Selective Hydrogenation of Ethyne in Ethene‐Rich Streams on Palladium Catalysts,Part 2: Steady‐State Kinetics and Effects of Palladium Particle Size,Carbon Monoxide,and Promoters

Developments in the last three decades of kinetics of selective hydrogenation of ethyne in ethene‐rich streams on palladium catalysts are reviewed. Most of the studies can be described comprehensively by a model that assumes carbonaceous deposits (i) create irreversibly on the palladium surface small A types of active site (selective to ethene) and large E types of active site (selective to ethane), and (ii) are involved in hydrogenation of ethene on E _s sites on the support. The relative importance of these sites, with varying (i) reaction conditions, (ii) palladium dispersion, (iii) process modifiers, and (iv) promoters, is discussed.     

The Mechanism of HDS Catalysis

The mechanism of heterogeneous catalytic reactions is much more difficult to elucidate than that of homogeneous systems. Despite the facilities provided by physical methods for investigating the surface of solids, obtaining detailed information on the structure of the active component in real heterogeneous catalysts presents difficulties due to the nonuniform chemical composition of the surface species. Some of these surface species are totally inactive in catalysis, and others can catalyze the given chemical reaction by different pathways and according to different mechanisms. This results in a change of selectivity to the desired product and the appearance of intermediates and reaction by-products. Furthermore, the effect of the reaction medium on the catalyst gains importance during a catalytic process when, at high temperature and pressure, one type of surface species is transformed into another, thus changing the mechanism and direction of the catalyzed reaction.

     

Bubble Column Reactors and Fischer-Tropsch Synthesis

Three-phase slurry bubble column reactors have been used extensively in a number of chemical, petrochemical, and biochemical process engineering applications. For the success of these operations and their large scale industrial exploitation, it is essential that their transport and chemical characteristics be adequately understood on a mechanistic basis so that appropriate design criteria and optimum operating conditions can be established. It is the purpose of this review to present such available knowledge in relation to chemical catalytic operations. The mass transfer characteristics, catalytic activity, and mixing patterns of different phases necessitate a detailed understanding of the hydrodynamic behavior and catalyst dispersion in slurry bubble column reactors. The current status of these aspects is presented, discussed, and assessed in this review. Chemical and biochemical reactions are exothermic in nature and hence efficient heat removal devices must be installed in the reactor to preserve its isothermal behavior and chemical catalytic activity by avoiding temperature runaway. Extensive work recently conducted from this heat transfer viewpoint is reviewed and appraised. The bubble dynamics, and slurry mixing and movement characteristics of such baffled bubble columns are significantly different from those of unbaffled bubble columns. Very limited information is available on baffled bubble column operations and this is reviewed and critically examined. An important application of the slurry bubble column is in the synthesis of fuel gases on suspended catalyst particle surface to produce chemicals. One such example is the Fischer-Tropsch synthesis of hydrogen and carbon monoxide in what is referred to as indirect coal liquefaction technology. Pilot plant efforts of this nature and their successes are briefly mentioned. Mathematical details and models developed from time to time to characterize catalytic bubble column operations are briefly described and discussed. In the context of available information and its integration presented here, the specific needs for future experimental and theoretical research work are pointed out.     

Dynamic Combinatorial Chemistry in Chemical Catalysis

Despite the progress in the field of dynamic combinatorial chemistry (DCC), dynamic combinatorial catalysis has received considerably less attention. Some first studies, however, have provided proof of principle and demonstrated that DCC-based approaches are also applicable in catalyst development. This provides interesting new tools that are complementary to rational catalyst design and traditional combinatorial strategies. As such, DCC may become highly valuable in the field of dynamic combinatorial catalysis, due also to the practical importance of catalysis. In this review we focus on the principles of dynamic combinatorial catalysis and provide an overview by the introduction of different concepts related to the development of libraries and selection procedures in catalysis.     

Regio‐ and Stereochemical Controlled Koenigs–Knorr‐Type Monoglycosylation of Secondary Hydroxy Groups in Carbohydrates Utilizing the High Site Recognition Ability of Organotin Catalysts

The catalytic regio‐ and stereoselective monoglycosylation of carbohydrates using organotin catalysts is demonstrated. The one‐step reaction affords various oligosaccharides linked at the secondary hydroxy group in high chemical yield and good regio‐ and stereoselectivities. The regioselectivity of the glycosylation is shown to depend on the spatial arrangement of the hydroxy groups in the carbohydrates.

     

Transfer and Reaction Performances of Selective Catalytic Reduction of N2O with CO over Monolith Catalysts

This work tries to identify the relationship between geometric configuration of monolith catalysts, and transfer and reaction performances for selective catalytic reduction of N2O with CO. Monolith cat...     

Study of Propylene Polymerization Catalyzed by Spherical MgCl2-Supported Ziegler-Natta Catalyst System: Preparation of Spherical Support

Abstract

A novel route to prepare the MgCl₂–EtOH adduct support was developed. Many factors which effect the morphology of the support were studied in detail. It was found that the stirring speed of dispersion and the molar ratio of EtOH/MgCl₂ had an important influence on the support particle size and particle size distribution. Through varying the stirring speed or changing the EtOH/MgCl₂ ratio, MgCl₂ adduct supports with different particle size and particle size distribution could be obtained.     

EPOXIDATION OF FUNCTIONALIZED OLEFINS OVER SOLID CATALYSTS

Heterogeneous catalytic epoxidation of functionalized olefins in the liquid phase has been reviewed, focusing on catalyst performance and its interrelation with the crucial parameters of the catalytic systems. Efficient catalysts include supported and mixed oxides, framework-substituted (“redox”) molecular sieves, layered-type materials, heterogenized homogeneous catalysts, and some others. Among the various substrates, allylic and homoallylic alcohols, and unsaturated carbonyl compounds have received most attention so far. The great variety of available catalysts enables selective epoxidation of most substituted olefins. The mechanistic understanding of heterogeneous catalytic epoxidation is still underdeveloped, rendering catalyst design rather empirical. A considerable potential for future development lies in the area of “heterogenization” of successful homogeneous catalysts especially for asymmetric epoxidation. Crucial requirements in the development of heterogeneous catalytic epoxidation catalysts are, besides good catalytic performance and cheap oxidant, recyclability and resistance to leaching of the active component. Some of the examples shown in the literature do not fulfill the latter requirement.     

Knowledge and Know‐How in Emission Control for Mobile Applications

Abstract

Concerns about emissions of carbon dioxide have created a need to develop more fuel‐efficient vehicles. Diesel engines are generally more efficient than gasoline engines but improvements in the latter can be achieved by operating under lean‐burn conditions. With both diesel and lean‐burn gasoline engines, the nitrogen oxides are emissted under oxidising conditions. It is scientifically very challenging to reduce nitrogen oxides under oxidising conditions. After a short survey of conventional three‐way catalysts, and the associated fundamental aspects of NO_x reduction under stoichoimetric conditions, this review focuses on the knowledge and know‐how that has been developed for lean engine emission control. Early research on hydrocarbon selective catalytic reduction on zeolite, oxide, and metal‐based systems is examined, and some of the key mechanistic models are described. Since none of these systems are of sufficient activity and stability to satisfy current legislation attention has turned to NO_x storage and reduction systems. The basic principles of these are described, and the present state of knowledge regarding the mechanisms of storage and regeneration are discussed. The many apparent discrepancies are highlighted and an attempt is made to rationalise the current state of knowledge by taking into account the varying experimental conditions reported nit he literature. For diesel engines, NO_x storage and reduction is not an ideal solution and so the final section of this review is concerned with silver‐based catalysts and especially with the dramatic effect of small amounts of hydrogen on the efficiency of these catalysts for hydrocarbons selective catalytic reduction.     

3,5-二羟基苯甲酸转移加氢动力学

研究了3,5-二羟基苯甲酸(DHB)为原料采用催化转移加氢法合成3,5-二氧代环己烷羧酸(DOC)的过程,得到了以5％Pd／C为催化剂、甲酸钠为氢供体的3,5-二羟基苯甲酸转移加氢宏观反应动力学。研究发现,在实验条件下原料3,5-二羟基苯甲酸的反应级数为0,供体甲酸钠和催化剂分别为一级;当氢供体大量过量时,3,5-二羟基苯甲酸的吸附速率是反应的控速步骤,初步探讨了反应过程的机理。