Industrial data catalytic

Accuracy of Catalytic Tests in Laboratory Units and Comparison with Industrial Data... 

Microflow reactors as shown in Figures 21 and 22 are now capable of generating most of the catalytic performance data for fixed-bed processes applied in the hydrocarbon process industry, a task that some 25 years ago had to be reserved for large pilot plants with catalyst volumes of 10 L or more which required tank farms and gas holders and even on-site production of hydrogen to enable their operation. 

Figure 3 shows the steady-state radial temperature profiles for the two adiabatic catalytic beds operating at conditions of the optimal point. The corresponding axial temperature profiles in the interbed heat exchanger are also included in Fig. 3, for the tube side (Tt) and shell side (Tsh). The simulation results have been compared with industrial data corresponding to a large scale ammonia converter. The deviations at the reactor outlet were less than 0.2% (relative error) in composition and 14 °C in temperature (Toutz)-... 

Overall, catalytic processes in industry are more commonly described by simple power rate law kinetics, as discussed in Chapter 2. However, power rate laws are simply a parameterization of experimental data and provide little insight into the underlying processes. A micro-kinetic model may be less accurate as a description, but it enables the researcher to focus on those steps in the reaction that are critical for process optimization. 

The use of highly dispersed metals at low concentration levels has found wide use In Industry, particularly for electronic and catalytic uses. The desire to optimize the size and mass uniformity of these metal particles Is of particular Interest. Characterization of these materials Is difficult especially when metal particle sizes are on the order of 5 nm or less and concentrations are below 1 wt-Z. Development of highly sophisticated techniques In recent years has provided new approaches to understanding the physical and chemical properties of these materials. Electron microscopy has proven quite valuable In the acquisition of data and subsequent generation of information, which Is necessary to understand the physical-chemical properties of Individual nm-slzed particles. 

This chapter contains a discussion of two intermediate level problems in chemical reactor design that indicate how the principles developed in previous chapters are applied in making preliminary design calculations for industrial scale units. The problems considered are the thermal cracking of propane in a tubular reactor and the production of phthalic anhydride in a fixed bed catalytic reactor. Space limitations preclude detailed case studies of these problems. In such studies one would systematically vary all relevant process parameters to arrive at an optimum reactor design. However, sufficient detail is provided within the illustrative problems to indicate the basic principles involved and to make it easy to extend the analysis to studies of other process variables. The conditions employed in these problems are not necessarily those used in current industrial practice, since the data are based on literature values that date back some years. 

The adsorption of gas can be of different types. The gas molecule may adsorb as a kind of condensation process it may under other circumstances react with the solid surface (chemical adsorption or chemisorption). In the case of chemiadsorption, a chemical bond formation can almost be expected. On carbon, while oxygen adsorbs (or chemisorbs), one can desorb CO or C02. Experimental data can provide information on the type of adsorption. On porous solid surfaces, the adsorption may give rise to capillary condensation. This indicates that porous solid surfaces will exhibit some specific properties. Catalytic reactions (e.g., formation of NH3 from N2 and Hj) give the most adsorption process in industry. 

A typical FCC operation can yield around 4-5 wt% propylene. The inclusion of ZSM-5 additives (Zeolite structural matrix-5) coupled with high reactor operating temperature (ROT) yields 5-10 wt% propylene with additive concentrations up to 10 wt% as per the industry standard as shown in the table below. This is based on data from commercially operating units around the world. A comparison of propylene yield from various catalytic cracking options is summarized below ... 

The oxidation of propene to acrolein has been one of the most studied selective oxidation reaction. The catalysts used are usually pure bismuth molybdates owing to the fact that these phases are present in industrial catalysts and that they exhibit rather good catalytic properties (1). However the industrial catalysts also contain bivalent cation molybdates like cobalt, iron and nickel molybdates, the presence of which improves both the activity and the selectivity of the catdysts (2,3). This improvement of performances for a mixture of phases with respect to each phase component, designated synergy effect, has recently been attributed to a support effect of the bivalent cation molybdate on the bismuth molybdate (4) or to a synergy effect due to remote control (5) or to more or less strong interaction between phases (6). However, this was proposed only in view of kinetic data obtained on a prepared supported catalyst. 

Most industrial reactors and high pressure laboratory equipment are built using metal alloys. Some of these same metals have been shown to be effective catalysts for a variety of organic reactions. In an effort to establish the influence of metal surfaces on the transesterification reactions of TGs, Suppes et collected data on the catalytic activity of two metals (nickel, palladium) and two alloys (cast iron and stainless steel) for the transesterification of soybean oil with methanol. These authors found that the nature of the reactor s surface does play a role in reaction performance. Even though all metallic materials were tested without pretreatment, they showed substantial activity at conditions normally used to study transesterification reactions with solid catalysts. Nickel and palladium were particularly reactive, with nickel showing the highest activity. The authors concluded that academic studies on transesterification reactions must be conducted with reactor vessels where there is no metallic surface exposed. Otherwise, results about catalyst reactivity could be misleading. 

It is well known, even from old literature data (ref. 1) that the presence of metal promotors like molybdenum and chromium in Raney-nickel catalysts increases their activity in hydrogenation reactions. Recently Court et al (ref. 2) reported that Mo, Or and Fe-promoted Raney-nickel catalysts are more active for glucose hydrogenation than unpromoted catalysts. However the effects of metal promotors on the catalytic activity after repeated recycling of the catalyst have not been studied so far. Indeed, catalysts used in industrial operation are recycled many times, stability is then an essential criterion for their selection. From a more fundamental standpoint, the various causes of Raney-nickel deactivation have not been established. This work was intended to address two essential questions pertinent to the stability of Raney-nickel in glucose hydrogenation namely what are the respective activity losses experienced by unpromoted or by molybdenum, chromium and iron-promoted catalysts after recycling and what are the causes for their deactivation ... 

For most gas-solid catalytic reactions, usually a rate equation corresponding to one form or another of the Hougen and Watson type described above can be found to fit the experimental data by a suitable choice of the constants that appear in the adsorption and driving force terms. The following examples have been chosen to illustrate this type of rate equation. However, there are some industrially important reactions for which rate equations of other forms have been found to be more appropriate, of particular importance being ammonia synthesis and sulphur dioxide oxidation 42 . 

The two industrial fluid catalytic cracking units that we consider are of type IV with U-bends. The two units vary in their input parameters which lead to different outputs. The following table contains the plant data for the two commercial FCC units under consideration. 

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