Catalyst Isotherm

Resin (BADGE) Anhydride Catalyst Isothermal (I) or Dynamic (D) method na lnA (s ) E kJ/mole Note Ref. 

For highly exothermic reactions, such as carbon monoxide oxidation, it may be hard to keep the catalyst isothermal, and if the rate of heat dissipation no longer keeps pace with heat generation it becomes hotter than the temperature shown by the sensing device the rate will then escalate... 

Alkene hydrogenation is significantly exothermic, and it is not always easy to keep the catalyst isothermal except at low rates. Heats of hydrogenation for a number of alkenes were measured many years ago (Table 7.1), the use of a catalyst ensuring that calorimetry could be conducted at ambient temperature. The values are similar to but perhaps more accurate than those derived from heats of combustion, where subtraction of two large numbers is involved they reflect the extents to which the jt electrons interact with the electrons in the C—H bonds by hyperconjugation. This electron delocalisation is also reflected in the relative stabilities of alkene complexes with Ag+ cations. ... 

Apparatus. The system was constructed by modifying an existing trickle-flow once through PDU reactor. A 2.5 cm diameter reactor was packed with a mixture of 100 cm of 1/16-inch extrudate catalyst and 100 cm of 1.0 mm silicon carbide non-porous Inerts, producing a 60 cm long catalyst bed. There were 25 cm long sections of Inerts above and below the catalyst. Isothermal conditions were maintained throughout the bed within about 5 C. 

Liu B, Fang Y, Terano M High resolution X-ray photoelectron spectroscopic analysis of transformation ofsur ce chromium species onPhiUips CrOx/Si02 catalysts isothermally calcined at various temperatures, J Mol Catal A Chem 219(1) 165—173, 2004a. 

Fig. XVII-29. Nitrogen isotherms the volume adsorbed is plotted on an arbitrary scale. The upper scale shows pore radii corresponding to various relative pressures. Samples A, Oulton catalyst B, bone char number 452 C, activated charcoal F, Alumina catalyst F12 G, porous glass S, silica aerogel. (From Ref. 196).

Emmett P H and Brunauer S 1937 The use of low temperature van der Waals adsorption isotherms in determining the surface area of iron synthetic ammonia catalysts J. Am. Chem. See. 59 1553-64... 

Navler-Stokes equation, 26 Non-isothermal catalyst pellet, 156-... 

Stea.m-Ra.ising Converter. There are a variety of tubular steam-raising converters (Fig. 7d) available, which feature radial or axial flow, with the catalyst on either shell or tube side. The near-isothermal operation of this reactor type is the most thermodynamically efficient of the types used, requiring the least catalyst volume. Lower catalyst peak temperatures also result in reduced by-product formation and longer catalyst life. 

The OLEFLEX process uses multiple side-by-side, radial flow, moving-bed reactors connected in series. The heat of reaction is suppHed by preheated feed and interstage heaters. The gas-phase reaction is carried out over a catalyst, platinum supported over alumina, under very near isothermal conditions. The first commercial installation of this technology, having an annual capacity of 100,000 t, was made in 1990 by the National Petrochemical Corporation in Thailand. A second unit, at 245,000 t capacity, has been built in South Korea by the ISU Chemical Company (70). 

Maintenance of isothermal conditions requires special care. Temperature differences should be minimised and heat-transfer coefficients and surface areas maximized. Electric heaters, steam jackets, or molten salt baths are often used for such purposes. Separate heating or cooling circuits and controls are used with inlet and oudet lines to minimize end effects. Pressure or thermal transients can result in longer Hved transients in the individual catalyst pellets, because concentration and temperature gradients within catalyst pores adjust slowly. 

Catalyst Effectiveness. Even at steady-state, isothermal conditions, consideration must be given to the possible loss in catalyst activity resulting from gradients. The loss is usually calculated based on the effectiveness factor, which is the diffusion-limited reaction rate within catalyst pores divided by the reaction rate at catalyst surface conditions (50). The effectiveness factor E, in turn, is related to the Thiele modulus,

first-order rate constant, a the internal surface area, and the effective diffusivity. It is desirable for E to be as close as possible to its maximum value of unity. Various formulas have been developed for E, which are particularly usehil for analyzing reactors that are potentially subject to thermal instabilities, such as hot spots and temperature mnaways (1,48,51). 

The Snamprogetti process utilizes a tubular isothermal reactor (tubes filled with catalyst) for the first reactor with cooling water on the shell side to control temperature. The Huls process uses either an adiabatic or isothermal reactor for the first reactor. 

Reactants must diffuse through the network of pores of a catalyst particle to reach the internal area, and the products must diffuse back. The optimum porosity of a catalyst particle is deterrnined by tradeoffs making the pores smaller increases the surface area and thereby increases the activity of the catalyst, but this gain is offset by the increased resistance to transport in the smaller pores increasing the pore volume to create larger pores for faster transport is compensated by a loss of physical strength. A simple quantitative development (46—48) follows for a first-order, isothermal, irreversible catalytic reaction in a spherical, porous catalyst particle. 

The ACR Process. The first step in the SCR reaction is the adsorption of the ammonia on the catalyst. SCR catalysts can adsorb considerable amounts of ammonia (45). However, the adsorption must be selective and high enough to yield reasonable cycle times for typical industrial catalyst loadings, ie, uptakes in excess of 0.1% by weight. The rate of adsorption must be comparable to the rate of reaction to ensure that suitable fronts are formed. The rate of desorption must be slow. Ideally the adsorption isotherm is rectangular. For optimum performance, the reaction must be irreversible and free of side reactions. 

Phenomena of multiple steady states and instabilities occur particularly with nonisothermal CSTRs. Some isothermal processes with hyperbohc rate equations and processes with porous catalysts also can have such behavior. 

The reaction kinetics approximation is mechanistically correct for systems where the reaction step at pore surfaces or other fluid-solid interfaces is controlling. This may occur in the case of chemisorption on porous catalysts and in affinity adsorbents that involve veiy slow binding steps. In these cases, the mass-transfer parameter k is replaced by a second-order reaction rate constant k. The driving force is written for a constant separation fac tor isotherm (column 4 in Table 16-12). When diffusion steps control the process, it is still possible to describe the system hy its apparent second-order kinetic behavior, since it usually provides a good approximation to a more complex exact form for single transition systems (see Fixed Bed Transitions ). 

Normally when a small change is made in the condition of a reactor, only a comparatively small change in the response occurs. Such a system is uniquely stable. In some cases, a small positive perturbation can result in an abrupt change to one steady state, and a small negative perturbation to a different steady condition. Such multiplicities occur most commonly in variable temperature CSTRs. Also, there are cases where a process occurring in a porous catalyst may have more than one effectiveness at the same Thiele number and thermal balance. Some isothermal systems likewise can have multiplicities, for instance, CSTRs with rate equations that have a maximum, as in Example (d) following. 

Oxide-supported metals constitute one of the most important classes of heterogeneous catalysts, and for this reason they have been investigated by many techniques adsorption isotherms, IR of chemisorbed molecules, electron microscopy, EXAFS, etc. Flowever, the fact that they have been studied by so many methods proves that no one technique is totally satisfactory. 

Figure 1.6.1 Comparison of asymptotic and exact solutions for a first order, non-isothermal reaction in a spherical catalyst pellet. ...

The use of CO is complicated by the fact that two forms of adsorption—linear and bridged—have been shown by infrared (IR) spectroscopy to occur on most metal surfaces. For both forms, the molecule usually remains intact (i.e., no dissociation occurs). In the linear form the carbon end is attached to one metal atom, while in the bridged form it is attached to two metal atoms. Hence, if independent IR studies on an identical catalyst, identically reduced, show that all of the CO is either in the linear or the bricked form, then the measurement of CO isotherms can be used to determine metal dispersions. A metal for which CO cannot be used is nickel, due to the rapid formation of nickel carbonyl on clean nickel surfaces. Although CO has a relatively low boiling point, at vet) low metal concentrations (e.g., 0.1% Rh) the amount of CO adsorbed on the support can be as much as 25% of that on the metal a procedure has been developed to accurately correct for this. Also, CO dissociates on some metal surfaces (e.g., W and Mo), on which the method cannot be used. 

Sampling of a two-fluid phase system containing powdered catalyst can be problematic and should be considered in the reactor design. In the case of complex reacting systems with multiple reaction paths, it is important that isothermal data are obtained. Also, different activation energies for the various reaction paths will make it difficult to evaluate the rate constants from non-isothermal data. 

Reactor type Sampling and analysis Isothermality Solid contact Fluid- decaying catalyst Ease of construction... 

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