Monte Carlo simulation of gas phase polymerization of 1,3‐butadiene. Part II: Kinetics optimization and confirmation

Studies on the deactivations and initiations of gas phase polymerizations of 1,3‐butadiene have been achieved by Monte Carlo simulation. Initiation and deactivation control the reaction before and after the peak of the polymerization rate, respectively. The influence of polymerization temperature has been studied. Monte Carlo modeling of polymerization kinetics and mechanism was confirmed by the agreement of experimental data and simulation results of polymerizations run with a temporary evacuation of monomer. The balance of catalysts and active chains is established by both initiation and chain transfer reactions with cocatalyst, which causes a ‘pseudo‐stability’ stage. © 2003 Society of Chemical Industry     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

Effects of hydrolysis on the physical properties of short glass-fibre reinforced poly(ethylene terephthalate)

The mechanical fracture strength and toughness of short-fibre composites, injection moulded from compounds of poly(ethylene terephthalate) (PET) containing 10 and 30% (by weight) (w/o) glass, have been investigated and the dependence upon matrix hydrolytic stability determined. Mouldings have been characterised by several physical techniques to evaluate molecular weight, degradation rates, crystallinity and morphology, whilst time-dependent gravimetric data were derived to quantify sorption kinetics and allow comparisons with theoretical reaction rates to be made. During melt processing, PET is hydrolysed extremely rapidly by traces of moisture (<0.02w/o). yet the inherent strength of moulded composites declines significantly only below an apparently critical molecular weight. However, on long-term humid ageing in hot water, impact behaviour especially is rendered more complex by simultaneous crystallisation, molecular reorder and losses of interfacial bond strength.     

Feasibility analysis of membrane reactors – discovery of reactive arheotropes

A feasibility analysis methodology adopted from reactive distillation is applied to membrane reactors. A model is formulated to depict the reactive liquid phase composition on the retentate side of a continuous type membrane reactor. The effects of both the chemical reaction kinetics and the membrane mass transfer kinetics on the feasible products are elucidated by means of retentate phase diagrams and bifurcation analysis. The proposed method can be applied to various membrane processes, independent of the specific structure of the membrane. Two quaternary reaction systems are considered to illustrate the methodology. In the first hypothetical system, it is shown how selective membranes can influence the sequence of effective volatilities which in turn affects the feasible products of the system. In the second example of practical importance, i.e. the heterogeneously catalysed synthesis of propyl acetate coupled with permeation through a porous polycarbonate membrane, the dusty gas model is applied to describe the component fluxes through the membrane. For the latter reaction system, the existence of reactive arheotrope is demonstrated. Arheotropes represent mass transfer controlled feasible products of membrane separation process.     

Study of liquid injection impact on the performance of new refrigerant mixtures

In this paper, the test results of liquid injection impact on the performance of new alternative refrigerant mixtures such as: R-410A, R-507, R-407C and R-404A are discussed, analysed and presented. The test results were obtained using an air-source heat pump set-up with enhanced surface tubing under various liquid injection ratios. Performance tests were conducted according to the ARI/ASHRAE standards. The performance data demonstrated that as liquid injection ratio increases, compressor head pressure and discharge temperature decrease. This has a positive effect in protecting the compressor. The effect of liquid injection on mixture behaviour varies from one mixture to another depending upon the mixture's composition. Furthermore, liquid injection appears to have a significant influence on R-410A behaviour compared to the other mixtures in question. Copyright © 2002 John Wiley & Sons, Ltd.     

探讨电石法PVC烟气治理方法

分析了电石法PVC生产链中电石炉烟气及电厂烟气二氧化硫的排放情况,指出利用电石炉烟气中的CO合成氨、再将合成氨用于燃煤电厂烟气的"氨法"脱硫是具有较大应用潜力的循环经济产业链。     

Effect of surfactants and liquid hydrocarbons on gas hydrate formation rate and storage capacity

Hydrate formation rate plays an important role in making hydrates for the storage and transport of natural gas. Micellar surfactant solutions were found to increase gas hydrate formation rate and storage capacity. With the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation reduced. Surfactants (an anionic surfactant, a non‐ionic surfactant and their mixtures) and liquid hydrocarbons (cyclopentane and methylcyclohexane) were used to improve hydrate formation. The experiments of hydrate formation were carried out in the pressure range 3.69–6.82 MPa and the temperature range 274.05–277.55 K. The experimental pressures were kept constant during hydrate formation in each experimental run. The effect of anionic surfactant (sodium dodecyl sulphate (SDS)) on natural gas storage in hydrates is more pronounced compared to a non‐ionic surfactant (dodecyl polysaccharide glycoside (DPG)). The induction time of hydrate formation was reduced with the presence of cyclopentane (CP). Cyclopentane and methylcyclohexane (MCH) could increase hydrate formation rate, but reduced hydrate storage capacity The higher methylcyclohexane concentration, the lower the hydrate storage capacity. Copyright © 2003 John Wiley & Sons, Ltd.     

Inverted Solution Processable OLEDs Using a Metal Oxide as an Electron Injection Contact.

A new type of bottom‐emission electroluminescent device is described in which a metal oxide is used as the electron‐injecting contact. The preparation of such a device is simple. It consists of the deposition of a thin layer of a metal oxide on top of an indium tin oxide covered glass substrate, followed by the solution processing of the light‐emitting layer and subsequently the deposition of a high‐workfunction (air‐stable) metal anode. This architecture allows for a low‐cost electroluminescent device because no rigorous encapsulation is required. Electroluminescence with a high brightness reaching 5700 cd m^–2 is observed at voltages as low as 8 V, demonstrating the potential of this new approach to organic light‐emitting diode (OLED) devices. Unfortunately the device efficiency is rather low because of the high current density flowing through the device. We show that the device only operates after the insertion of an additional hole‐injection layer in between the light‐emitting polymer (LEP) and the metal anode. A simple model that explains the experimental results and provides avenues for further optimization of these devices is described. It is based on the idea that the barrier for electron injection is lowered by the formation of a space–charge field over the metal‐oxide–LEP interface due to the build up of holes in the LEP layer close to this interface.     

谢尔渣油气化油改气控制系统的改造

介绍了Shell渣油气化装置将渣油原料改为天然气时控制系统的改造方案。提出的改造思路不但可用于Shell渣油气化，也可用于德士古渣油气化的油改气工程中。     

Schwingfestigkeit von Schraube‐Mutter‐Verbindungen

High cycle fatigue of bolted connections Extensive tests regarding the influences on the fatigue of bolt‐nut‐connections of preloading with torsion, of preloading with yielding, of loading with superimposed bending and of the tested lot are processed. These influences are not yet known according to VDI 2230. New testing devices were designed for these tests, which allow a far less expensive operation and may easily be used for bolts of diameters up to M100 and testing frequencies up to 1000 Hz. The validity of fatigue resistance according to VDI 2230 is specified with respect to the test results. The determined influence of the tested lots is unexpectedly high. The manufacturing process of bolts should be improved to minimize this influence.