Mixed oxide supported hydrodesulfurization catalysts—a review

Support effects form important aspect of hydrodesulfurization (HDS) studies and mixed oxide supports received maximum attention in the last two decades. This review will focus attention on studies on mixed oxide supported Mo and W catalysts. For convenience of discussion, these are divided into Al₂O₃ containing mixed oxide supports, TiO₂ containing mixed oxide supports, ZrO₂ containing mixed oxide supports and other mixed oxide supports containing all the rest. TiO₂ containing mixed oxides received maximum attention, especially TiO₂–Al₂O₃ supported catalysts. A brief discussion about their prospects for application to ultradeep desulfurization is also included. An overview of the available literature with emphasis on research carried out in our laboratory form the contents of this publication.     

小剂量辐射对肿瘤细胞K_（562）及肿瘤病人天然杀伤细胞（NK）活性的影响

已知小剂量辐射可增强机体免疫功能。从对高本底地区的调查发现，该地区居民肿瘤死亡率及某些肿瘤发病率有所降低（１）。ＮＫ细胞能直接杀伤肿瘤细胞，在肿瘤免疫中起着重要的作用。本文观察小剂量辐射对肿瘤病人和正常人外周血淋巴细胞ＮＫ活性的相对效应以及对人红白血病细胞（Ｋ（５６２）细胞）的影响，以期从体外买验来探索较小剂量辐射对肿瘤治疗的影响     

软X射线对血液有形成分表面电荷的影响——2、淋巴细胞和血小板膜电荷的变化

软X射线不仅能引起红细胞表面电荷的变化,同时也能导致淋巴细胞和血小板表面电荷下降,表现为照射后它们的电泳率下降。低剂量范围内,这种电荷的变化是暂时性的,照后4小时降到最低点,24小时后恢复到对照的水平。细胞电泳率的下降与辐射剂量相关。淋巴细胞是一个复杂的细胞群,正常状态下,按细胞在电场中泳动速度的快慢,可分为两个组分:快峰为T细胞,慢峰为B细胞。软X射线照射以后,T和B细胞的电泳率皆减慢,频数分布峰值下降,离散度加大。血小板成分单一,电泳率较一致。 从照射浓集的血小板再加回自身血浆中电泳率的下降较照射血浆再加到血小板中的电泳率下降大得多;受照射的血小板在磷酸缓冲液中电泳率下降较在血浆悬液中严重得多;2000 rad照后,悬浮于血浆中的血小板电泳率能恢复,而悬浮于磷酸缓冲液中则不能恢复,三个方面来看,血浆中可能存在抗辐射因子。超氧化物岐化酶能有效地预防血小板电泳率的下降,从而可阻止血小板的凝聚。     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Analysis of supersaturation and nucleation in a moving solution droplet with flowing supercritical carbon dioxide

A supercritical antisolvent (SAS) process is employed for production of solid nanoparticles from atomized droplets of dilute solution in a flowing supercritical carbon dioxide (SC CO₂) stream by attaining extremely high, very rapid, and uniform supersaturation. This is facilitated by a two‐way mass transfer of CO₂ and solvent, to and from the droplet respectively, rendering rapid reduction in equilibrium solubility of the solid solute in the ternary solution. The present work analyses the degree of supersaturation and nucleation kinetics in a single droplet of cholesterol solution in acetone during its flight in a flowing SC CO₂ stream. Both temperature and composition are assumed to be uniform within the droplet, and their variations with time are calculated by balancing the heat and mass transfer fluxes to and from the droplet. The equilibrium solubility of cholesterol with CO₂ dissolution has been predicted as being directly proportional to the Partial Molar Volume Fraction (PMVF) of acetone in the binary (CO₂–acetone) system. The degree of supersaturation has been simulated up to the time required to attain almost zero cholesterol solubility in the droplet for evaluating the rate of nucleation and the size of the stable critical nuclei formed. The effects of process parameters have been analysed in the pressure range of 7.1–35.0 MPa, temperature range of 313–333 K, SC CO₂ flow rate of 0.1136–1.136 mol s^?1, the ratio of the volumetric flow rates of CO₂‐to‐solution in the range of 100–1000, and the initial mole fraction of cholesterol in acetone solution in the range of 0.0025–0.010. The results confirm an extremely high and rapid increase in degree of supersaturation, very high nucleation rates and stable critical nucleus diameter of the order of a nanometre. Copyright © 2005 Society of Chemical Industry     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Catalytic dehydrogenation of ethylbenzene with carbon dioxide: promotional effect of antimony in supported vanadium–antimony oxide catalyst

Alumina-supported vanadium oxide, VO_x/Al₂O₃, and binary vanadium–antimony oxides, VSbO_x/Al₂O₃, have been tested in the ethylbenzene dehydrogenation with carbon dioxide and characterized by S_BET, X-ray diffraction, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction and CO₂ pulse methods. VSbO_x/Al₂O₃ exhibited enhanced catalytic activity and especially on-stream stability compared to VO_x/Al₂O₃ catalyst. Incorporation of antimony into VO_x/Al₂O₃ increased dispersion of active VO_x species, enhanced redox properties of the systems and formed a new mixed vanadium–antimony oxide phase in the most catalytically efficient V_0.43Sb_0.57O_x/Al₂O₃ system.     

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.     

Properties and Performance of Cation-Doped Ceria Electrolyte Materials in Solid Oxide Fuel Cell Applications

Cation-doped CeO₂ electrolyte has been evaluated in single-cell and short-stack tests in solid oxide fuel cell environments and applications. These results, along with conductivity measurements, indicate that an ionic transference number of ∼0.75 can be expected at 800°C. Single cells have shown a power density >350 mW/cm². Multicell stacks have demonstrated a peak performance of >100 mW/cm² at 700°C using metallic separators.