Online Model-Based Process Safety Concepts in Polymerization

Summary: To safeguard runaway reactions in industrial scale, qualified methods have to be used. While mechanical safety devices are usually installed, their design may be problematic as the runaway kinetics must be known. This may not be the case for many processes due to the required flexibility and possible unanticipated deviations from recipes. It is shown that runaway kinetics can be very fast and can lead to high conversions. Therefore, a method is proposed that does not depend on kinetics but limits the amounts of unreacted monomer in the reactor by monitoring the conversion and by quantitatively determining the hazardous potential. If a potential violation is observed, feeds to the reactor are interrupted.     

Evolution of products during the degradation of polyethylene in a batch reactor

The thermal degradation of two polyethylene samples (LDPE and HDPE) has been carried out in a batch reactor under dynamic conditions. The evolution of products generated after regular intervals of 5 min (temperature increments of approximately 25 °C) has been analyzed. The behaviour of LDPE and HDPE has been compared, and no differences in the quantity and weight fraction of the gaseous products obtained have been found. For both polymers, n-paraffins are the major products at the very beginning of the process, while as the decomposition proceeds 1-olefins are more abundant. The condensed fraction is much larger than the gaseous fraction and its analysis reveals some differences between the behaviour of LDPE and HDPE at the beginning of the degradation process. These differences disappear at higher temperatures where more similar trends are observed. 1-Olefins, n-paraffins, dienes and olefins with wide carbon number distributions are the most important condensed compounds obtained in the thermal degradation of both polyethylenes. The formation of 1-olefins and n-paraffins begins at slightly lower temperatures than for dienes and olefins. On the other hand, as the temperature increases, the amount of low and high molecular weight compounds increases at the expense of intermediate molecular weight products and the former become the most important by the end of the degradation process. This behaviour could be related to the thermal cracking of waxes through secondary reactions.     

Ni-based amorphous alloy membranes for hydrogen separation at 400 °C

Amorphous alloy membranes composed primarily of Ni and early transition metals (ETMs) are an inexpensive alternative to Pd-based alloy membranes, and these materials are therefore of particular interest for the large-scale production of hydrogen from carbon-based fuels. Catalytic membrane reactors can produce hydrogen directly from coal-derived synthesis gas at 400 °C, by combining a commercial water–gas-shift (WGS) catalyst with a hydrogen-selective membrane. In order to explore the suitability of Ni-based amorphous alloys for this application, the thermal stability and hydrogen permeation characteristics of Ni–ETM amorphous alloy membranes has been examined. A fundamental limitation of these materials is that hydrogen permeability is inversely proportional to the thermal stability of the alloy. Alloy design is therefore a compromise between hydrogen production rate and durability. Amorphous Ni₆₀Nb_40−XZr_X membranes have been tested at 400 °C in pure hydrogen, and in simulated coal-derived gas streams with high steam, CO and CO₂ levels, without severe degradation or corrosion-induced failure. Ni–Nb–Zr amorphous alloys are therefore prospective materials for use in a catalytic membrane reactor for coal-derived syngas.     

Totally knotted Seifert surfaces with accidental peripherals

We show that if there exists an essential accidental surface in the knot exterior, then a closed accidental surface also exists. As its corollary, we know boundary slopes of accidental essential surfaces are integral or meridional. It is shown that an accidental incompressible Seifert surface in knot exteriors in is totally knotted. Examples of satellite knots with arbitrarily high genus Seifert surfaces with accidental peripherals are given, and a Haken 3-manifold which contains a hyperbolic knot with an accidental incompressible Seifert surface of genus one is also given.

     

核能和物理学

本文分别讨论了实现裂变和聚变核能的利用与物理学各学科（核物理、中子物理、等离子体物理、磁流体力学、材料物理、热物理、剂量防护、堆物理）研究工作的相互促进关系。     

Engineering development and safety back-up for nuclear power programme

This article reviews the engineering development and safety aspects that are relevant to the nuclear power programme being pursued in the country. Some of the important aspects have been discussed in detail bringing out the current status and also the directions for further work.     

TEXONO中微子实验屏蔽效果的Monte Carlo研究

TEXONO实验采用CsI (T1)晶体量能器测量反应堆低能中微子的能谱和通量,确定中微子ν_e的反常磁矩并为中微子振荡实验做技术准备.详细描述了屏蔽体的安排,本底的主要来源,基于GEANT3软件包做了Monte Carlo研究,得到屏蔽体对本底的屏蔽效果.     

Synthesis,Characterization and Photocatalytic Activity of TiO<Subscript>2</Subscript> Powders Prepared Under Different Gelling and Pressure Conditions

Homogeneous TiO₂ gel powders were prepared by hydrolysis and condensation of titanium(IV) isopropoxide with HCl or SnCl₂ catalysts, by working under reduced pressure or in air. Ti(IV) alkoxide was previously modified by reaction with formic or acetic acid, used as chelating ligands, when gelation was performed in acidic catalysis. Crude TiO₂ xerogels were purified by water reflux treatment in order to induce a low temperature crystallisation to the anatase phase. Both crude and purified TiO₂ samples were characterised by XRD, FT-IR, SEM, and N₂ adsorption analysis. Thermoanalyses (TG, DTA, DTG, TG-MS, TG-GC-MS) were carried out to quantify the residual organic components in the crude TiO₂ gels and to obtain stoichiometric formulas to describe their chemical compositions. XRD data of purified TiO₂ powders were processed by means of a Rietveld refinement procedure to determine TiO₂ polymorphs, crystallite sizes and cell parameters, before their use in photocatalytic tests. The photoactivity of the purified TiO₂ anatase powders was studied by using 4-nitrophenol degradation as probe reaction carried out in a batch and/or a membrane photoreactor. Samples prepared by using formic acid or SnCl₂ were the most photoactive, whereas specimens gelled under vacuum treatment showed detrimental effects.     

Accelerator development in India for ADS programme

At BARC, development of a Low Energy High Intensity Proton Accelerator (LEHIPA), as front-end injector of the 1 GeV accelerator for the ADS programme, has been initiated. The major components of LEHIPA (20 MeV, 30 mA) are a 50 keV ECR ion source, a 3 MeV Radio Frequency Quadrupole (RFQ) and a 20 meV drift tube linac (DTL). The Low Energy Beam Transport (LEBT) and Medium Energy Beam Transport (MEBT) lines match the beam from the ion source to RFQ and from RFQ to DTL respectively. Design of these systems has been completed and fabrication of their prototypes has started. Physics studies of the 20–1000 MeV part of the Linac are also in progress. In this paper, the present status of this project is presented.      

反向载气注入下等离子体反应器二维数值模拟

本文对有反向载气注入条件下等离子体反应器内的传热与流动特性进行了二维数值模拟.数值计算结果表明,由于反向载气的注入,在等离子体发生器喷嘴出口与载气喷口之间的空间区域会形成一个滞止层,而且该滞止层的位置随着反向注入的载气速度(流量)的增加向等离子体发生器出口移动,数值模拟结果与实验观察结果定性一致.