5-dimethyl-furan and ethylene to renewable p-xylene. The phosphorus-containing solid catalysts are also active and selective for dehydration of alcohols to alkenes.
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