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.     

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.     

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.     

Analysis of the Datagram Congestion Control Protocol’s connection management procedures using the sweep-line method

State space explosion is a key problem in the analysis of finite state systems. The sweep-line method is a state exploration method which uses a notion of progress to allow states to be deleted from memory when they are no longer required. This reduces the peak number of states that need to be stored, while still exploring the full state space. The technique shows promise but has never achieved reductions greater than about a factor of 10 in the number of states stored in memory for industrially relevant examples. This paper discusses sweep-line analysis of the connection management procedures of a new Internet standard, the Datagram Congestion Control Protocol (DCCP). As the intuitive approaches to sweep-line analysis are not effective, we introduce new variables to track progress. This creates further state explosion. However, when used with the sweep-line, the peak number of states is reduced by over two orders of magnitude compared with the original. Importantly, this allows DCCP to be analysed for larger parameter values. Somsak Vanit-Anunchai was partially supported by an Australian Research Council Discovery Grant (DP0559927) and Suranaree University of Technology. Guy Edward Gallasch was supported by an Australian Research Council Discovery Grant (DP0559927).     

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。     

Characterization and modification of fillers for paints and coatings

This paper highlights the possibility of inverse gas chromatography for the surface characterization of common fillers (CaCO₃, talc, SiO₂,) for paints and coatings. Divided solids are described, on the one hand, by the dispersive component of their surface energy and, on the other, by a specific parameter indicating their acid-base interaction potential. The role of the surface morphology at a molecular level is also examined. It is demonstrated that steric effects play an important role in the adsorption of probes on lamellar solids like talc. The consequences of surface treatments as well as examples of practical applications are also reported.     

Municipal solid waste conversion to energy

In recent years it has been recognised by an increasing number of nations that there is considerable energy potential within MSW. As a result many countries have established R,D& D programmes to examine methods of exploiting this potential. The IEA's MSW Conversion Activity was set up in 1986 to provide an infrastructure for sharing information and co-ordinating work in this area internationally. This Activity was extended in 1989 and currently a total of 9 nations participate in it.

To cope with the wide scope of the area (encompassing both biological and thermal processing of MSW) the Activity was divided into three subgroups or Expert Working Groups (EWGs). Each of these dealt with a distinct area of expertise:

1. •Downstream effects of source separation and screening of MSW

2. •Sampling and analytical protocols

3. •Landfill gas

In addition to these groups a central secretariat based at Harwell (UK) has provided guidance, established and administered databases of contacts and produced a series of national reports.

This paper describes the achievements of the Activity and discusses work proposed for the future.     

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本文根据四川天然气产能建设多年的实践,分析了产能建设的特点和存在问题,着重强调了当前搞好产能建设应注意的几个问题,供决策和工作参考。