Fixed bed solid catalysis

TABLE 17.11. Jacketed Vessels Overall Heat Transfer Coefficients 

Jacket Buid Fluid in vessel Wall materia] Overall V bu/(h ft -°F) J/(ms-s-K)  

Heat-transfer oil Aqueous solution Stainless steel 40-170 230- 965 

A granular catalyst sometimes serves simultaneously as tower packing for reaction and separation of the participants by 

Jacket fluid Fluid in vessel Wall material Overall Btu/(h-ft - F) V J/(m K) 

TABLE 17.12. Overall Heat Transfer Coefficients with Immersed Colls lU expressed in Btu/(h. °F)] 

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Fittings, pipe, resistances, 95, 98-100 Fixed bed solid catalysis, 596 name reactor, 573 Flash conditions, 375-377 example, 378... 

In any catalyst selection procedure the first step will be the search for an active phase, be it a. solid or complexes in a. solution. For heterogeneous catalysis the. second step is also deeisive for the success of process development the choice of the optimal particle morphology. The choice of catalyst morphology (size, shape, porous texture, activity distribution, etc.) depends on intrinsic reaction kinetics as well as on diffusion rates of reactants and products. The catalyst cannot be cho.sen independently of the reactor type, because different reactor types place different demands on the catalyst. For instance, fixed-bed reactors require relatively large particles to minimize the pressure drop, while in fluidized-bed reactors relatively small particles must be used. However, an optimal choice is possible within the limits set by the reactor type. 

This chapter is devoted to fixed-bed catalytic reactors (FBCR), and is the first of four chapters on reactors for multiphase reactions. The importance of catalytic reactors in general stems from the fact that, in the chemical industry, catalysis is the rule rather than the exception. Subsequent chapters deal with reactors for noncatalytic fluid-solid reactions, fluidized- and other moving-particle reactors (both catalytic and noncatalytic), and reactors for fluid-fluid reactions. 

Agitated tank reactors Batch agitated reactor This is a batch stirred tank reactor. For liquid-solid systems, the liquid is agitated by a mechanical apparatus (impeller) and the reactor is of tank shape. For gas-solid systems, the gas is agitated and rapidly circulated through a fixed-bed of solids. This reactor is basically an experimental one used for adsorption, ion exchange, and catalysis studies. 

As a consequence of the line broadening effects of internal magnetic interactions on solid-state NMR spectra (Section ILA), experiments that characterize working solid catalysis require the application of the MAS technique. Because of the salient feature of MAS NMR spectroscopy (rapid sample spinning during the measurement), specific techniques had to be developed to allow characterization of solids in sealed vessels under batch reaction conditions and in fixed-bed reactors under flow conditions. 

There are indeed significant fundamental and practical differences between classical organic reactions (either stoichiometric or homogeneously catalysed ones) and those catalysed by solids and especially zeolites (Table 2.1). It is also the case when one compares the relatively simple transformations generally studied by the specialists in Heterogeneous Catalysis and the transformation of complex molecules involved in the synthesis of Fine Chemicals. The operating conditions are very different high temperature, gas phase, fixed bed reactors on the one hand low... 

A rough scheme of a continuously operated flow-type unit for studying a gas phase reaction on a solid catalyst is depicted in Figure 1. Arbitrarily, a fixed-bed reactor [3] was chosen. In fact, fixed-bed reactors are most popular in heterogeneous catalysis, because they are easy to construct, relatively inexpensive (even if designed for high pressure), robust (since there are no... 

Various kinds of oxide materials, including single oxides, mixed oxides, molybdates, heteropoly-ions, clays, and zeolites, are used in catalysis they can be amorphous or crystalline, acid or basic. Furthermore the oxides can be the actual catalysts or they can act as supports on which the active catalysts have been deposited. Silica and alumina are commonly used to support both metals and other metal oxide species. Amorphous silica/alumina is a solid acid catalyst, it is also used as a support for metals, when bifunctional (acid and metal) catalysis is required, e.g., in the cracking of hydrocarbons. Other acid catalysts are those obtained by the deposition of a soluble acid on an inert support, such as phosphoric acid on silica (SPA, used in the alkylation of benzene to cumene. Section 5.2.3). They show similar properties to those of the soluble parent acids, while allowing easier handling and fixed bed operation in commercial units. 

In the previous sections the use of catalysts dissolved in ionic liquids has been documented with a variety of examples from the most recent literature. They were classified are catalytic systems based on the adoption of Strategies A, B and C, when solvent-less conditions were not adopted. In an ideal liquid-liquid biphasic system, the IL must dissolve the catalytic intermediates and, in part, the substrate to avoid that mass transfer limits reaction rates. Moreover, products should have a limited solubility in the IL to allow a facile product removal or extraction, and, possibly, the recycle of the ionic liquid-trapped catalyst. The separation of the catalyst from the products is made easier if solid support-immobilised ILs are used. The preference for a solid catalyst is dictated not only by the easier separation but also, as outlined by Mehnert in an excellent review article, " by (i) the possible use of fixed bed reactors, and (ii) the use of a limited amount of IL, a generally expensive chemical which can limit the economic viability of the process. In this section attention will be focused only on the most recent examples of solid-phase assisted catalysis using ionic liquids, following Strategy D. Examples prior to 2006 are covered in recent reviews and will not be discussed here. " ... 

To apply continuous flow technologies, the choice of solid catalysts is highly recommended not only for the easier separation process involved but also for the use of fixed bed reactors. In this section attention is focused only on the most recent examples of solid-phase assisted catalysis using ionic liquids as the... 

If the transport limitation is significant, the catalysis occurs predominantly near the surface of the ionic liquid, and the [Rh(CO)2l2] dissolved in the bulk is not fully utilized. One attempt to address these issues was to use a supported ionic liquid phase (SILP) catalyst, as reported by Riisager et al. [Ill], In this system, the ionic liquid (l-butyl-3-methylimidazolium iodide) was supported as a thin film on solid silica (the thin film offers little mass-transport resistance) and used in a fixed-bed continuous reactor with gas-phase methanol. Rates were achieved that were comparable to those in Eastman s bubble column carbonylation reactor with gas-phase reactants [109], but using a much smaller amount of ionic liquid. 

Ragaini, V., G. Verzella, A. Ghigone, and G. Colombo, Fixed-Bed Reactors for Phase-Transfer Catalysis A Study of a Liquid-Liquid-Solid Reaction, Ind. Eng. Chem. Process Des.Dev., 25, 878 (1986). 

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