Fixed-Bed Reactors - Monoliths

Fixed-Bed Reactors - Monoliths 1189 Figure 9.10 Stack of SCR honeycombs. 

Scale-up in fixed-bed reactors is limited by the maximum size of the matrix that can be manufactured as a monolith. Hence, this system is appHcable for small- to medium-scale production of antibodies and other proteins, usually for the diagnostic market. This system has been described in greater detail ia the Hterature (22). 

Scientists from Politecnico di Milano and Ineos Vinyls UK developed a tubular fixed-bed reactor comprising a metallic monolith [30]. The walls were coated with catalytically active material and the monolith pieces were loaded lengthwise. Corning, the world leader in ceramic structured supports, developed metallic supports with straight channels, zig-zag channels, and wall-flow channels. They were produced by extrusion of metal powders, for example, copper, fin, zinc, aluminum, iron, silver, nickel, and mixtures and alloys [31]. An alternative method is extrusion of softened bulk metal feed, for example, aluminum, copper, and their alloys. The metal surface can be covered with carbon, carbides, and alumina, using a CVD technique [32]. For metal monoliths, it is to be expected that the main resistance lies at the interface between reactor wall and monolith. Corning... 

Compared with laboratory fixed-bed reactors or conventional extruded monoliths, such a microstructured monolith is smaller in characteristic dimensions, lower in pressure loss by optimized fluid guiding and constructed from the catalytic material solely [3]. The latter aspect also leads to enhanced heat distribution within the micro channels, giving more uniform temperature profiles. 

Most industrial catalysts are heterogeneous catalysts consisting of solid active components dispersed on the internal surface of an inorganic porous support. The active phases may consist of metals or oxides, and the support (also denoted the carrier) is typically composed of small oxidic structures with a surface area ranging from a few to several hundred m2/g. Catalysts for fixed bed reactors are typically produced as shaped pellets of mm to cm size or as monoliths with mm large gas channels. A catalyst may be useful for its activity referring to the rate at which it causes the reaction to approach chemical equilibrium, and for its selectivity which is a measure of the extent to which it accelerates the reaction to form the desired product when multiple products are possible [1],... 

The ANL catalyst (not identified, but presumably a Pt supported on Gd-doped ceria) was also successfully used for ATR of diesel fuel. Tests of three different types of diesel fuels (n-Cie, low-sulfur diesel, and regular diesel) showed complete conversion of hydrocarbons at 800°C. The diesel surrogate n-Ci6 yielded 60% H2 on a dry, N2-free basis at 800°C, whereas the other two diesel fuels required higher temperatures (>850°C) to yield similar levels of H2 in the product gases. Similar or improved H2 yields from diesel ATR were observed with a microchannel monolith catalyst, compared with extruded pellets in a fixed-bed reactor. ... 

Fixed bed reactors still predominate for fuel processing. However, fixed beds are susceptible to vibrational and mechanical attrition. Recently, monolithic reactors, either metallic or ceramic, have attracted interest for reforming processes since they offer higher available active surface areas and better thermal conductivity than conventional fixed beds. Low-pressure drop and robustness of the structure are major advantages of monolithic reactors. 

The basic equations that describe fixed-bed reactors have been presented in Section 3.6.2. In the present Section Isothermal, Adiabatic and Non-isobaric fixed bed operations as well as the case of Monolithic catalysts are presented. 

Then, a survey of micro reactors for heterogeneous catalyst screening introduces the technological methods used for screening. The description of microstructured reactors will be supplemented by other, conventional small-scale equipment such as mini-batch and fixed-bed reactors and small monoliths. For each of these reactors, exemplary applications will be given in order to demonstrate the properties of small-scale operation. Among a number of examples, methane oxidation as a sample reaction will be considered in detail. In a detailed case study, some intrinsic theoretical aspects of micro devices are discussed with respect to reactor design and experimental evaluation under the transient mode of reactor operation. It will be shown that, as soon as fluid dynamic information is added to the pure experimental data, more complex aspects of catalysis are derivable from overall conversion data, such as the intrinsic reaction kinetics. 

Alternatively it may take the form of a ceramic or metallic monolith, of which a variety of physical shapes is available monoliths are now widely used as supports for the active catalyst, which lines the channels which permeate the structure. They find particular application for the control of exhaust from vehicles powered by internal combustion or diesel engines. If the catalyst particles are small enough, a fast flow of reactants causes the bed to expand and the particles to move about like molecules in a liquid. We then have a fluidised bed reactor, which affords a more uniform temperature profile than is possible in fixed bed reactors, and is therefore more apposite to strongly exothermic reactions. 

Adiabatic fixed-bed reactors constitute the oldest fixed-bed reactor configuration. In the simplest case they consist of a cylindrical jacket in which the catalyst is loosely packed on a screen support and is traversed in the axial direction (Fig. 9A). To avoid catalyst abrasion by partial fluidization, random catalyst packings arc always traversed from top to bottom. If fixed-beds composed of monolith catalyst sections are used, the flow direction is arbitrary. 

Reference is made in Section 10.1.2.3 to the importance of uniform flow into and through adiabatic fixed-bed reactors. This is not easy to achieve, particularly with low-pressure-loss monolith reactors, and requires a careful design of the inflow hood. On account of the low pressure loss, unfavorable flow conditions in the outflow hood may also aflcct the flow behavior through the catalyst bed. 

There are many different reactor designs but the two most commonly used are fixed bed and batch slurry phase. For a fixed bed reactor a given volume of solid particulate or monolith supported catalyst is fixed in a heated tube located within a furnace and liquid and/or gaseous reactants flow through the bed. This type of process is commonly used for large continuous-volume production where the reactor is dedicated to making only one product such as a bulk chemical or petroleum product. 

The essence of monolithic catalysts is the very thin layers, in which internal diffusion resistance is small. As such, monolithic catalysts create a possibility to control the selectivity of many complex reactions. Pressure drop in straight, narrow channels through which reactants move in the laminar regime is smaller by two or three orders of magnitude than in conventional fixed-bed reactors. Provided that feed distribution is optimal, flow conditions are practically the same across a monolith due to the very high reproducibility of size and surface characteristics of individual monolith passages. This reduces the probability of occurrence of hot spots resulting from maldistributions characteristic of randomly packed catalyst beds. 

An interesting monolithic configuration has recently been disclosed that can be suitable for three-phase processes carried out in countercurrent mode [10]. This can be particularly important for processes in which both thermodynamic and kinetic factors favor countercurrent operation, such as catalytic hydrodesulfurization. The flooding of a reactor is a considerable limitation for the countercurrent process run in conventional fixed-bed reactors. Flooding will not occur to that extent in the new monolith. A configuration of channels of the new monolith is such that subchannels open to the eentcrline are formed at the walls. The liquid flows downward, being confined in these subchannels and kept there by surface tension forces. The gas flows upward in the center of the channel. The results of studies on the new monolith concept are presented in Chapter 11 of this book. 

The internally finned monolith as catalyst in a fixed-bed reactor can be designed for similar volumes of active catalyst material per unit of reactor space and similar surface-area-to-volume ratios as common particulate catalysts in fixed beds. 

The oxidation and reduction steps in the RAQ/RAHQ cycle are performed in two separate reactors. A bubble column is applied for the oxidation of the RAHQ, during which HP is produced. For the Pd-catalyzed hydrogenation of the quinones, a slurry, fixed-bed or monolith reactor can be used. After the reactor and L/L settler, a diluted H P-containing water-methanol stream is finally obtained. After the epoxidation step, crude PO is separated and the water-methanol mixture is returned to the HP synthesis process, thus realizing an efficient process integration. 

Figure 3 shows two examples of reactors with a fixed catalyst for gas-liquid reactions, viz. the trickle-bed reactor and the three-phase monolith reaetor. In these reactors the flow of liquid phase usually approaches plug flow. The figure also shows an example of a batch reactor system for a liquid-liquid reaction consisting of a mixing tank and a fixed-bed reactor with upward flow. This set-up is applied in aromatic acylation. 

On the other hand, the mechanical properties of monolithic carbon gels are of importance when they are to be used as adsorbents and catalyst supports in fixed-bed reactors, since they must resist the weight of the bed and the stress produced by its vibrations or movements. A few smdies have been published on the mechanical properties of resorcinol-formaldehyde carbon gels under compression [7,36,37]. The compressive stress-strain curves of carbon aerogels are typical of brittle materials. The elastic modulus and compressive strength depend largely on the network connectivity and therefore on the bulk density, which in turn depends on the porosity, mainly the meso- and macroporosity. These mechanical properties show a power-law density dependence with an exponent close to 2, which is typical of open-cell foams. 

The physical form of the support has to be chosen with a view to the type of reactor in which its use is intended. Silica and alumina are available as coarse granules or fine powders, and may be formed into various shapes with the aid of a binder (stearic acid, graphite) they can then be used in fixed bed reactors. For fluidised beds, or for use in liquid media, fine powders are required. Ceramic monoliths having structures resembling a honeycomb are used where (as in vehicle exhaust treatment) very high space velocities have to be used, but they are made of a non-porous material (a-alumina, muUite) and have to have a thin wash-coat of high area alumina applied, so that the metal can be firmly affixed. 

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