High‐Resolution Single‐Molecule Fluorescence Imaging of Zeolite Aggregates within Real‐Life Fluid Catalytic Cracking Particles

Fluid catalytic cracking (FCC) is a major process in oil refineries to produce gasoline and base chemicals from crude oil fractions. The spatial distribution and acidity of zeolite aggregates embedded within the 50–150 μm‐sized FCC spheres heavily influence their catalytic performance. Single‐molecule fluorescence‐based imaging methods, namely nanometer accuracy by stochastic chemical reactions (NASCA) and super‐resolution optical fluctuation imaging (SOFI) were used to study the catalytic activity of sub‐micrometer zeolite ZSM‐5 domains within real‐life FCC catalyst particles. The formation of fluorescent product molecules taking place at Brønsted acid sites was monitored with single turnover sensitivity and high spatiotemporal resolution, providing detailed insight in dispersion and catalytic activity of zeolite ZSM‐5 aggregates. The results point towards substantial differences in turnover frequencies between the zeolite aggregates, revealing significant intraparticle heterogeneities in Brønsted reactivity.     

Substrate‐Tuned Catalysis of the Radical S‐Adenosyl‐L‐Methionine Enzyme NosL Involved in Nosiheptide Biosynthesis

NosL is a radical S‐adenosyl‐L ‐methionine (SAM) enzyme that converts L ‐Trp to 3‐methyl‐2‐indolic acid, a key intermediate in the biosynthesis of a thiopeptide antibiotic nosiheptide. In this work we investigated NosL catalysis by using a series of Trp analogues as the molecular probes. Using a benzofuran substrate 2‐amino‐3‐(benzofuran‐3‐yl)propanoic acid (ABPA), we clearly demonstrated that the 5′‐deoxyadenosyl (dAdo) radical‐mediated hydrogen abstraction in NosL catalysis is not from the indole nitrogen but likely from the amino group of L ‐Trp. Unexpectedly, the major product of ABPA is a decarboxylated compound, indicating that NosL was transformed to a novel decarboxylase by an unnatural substrate. Furthermore, we showed that, for the first time to our knowledge, the dAdo radical‐mediated hydrogen abstraction can occur from an alcohol hydroxy group. Our study demonstrates the intriguing promiscuity of NosL catalysis and highlights the potential of engineering radical SAM enzymes for novel activities.     

WIDECARS spectra fitting in a premixed ethylene–air flame

WIDECARS measures temperature and mole fractions of most of the major species in ethylene–air flames. One of the issues in implementing this technique is fitting the experimental spectra to theory to obtain flame conditions (temperature, species mole fractions). Individual spectra contain many species resonances, and theory is slow to compute. Libraries of precalculated spectra can be used, but a library of sufficient density for accurate interpolation is large given the many variables. A new fitting algorithm is presented which utilizes a less‐dense library, and additional spectra are calculated during fitting to maintain accuracy. The iterative convergence method converts the problem of minimizing fit error, which converges slowly, to a zero finding problem, which converges reliably, rapidly, and accurately to best fit. Various practical fitting issues, such as the effects of dye laser mode noise and variability, phase‐matching efficiency, and shifts of the spectrum on the spectrometer are addressed. The technique is demonstrated in the analysis of experimental measurements in an equivalence ratio 2.1 ethylene–air flame above the surface of a McKenna burner. Precision errors because of experimental and fitting effects are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Modeling of dynamics, heat transfer, and combustion in two-phase turbulent flows: 2. Flows with heat transfer and combustion

The objective of this part of the paper is to summarize the information concerning the authors' works in the field of simulation of two-phase gas-particle turbulent flows with heat transfer and combustion. A kinetic equation had been derived for the probability density function (PDF) of the particle velocity, temperature, and mass distributions in turbulent flows. This PDF equation is used for the construction of the governing conservation equations of mass, momentum, and heat transfer in the dispersed particle phase.The numerical scheme incorporates two-phase fluid dynamics, convective and radiative heat transfer, and combustion. The proposed models have been applied to the calculation of various particle-laden turbulent flows in jets, combustion and gasification chambers, and furnaces.     

球形封闭容器内一个简单的煤粉燃烧爆炸模型

在分析了大量球形封闭容器内煤粉燃烧爆炸实验数据基础上，考虑了煤粉燃烧爆炸机理所涉及的湍流燃烧、相变、各种化学反应动力学过程等复杂因素，并且对球形封闭容器内由于煤粉混合不均匀造成的燃烧不充分给予了考虑，得到了球形封闭容器内煤粉燃烧爆炸特征的数值计算结果，计算的压力－时间曲线与实验结果符合较好。     

Experimental Study on Stabilization of Lifted Swirl Flames in a Model GT Combustor

This study reports on experimental investigations on isothermal and reacting swirled non-premixed flows under varying pressure conditions. In this configuration, a central high speed fuel jet was surrounded by a heated swirling air flow. For the reacting case natural gas served as fuel whereas for isothermal conditions fuel was replaced by a mixture of helium and air to achieve Reynolds-similarity. The optically accessible combustor allowed for application of laser diagnostics. Here we report on Laser Doppler Anemometry and planar laser-induced fluorescence (PLIF) experiments used to characterize the flow field and visualize selected scalars, respectively. Acetone served as a fluorescence marker for mixture fraction investigations. The hydroxyl radical was used to provide general features of the reaction zone such as flame shape and mean stabilization. To expose the influence of pressure on the flame structure three different operating points were investigated varying the combustor pressure between 2 and 6 bar while the inflow bulk velocities remained the same. Striking features of the present configuration are a detached flame, multiple recirculation zones, and complex coherent flow structures.     

开区注氮采空区自燃温度场的数值模拟研究

为了研究开区注氮采空区遗煤自燃和被抑制的力学过程，用非均质多孔介质中的渗流连续性方程、气体弥散方程和综合传热方程的联立，建立了采空区注氮非定常数值模型．结合实例，用迎风格式有限元方法求解．给出了采空区的漏风流态、氮气流态，描绘了采空区自燃过程中氧、CO浓度和温度分布的变化过程．计算考虑了瓦斯涌出和工作面推进的影响．得到注氮条件下采空区高温区形状变窄；随着注氮量的提高，使自然发火期逐渐变长，直至不自燃．理论计算与实际情况吻合．     

CFD SIMULATION OF FLUID CATALYTIC CRACKING IN DOWNER REACTORS

A mathematical model has been developed for the simulation of gas-particle flow and fluid catalytic cracking in downer reactors. The model takes into account both cracking reaction and flow behavior through a four-lump reaction kinetics coupled with two-phase turbulent flow. The prediction results show that the relatively large change of gas velocity affects directly the axial distribution of solids velocity and void fraction, which significantly interact with the chemical reaction. Furthermore, model simulations are carried out to determine the effects of such parameters on product yields, as bed diameter, reaction temperature and the ratio of catalyst to oil, which are helpful for optimizing the yields of desired products. The model equations are coded and solved on CFX4.4.     

Direct Numerical Simulation of Statistically Stationary One- and Two-Phase Turbulent Combustion: A Turbulent Injection Procedure

A new turbulent injection procedure dedicated to fully compressible direct numerical simulation (DNS) or large eddy simulation (LES) solvers is proposed. To avoid the appearance of spurious acoustic waves, this method is based on an accurate tracking of the turbulent structures crossing the boundary at the inlet of the domain. A finite difference DNS solver has been coupled with a spectral simulation in which a statistically stationary homogeneous turbulence evolves to provide fluctuating boundary conditions.A new turbulence forcing method, dedicated to spectral solvers, has been developed as well to control the major properties of the injected flow (turbulent kinetic energy, dissipation rate and integral length scale). One-dimensional Navier–Stokes characteristic boundary conditions extended to non-stationary flows are coupled with the injection procedure to evaluate is potential in four various configurations: spatially decaying turbulence, dispersion of vaporizing sprays, propagation of one- and two-phase V-shape turbulent flames.     

CARBON NANOTUBES VIA METHANE DECOMPOSITION ON AN ALUMINA SUPPORTED COBALT AEROGEL CATALYST

An alumina-supported cobalt aerogel catalyst prepared from a sol-gel and a supercritical drying method was used in the catalytic decomposition of methane.The physical-chemical properties of the catalyst were characterized and its activity for methane decomposition was investigated.The effects of calcination and reaction temperatures on the activity of the catalyst and the morphology of the carbon nanotubes produced were discussed.A COAl2O4 spinel structure formed in the calcined catalyst.The quantity of the nanotubes produced in the reaction increases with the amount of cobalt in the reduced catalyst.A higher reaction temperature leads to a higher reaction rate,though faster deactivation of the catalyst occurs with the change.The carbon nanotubes grown on the catalyst have smooth walls and uniform diameter distribution.