氯甲烷在镁修饰的ZSM-5分子筛催化剂上催化转化研究

在镁修饰的ZSM-5分子筛催化剂上,氯甲烷可以被催化转化为烃类产品。分别采用了离子交换和浸渍的方法来修饰ZSM-5分子筛。离子交换的Mg-ZSM-5催化剂和浸渍的Mg/ZSM-5催化剂都可以提高反应产物中的低碳烯烃的选择性,降低烷烃的选择性,并且保持较高的反应活性,但高的浸渍量对反应活性有一定的影响。NH3-TPD的结果表明,浸渍镁的ZSM-5催化剂的强酸中心数目明显减少。镁的修饰对催化剂酸性的影响导致了产物中低碳烯烃的增加。浸渍Mg的ZSM-5催化剂是潜在氯甲烷转化生成低碳烯烃的催化剂。     

Biotransformation of l‐menthol by twelve isolates of soil‐borne plant pathogenic fungi (Rhizoctonia solani) and classification of fungi

The microbial transformation of l‐menthol ( 1 ) was investigated by using 12 isolates of soil‐borne plant pathogenic fungi, Rhizoctonia solani (AG‐1‐IA Rs24, Joichi‐2, RRG97‐1; AG‐1‐IB TR22, R147, 110.4; AG‐1‐IC F‐1, F‐4, P‐1; AG‐1‐ID RCP‐1, RCP‐3, and RCP‐7) as a biocatalyst. Rhizoctonia solani F‐1, F‐4 and P‐1 showed 89.7–99.9% yields of converted product from 1 , RCP‐1, RCP‐3, and RCP‐7 26.0–26.9% and the other isolates 0.1–12.0%. In the cases of F‐1, F‐4 and P‐1, substrate 1 was converted to (?)‐(1S,3R,4S,6S)‐6‐hydroxymenthol ( 2 ), (?)‐(1S,3R,4S)‐1‐hydroxymenthol ( 3 ) and (+)‐(1S,3R,4R,6S)‐6,8‐dihydroxymenthol ( 4 ), which was a new compound. Substrate 1 was converted to 2 and/or 3 by RRG97‐1, 110.4, RCP‐1, RCP‐3 and RCP‐7. The structures of the metabolic products were elucidated on the basis of their spectral data. In addition, metabolic pathways of the biotransformation of 1 by Rhizoctonia solani are discussed. Finally, from the main component analysis and the differences in the yields of converted product from 1 , the 12 isolates of Rhizoctonia solani were divided into three groups based on an analysis of the metabolites. Copyright © 2003 Society of Chemical Industry     

Cd-ZSM-5沸石催化剂的制备、表征和芳构化催化性能

采用离子交换、浸渍和混合三种方法制备镉改性ZSM-5沸石催化剂,考察了改性方法和镉含量对催化剂的表面酸性和Cd状态以及芳构化性能的影响。结果表明,加入镉降低了B酸性,Cd~(2+)与沸石结合形成了L_(1612)酸中心,其生成量取决于改性方法和Cd含量,并与芳构化活性提高有直接关系。     

Comparison of inward and outward grown Pt modified aluminide diffusion coatings on a Ni based single crystal superalloy

Two commercial Pt modified aluminide coatings (RT22 and MDC150L) on the same single crystal Ni-based superalloy (CMSX-4) were studied by: scanning electron microscopy; transmission electron microscopy; energy dispersive X-ray spectrometry; and gravimetry. The RT22 coating is an inward grown coating (high activity), while MDC150L is produced by outward growth (low activity). Samples were oxidised in still laboratory air at 1050 °C for various times up to 2000 h. It was found that the outward grown coating produced a slower growing oxide that was more spallation resistant. Several possible reasons for this were identified including: coating purity; coating surface topography; and ductile to brittle transition temperature. The microstructural differences between the two coatings in the as-coated condition were investigated and the development of their microstructure during heat treatment was described. A model for coating growth during heat treatment was proposed.     

R22替代制冷剂的生产控制评价

本文详细介绍了R2 2替代制冷剂的生产过程控制和整机可靠性评价 ,并介绍了一些具体做法。     

A STUDY ON ACIDITY AND CATALYTIC PROPERTY OF [B] ZSM-5 CATALYST MODIFIED WITH SILICON COMPOUND BY CHEMICAL SURFACE DEPOSITION OF LIQUID-PHASE TECHNIQUE

The boron heteroatom zeolite catalyst has been modified with silicon compound by Chemical Surface Deposition of Liquid-phase (CLD) technique and the catalytic property of the modified catalyst is studied. Meanwhile, the acidity of the modified zeolite catalysts is characterized through TPD and IR technique, and the fluid adsorption method is used to determine its pore structure. The relationship between the catalytic property of the zeolite catalyst and its pore structure, its acidity has been found. The results of toluene-ethylene alkylation reaction indicate that the selectivity of p-ethyltoluene on the modified zeolite catalyst is higher than that on the zeolite catalyst before silanizated, reaching 94.14%.     

Semiparametric Estimation in Time‐Series Regression with Long‐Range Dependence

Abstract. We consider semiparametric estimation in time‐series regression in the presence of long‐range dependence in both the errors and the stochastic regressors. A central limit theorem is established for a class of semiparametric frequency domain‐weighted least squares estimates, which includes both narrow‐band ordinary least squares and narrow‐band generalized least squares as special cases. The estimates are semiparametric in the sense that focus is on the neighbourhood of the origin, and only periodogram ordinates in a degenerating band around the origin are used. This setting differs from earlier studies on time‐series regression with long‐range dependence, where a fully parametric approach has been employed. The generalized least squares estimate is infeasible when the degree of long‐range dependence is unknown and must be estimated in an initial step. In that case, we show that a feasible estimate which has the same asymptotic properties as the infeasible estimate, exists. By Monte Carlo simulation, we evaluate the finite‐sample performance of the generalized least squares estimate and the feasible estimate.     

Influence of Reaction Parameters on the Hydrogenolysis of Hydroxymatairesinol Over Carbon Nanofibre Supported Palladium Catalysts

The density functional theory (DFT/B3LYP) calculations were applied to investigate the interaction of a Pt₆ particle with the ZSM-5 zeolite framework. The electronic structure of the metal particle is strongly affected by the interaction with basic framework oxygens and acid sites of the zeolite support. Adsorption on basic sites (E_ads = 6 kcal/mol) favors the formation of the electron enriched metal cluster. Interaction of the platinum cluster with the acid site characterized by stabilization energy of 47 kcal/mol results in oxidation of the metal particle and suppression of Brønsted acidity of the support. The hypothesis is put forward that the oxidized platinum particle can function as an active site for the alkane isomerisation on platinum supported high silica zeolites.     

Second-law-based thermodynamic analysis of two-stage and mechanical-subcooling refrigeration cycles

Thermodynamic analysis of HFC-134a vapor-compression refrigeration cycles is investigated by both the first and second laws of thermodynamics. Second-law analysis is carried out for both two-stage and mechanical-subcooling refrigeration cycles. The analysis is performed on each of the system components to determine their individual contribution to the overall system irreversible losses. It is found that most of the losses are due to a low compressor efficiency. Irreversibilities of expansion valves and condenser are also significant. In addition, it is shown that the optimum inter-stage pressure for two-stage and mechanical-subcooling refrigeration systems is very close to the saturation pressure corresponding to the arithmetic mean of the refrigerant condensation and evaporation temperatures. These results are compared with the existing practice in the industry. Furthermore, theoretical results of a two-stage refrigeration system performance are also compared with experimental values for a CFC-22 system.