55,924 research outputs found
A temporal analysis of products (TAP) study of C2-C4 alkene reactions with a well-defined pool of methylating species on ZSM-22 zeolite
No full textReactions between alkenes and methanol or dimethyl ether (DME) on zeolite catalysts are involved in industrial processes that are highly relevant for the transition to renewable carbon sources, such as the Methanol-To-Hydrocarbons (MTH) process. In MTH chemistry, alkene methylation increases the length of product carbon chains, and its relative rate with respect to other reactions largely controls the overall selectivity. Experimental studies of alkene methylation present a considerable challenge because they are typically accompanied by cracking, hydrogen transfer, and aromatization reactions. Herein, the pulse-response Temporal Analysis of Products (TAP) methodology and complementary FTIR measurements were employed to isolate a well-defined population of surface species, consistent with Surface Methoxy Species (SMS) on Bronsted acid sites that are reactive in alkene methylation on a ZSM-22 (TON) zeolite. Their coverage was determined by TAP titration to be ca. 5% of the total amount of Brønsted acid sties, which was also indirectly suggested by FTIR data. C2-C4 alkenes were quantitatively reacted with SMS to precisely measure the intrinsic kinetic parameters of isolated alkene methylation steps. The rate constants increased and the activation energies decreased as functions of the carbon number (EC2H4 = 52 kJ/mol > EC3H6 = 32 kJ/mol > Ec-C4H8 = 16 kJ/mol). However, the rate constant for iso-butene was comparable to propene, despite its activation energy (Ei-C4H8 = 19 kJ/mol) being much lower than propene's. This effect is in agreement with the increased steric hindrance predicted by DFT for isobutene adsorption and methylation in TON zeolites. Our results considerably extend previously available TAP data on alkene methylation reactions and furthermore validate ab initio models of these crucial steps in the complex MTH chemistry on acidic zeolites
Catalyst sites and active species in the early stages of MTO conversion over cobalt AlPO-18 followed by IR spectroscopy
No full textThe isomorphic insertion of cobalt(ii) confers strong acidity to the AlPO-18 zeotype. This makes it a suitable catalyst for the acid catalysed conversion of methanol to olefins (MTO). However, due to the tendency of Co(ii) to be oxidised into Co(iii) or to acquire distorted tetrahedral coordination, the concentration of strong Brønsted acidic sites (BAS) in CoAPO-18 is highly susceptible to catalyst activation conditions. The use of vibrational and electron spectroscopy coupled with the use of probe molecules sheds light on the conditions under which the concentration of active sites can be maximized, limiting the formation of species of different nature. The MTO reaction was followed by in situ FT-IR spectroscopy, revealing that the population of strong BAS profoundly affects the methanol conversion in the very early stages of the process. Indeed, spectroscopic evidence of the consumption of CO (produced in situ from the decomposition of methanol itself) was obtained, when the concentration and availability of BAS are optimized. This gives support to the occurrence of Koch carbonylation of surface methoxides, at the early stages of MTO
A Dynamic Subfilter-scale Stress Model for Large Eddy Simulations Based on Physical Flow Scales
No full textWe propose a new definition of the length scale in an eddy-viscosity model for large-eddy simulations (LES). This formulation extends and generalizes a previous proposal [Piomelli, Rouhi and Geurts, Proc. ETMM10, 2014], in which the LES length scale was expressed in terms of the integral length-scale of turbulence determined by the flow characteristics and explicitly decoupled from the simulation grid; this approach was named Integral Length-Scale Approximation (ILSA). As in the original ILSA, the model coefficient was determined by the user, and required to maintain a desired contribution of the unresolved, subfilter scales (SFS) to the global transport. We propose a local formulation (local ILSA) in which the model coefficient is local in space, allowing a precise control over SFS activity as a function of location. This new formulation preserves the properties of the global model; application to channel flow and backward-facing step verifies its features and accuracy
Large-eddy simulation of a separated flow with a sub-filter scale model based on the integral length-scale
No full textA new sub-filter scale model for large-eddy simulations, which uses a length-scale proportional to the integral scale of the turbulence instead of the grid resolution to parametrize the modelled stresses, will be assessed in the prediction of the flow of a boundary-layer over a rough surface, which includes separation and reattachment
Near Wall PIV-Measurements on the Windward Slope of a Hill
No full textThe turbulent flow over periodic hills was measured near to the wall, using planar Particle-Image-Velocimetry (PIV) at high spatial resolution. Our focus is on the near wall turbulence structure on the windward slope of the hill. For large-eddy simulation (LES) we suspect that, if this was not predicted accurately, it affects the prediction of the velocity profiles over the hill crest which in turn will affect the recirculation length downstream of the hill. Regarding the time averaged velocities, we were able to resolve the linear viscous region of the boundary layer. The velocity distribution and also the Reynolds stress does not comply with the law of the wall as it is valid for a turbulent boundary layer at equilibrium
Energy dissipation and flux laws for unsteady turbulence
No full textDirect Numerical Simulations of spatially periodic unsteady turbulence show that the high Reynolds number scalings of the instantaneous energy dissipation rate and interscale energy flux at intermediate wavenumbers are qualitatively different from the well-known cornerstone scalings of equilibrium turbulence where and are time-dependent rms velocity and integral length-scales. Instead, they both scale as where and are length and velocity scales characterizing initial/overall unsteady turbulence conditions
Direct numerical simulation of turbulent Couette-Poiseuille flow with zero skin friction
No full textThe near-wall scaling of mean velocity U(y) is addressed for the case of zero skin friction on one wall of a fully turbulent channel flow. The present DNS results can be added to the evidence in support of the conjecture that U is proportional to √yw in the region just above the wall at which the mean shear dU/dy = 0
Real-space Manifestations of Bottlenecks in Turbulence Spectra
No full textAn energy-spectrum bottleneck, a bump in the turbulence spectrum between the inertial and dissipation ranges, is shown to occur in the non-turbulent, one-dimensional, hyperviscous Burgers equation and found to be the Fourier-space signature of oscillations in the real-space velocity, which are explained by boundary-layer-expansion techniques. Pseudospectral simulations are used to show that such oscillations occur in velocity correlation functions in one- and three-dimensional hyperviscous hydrodynamical equations that display genuine turbulence
Braid Entropy of Faraday Waves driven 2D Turbulence
No full textWe report new experimental results that use tools from braid theory to characterize two-dimensional turbulent flows driven by Faraday waves. The average topological length of the material fluid lines is found to grow exponentially with time. It allows us to compute the braid’s topological entropy SBraid. We show that SBraid increases as the square root of the turbulence kinetic energy E ~ u^2, where u^2 is the horizontal velocity variance . At long times, the PDFs of Lbraid are positively skewed and present strong exponential tails
Mean flow generation by Görtler Vortices in a rotating annulus with librating side walls
No full textLongitudinal libration of the cylinder side walls of a rotating annulus in the supercritical regime induces a centrifugally unstable Stokes boundary layer which generates Görtler vortices only in a portion of a libration cycle. We show for the first time that these vortices propagate into the fluid bulk and generate an azimuthal mean flow which is retrograde (prograde) over the outer (inner) cylinder side wall. Direct numerical simulations (DNS) are carried out and Reynolds-averaged equations and kinetic energy budget of mean and fluctuating flow are used as diagnostic equations to discuss the generation mechanism and scaling behavior of the azimuthal mean flow in the fluid bulk
- …
