Catalysts, classification example

Referring to a mechanistic classification of organocatalysts (Seayad and List 2005), currently the two most prominent classes are Brpnsted acid catalysts and Lewis base catalysts. Within the latter class chiral secondary amines (enamine, iminium, dienamine activation for a short review please refer to List 2006) play an important role and can be considered as—by now—already widely extended mimetics of type I aldolases, whereas acylation catalysts, for example, refer to hydrolases or peptidases (Spivey and McDaid 2007). Thiamine-dependent enzymes, a versatile class of C-C bond forming and destructing biocatalysts (Pohl et al. 2002) with their common catalytically active coenzyme thiamine (vitamin Bi), are understood to be the biomimetic roots ofcar-bene catalysis, a further class of nucleophilic, Lewis base catalysis with increasing importance in the last 5 years. 

Proposed mechanisms for C-C bond formation can be organized into the following classifications carbene [70,71], carbocation [72], oxonium ylide [73,74], and free radical [75]. Some of these mechanisms [72-74] invoke a framework-bound methoxy species as a methylating agent or intermediate in the reaction. Dybowski and coworkers reported a C NMR study that supported the formation of methoxy groups in HZSM-5 [76], but the existence of these species is still controversial [77]. Framework-bound alkoxy species clearly do form on other molecular sieve catalysts. For example, Anderson and Klinowski have shown that when methanol is heated to 573 K on the silicoaluminophosphate catalyst SAPO-5, a framework-bound methoxy species forms, which is readily seen in a C MAS spectrum obtained after heating [77]. 

The classification of hydrocarbons as aliphatic or aromatic took place m the 1860s when It was already apparent that there was something special about benzene toluene and their derivatives Their molecular formulas (benzene is CgHg toluene is C7Hj ) indicate that like alkenes and alkynes they are unsaturated and should undergo addition reac tions Under conditions m which bromine for example reacts rapidly with alkenes and alkynes however benzene proved to be inert Benzene does react with Bi2 m the pres ence of iron(III) bromide as a catalyst but even then addition isn t observed Substitu tion occurs instead ... 

We first present further examples of the types of reactions involved in two main classifications, and then a preliminary discussion of various types of reactors used. Following an examination of some factors affecting the choice of reactor, we develop design equations for some reactor types, and illustrate their use with examples. The chapter concludes with a brief introduction to trickle-bed reactors for three-phase gas-liquid-solid (catalyst) reactions. 

The use of enzymes and whole cells as catalysts in organic chemistry is described. Emphasis is put on the chemical reactions and the importance of providing enantiopure synthons. In particular kinetics of resolution is in focus. Among the topics covered are enzyme classification, structure and mechanism of action of enzymes. Examples are given on the use of hydrolytic enzymes such as esterases, proteases, lipases, epoxide hydrolases, acylases and amidases both in aqueous and low-water media. Reductions and oxidations are treated both using whole cells and pure enzymes. Moreover, use of enzymes in sngar chemistiy and to prodnce amino acids and peptides are discnssed. 

The production model just discussed permits the classification of innovations into four main categories. The most obvious type of innovation is one which reduces the amount of one or more inputs required for the ith process that is, one which reduces the anl, ki> 07 i For example, such innovations may result from improvements in catalysts, or from improvements in the physical arrangements or efficiencies of equipment. 

Two-way analysis of variance (and higher classifications) leads to the presence of interactions. If, for example, an additive A is added to a lube oil stock to improve its resistance to oxidation and another additive, B, is added to inhibit corrosion by the stock under load or stress, it is entirely possible that the performance of the lube oil in a standard ball-and-socket wear test will be different from that expected if only one additive has present. In other words, the presence of one additive may adversely or helpfully affect the action of the other additive in modifying the properties of the lube oil. The same phenomenon is clearly evident in a composite rocket propellant where the catalyst effect on burning rate of the propellant drastically depends on the influence of fine oxidizer particles. These are termed antagonistic and synergistic effects, respectively. It is important to consider the presence of such interactions in any treatment of multiply classified data. To do this, the two-way analysis of variance table is set up as shown in Table 1.24. 

Another classification of chemical reactors is according to the phases being present, either single phase or multiphase reactors. Examples of multiphase reactors are gas liquid, liquid-liquid, gas solid or liquid solid catalytic reactors. In the last category, all reactants and products are in the same phase, but the reaction is catalysed by a solid catalyst. Another group is gas liquid solid reactors, where one reactant is in the gas phase, another in the liquid phase and the reaction is catalysed by a solid catalyst. In multiphase reactors, in order for the reaction to occur, components have to diffuse from one phase to another. These mass transfer processes influence and determine, in combination with the chemical kinetics, the overall reaction rate, i.e. how fast the chemical reaction takes place. This interaction between mass transfer and chemical kinetics is very important in chemical reaction engineering. Since chemical reactions either produce or consume heat, heat removal is also very important. Heat transfer processes determine the reaction temperature and, hence, influence the reaction rate. 

Molybdenum complexes are the most effective catalysts known for the selective epoxidation of olefins with alkyl hydroperoxides (210-212). Commonly known is the Arco or Halcon process for the large-scale manufacture of propylene oxide from propylene. This process uses t-BuOOH or ethyl benzene hydroperoxide (EBHP) as an oxidant and Mo(CO)6, for example, as a source of Mo. The Mo(CO)6 acts as a catalyst precursor, which is converted into a soluble active form by complexation with diols (3). Chemists have designed several supported versions of the catalysts for this epoxidation chemistry. A clear classification can be made on the basis of the nature of the support. 

The names of the examples of textile-relevant enzymes follow the nomenclature of Duclaux from 1898, characterising an enzyme by the end-syllable ase , added to the name of the snbstrate that is split, synthesised or otherwise catalysed. As with all catalysts, enzymes reduce the activation energy of a specific reaction. The discovery of large qnantities of new enzyme systems afforded a more differentiated nomenclatnre, realised in 1964 by the International Union of Pure and Applied Chemistry (lUPAC) and the International Union for Biochemistry (lUB). In the new enzyme classification (EC) the first nnmber refers to one of the six main gronps and the following numbers to subgroups, for example EC 3.4.S.6, where 3 stands for hydrolases. ... 

The order of stability also depends on the nature of the central atom (Si > Zr, Ti > Ge > P > As) and on the nature of the surrounding anion groups (W > Mo > V). This classification has some relevance to hydrotreating catalysts if, for example, introduction of Si into alumina as a support (giving silica-alumina, zeolite, etc.) leads to the formation of Mo —Si or W —Si heteropoly compounds, they will not be degraded during calcination. 

This chapter is intended to focus on catalysis in both thermal and photoinduced electron transfer reactions between electron donors and acceptors by investigating the effects of an appropriate substance that can reduce the activation barrier of electron transfer reactions. It is commonly believed that a catalyst affects the rate of reaction but not the point of equilibrium of the reaction. Thus, a substance is said to act as a catalyst in a reaction when it appears in the rate equation but not in the stoichiometric equation. However, autocatalysis involves a product acting as a catalyst. In this chapter, a catalyst is simply defined as a substance which affects the rate of reaction. This is an unambiguous classification, albeit not universally accepted, including a variety of terms such as catalyzed, sensitized, promoted, accelerated, enhanced, stimulated, induced, and assisted. Both thermal and photochemical redox reactions which would otherwise be unlikely to occur are made possible to proceed efficiently by the catalysis in the electron transfer steps. First, factors that accelerate rates of electron transfer are summarized and then each mechanistic viability is described by showing a number of examples of both thermal and photochemical reactions that involve catalyzed electron transfer processes as the rate-determining steps. Catalytic reactions which involve uncatalyzed electron transfer steps are described in other chapters in this section [66-68]. 

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