Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 2: numerical simulations

The factors affecting the adsorption and desorption kinetics in a TEOM are reviewed in detail with particular attention given to the assumptions required to obtain physical transport parameters from the data. Two models are presented to simulate TEOM adsorption data in the case that concentration differences down the catalyst bed can be neglected, as is appropriate when the amount of catalyst used is small, the carrier gas flowrate is large, and/or the adsorbate partial pressure is low. In the first model, the effective diffusion coefficient, D_e, is taken to be constant. In the second model, the effective diffusion coefficient is assumed to obey the Darken equation, D_e=D₀/(1−θ). The TEOM results obtained on n-hexane, n heptane, n-octane, toluene and p-xylene on a commercial FCC catalyst and on pure rare-earth exchanged zeolite Y under non-reacting conditions (373-) are analysed in detail. It is found that intracrystalline diffusion is not the limiting factor affecting the overall rates of adsorption and desorption for the systems studied. Instead, it is the transport of molecules between the adsorbed and vapour phases at the edge of zeolite crystallites that is the limiting transport step affecting the overall kinetics. For the FCC catalyst, the limiting step is the transport of molecules at the zeolite-matrix interface rather than, say, the matrix-vapour interface. Local rate constants for the desorption of the hydrocarbons at the rate-controlling interface have been obtained.     

Fast training procedure for Viola–Jones type object detectors using Laplacian clutter models

This paper presents a fast training strategy for the Viola–Jones (VJ) type object-detection systems. The VJ object- detection system, popular for its high accuracy at real-time testing speeds, has a drawback that it is slow to train. A face detector, for example, can take days to train. In content-based image retrieval (CBIR), where search needs to be performed instantaneously, VJ’s long training time is not affordable. Therefore, VJ’s method is hardly used for such applications. This paper proposes two modifications to the training algorithm of VJ-type object detection systems which reduces the training time to the order of seconds. Firstly, Laplacian clutter (non-object) models are used to train the weak classifier, thus eliminating the need to read and evaluate thousands of clutter images. Secondly, the training procedure is simplified by removing the time-consuming AdaBoost-based feature selection procedure. An object detector, trained with 500 images, approximately takes 2 s for training in a conventional 3 GHz machine. Our results show that the accuracy of the detector, built with the proposed approach, is inferior to that of VJ for difficult object class such as frontal faces. However, for objects with lesser degree of intra-class variations such as hearts, state-of-the-art accuracy can be obtained. Importantly, for CBIR applications, the fast testing speed of the VJ type object detector is maintained.     

Uniaxial stretching of poly(keto‐ether‐imide) films

Narrow strips of various fully imidized polyimide films were stretched under constant load either isothermally or during a temperature ramp. The effects of process variables (load and temperature) on modulus, failure strain, and tensile strength of the stretched films were characterized and room temperature moduli of up to 16 GPa were documented. Several materials that undergo strain‐induced crystallization were identified as candidates for further property optimization. Polym. Eng. Sci. 44:1360–1367, 2004. © 2004 Society of Plastics Engineers.     

Oxygen permeation of blends of copolymers of siloxanes and poly(methylmethacrylate)

A series of low molecular weight (≈40000) copolymers of methylmethacrylate (MMA) and 4-(methacryloyloxy)butylpentamethyldisiloxane (MBPD) have been synthesized by free radical polymerization in dimethylformamide solution. The microstructure, as derived from ¹³C NMR spectra, indicates that the copolymers are about 80% syndiotactic with an overall random distribution of mers. At room temperature, copolymers rich in MMA are clear, rigid glasses but become liquid at high MBPD content. Blends of these copolymers with PMMA are all heterogeneous with visible phase separation over most of the composition range. Differential scanning calorimetry studies show the presence of two T_g's when the relative concentration of PMMA to copolymer is high. Blends of two co-polymers of similar siloxane content produce clear films with no indication of phase separation. The permeability to oxygen at 25°C increases from 0.20 for pure PMMA to 3.0 (fmol/m·s·Pa.) for a copolymer of MMA/MBPD of the mole ratio of 3:1. Evaluation of the permeation behaviors of the blends suggests that blends rich in siloxane exist as a layered structure with the PMMA rich component dominating the observed permeability.     

Service of forsterite refractories in regenerator roofs of open-hearth furnaces

Conclusions The Panteleimonov Refractories Plant produced a large industrial batch of forsterite roof brick for the lower structure of open-hearth furnaces. Tests carried out at the Donetsk Metallurgical Factory showed that it is desirable to use these forsterite refractories: the life of the regenerator roofs was four campaigns in the main roof with an adequately large residual thickness.Investigations established that the changes in the forsterite brick during service in the roof of regenerators are similar to the changes in bricks during service in other structural elements, but the destruction processes occur much more slowly.Translated from Ogneupory, No. 8, pp. 31–38, August, 1968.     

Hot-Pressing Behavior of Si3N4

The densification behavior of Si₃N₄ containing MgO was studied in detail. It was concluded that MgO forms a liquid phase (most likely a magnesium silicate). This liquid wets and allows atomic transfer of Si₃N₄. Evidence of a second-phase material between the Si₃N₄ grains was obtained through etching studies. Transformation of α- to β-Si₃N₄ during hot-pressing is not necessary for densification.     

Dielectric relaxation of poly(chlorostyrenes) and their copolymers in the primary transition region

Dielectric relaxation measurements were carried out on a series of bulk poly(chlorostyrene) homopolymers and random copolymers over the frequency range from 50 to 100 kHz and at temperatures in the neighbourhood of the glass transitions of the polymers thus encompassing the α relaxation. Homopolymers examined were polystyrene (PS), poly(2-chlorostyrene) (P2CS), poly(3-chlorostyrene) (P3CS), and poly(4-chlorostyrene) (P4CS). Copolymers were poly(styrene-co-2-chlorostyrene) (PS2CS), poly(styrene-co-4-chlorostyrene) (PS4CS), and poly(2-chlorostyrene-co-4-chlorostyrene) (P2CS4CS). The dielectric data were analysed to yield dipole moments and Kirkwood—Fröhlich correlation parameters. The shapes of the dielectric loss curves were also taken into account. Glass transition temperatures were determined by differential scanning calorimetry (d.s.c.). It was concluded that the phenyl ring rotates freely in the α relaxation regions of PS, P4CS, and P3CS, but not in P2CS. The dipole moments of the copolymers are correlated with dyad distributions calculated from reactivity ratios.     

Heat transfer

Conclusions Numerous new heat transfer developments have been reported in the last few years. These developments are useful for a better understanding of the basic theory and for developing improved equipment. In many cases both heat and mass transfer occur simultaneously in commercial operations.     

Technical new feature

A continuous process for the commercial production of isopropenyl stearate (IPS) from triple pressed stearic acid and a stabilized form of propyne has been developed. Cost estimates, including capital costs, operating costs, and profitability, for commercial scale plant production which show the process to be economically feasible are presented. This potentially profitable process offers the advantages of reliable raw material sources, minimal external thermal requirements, and usable process waste streams. For a plant producing 5 million pounds of IPS per year, the selling price range is 80 to 107 cents/lb IPS, corresponding to a raw material cost range of 27 to 54 cents/lb of IPS. For a 20 million pound per year plant, the selling price range is 58 to 85 cents/lb IPS. The selling prices include a 20% annual return on fixed capital investment. Fixed capital requirement ranges from 2.7 to 10.9 million dollars (3rd quarter, 1975) for plants ranging in size from 5 to 50 million pounds of IPS per year, respectively.     

Stereochemistry and mechanism of the hydrogenation of dialkyl cyclohexenes

In order to investigate the steric effect of the substituents to determine the product distribution, disubstituted cyclohexenes were hydrogenated over several transition metal catalysts. Some cyclohexenes which have two large substituents at the vicinal carbon atoms, at least one of which is trigonal, were not hydrogenated over Raney Ni at all but were hydrogenated over Pt catalyst under our experimental conditions. Presumably, the stereoselectivity depends on the competitive operation of the torsional angle strain and the catalyst hindrance with substituents. In the hydrogenation over Pd catalyst, thermodynamically more stable products were dominant at the standard condition but at high substrate to catalyst ratio the less stable products were slightly preferred. No appreciable stereoselectivity was observed in the hydrogenation of 1,4-disubstituted cyclohexenes.