Fixed-bed catalysis

The abatement of chlorine vents and the subsequent destruction of the resulting sodium hypochlorite has been the subject of many studies. There are a variety of approaches to the waste hypochlorite destruction including chemical dosing, homogeneous and slurry catalysis as well as fixed-bed catalysis. For the most part these processes treat the hypochlorite at its natural strength the stoichiometric equivalent strength of the caustic soda fed to the scrubber. 

Yavorsky, Paul M., Akhtar, Sayeed, and Friedman, Sam. Process Developments Fixed-Bed Catalysis of Coal to Fuel Oil. AIChE Symposium Series, v. 70, No. 137, pp. 101-105, 1974. 

Following completion of the bench scale test program, an engineering contractor conducted a study and prepared the preliminary design for a pilot plant having a nominal production capacity of 20 short tons of sulfur/day when treating pure sulfur dioxide. This study found that fixed-bed catalysis was more practical. The preliminary pilot plant design, therefore, provided for a fixed-bed primary reactor of the shell-and-tube type in which the catalyst would be in the tubes. 

Even ia 1960 a catalytic route was considered the answer to the pollution problem and the by-product sulfate, but nearly ten years elapsed before a process was developed that could be used commercially. Some of the eadier attempts iacluded hydrolysis of acrylonitrile on a sulfonic acid ion-exchange resia (69). Manganese dioxide showed some catalytic activity (70), and copper ions present ia two different valence states were described as catalyticaHy active (71), but copper metal by itself was not active. A variety of catalysts, such as Umshibara or I Jllmann copper and nickel, were used for the hydrolysis of aromatic nitriles, but aUphatic nitriles did not react usiag these catalysts (72). Beginning ia 1971 a series of patents were issued to The Dow Chemical Company (73) describiag the use of copper metal catalysis. Full-scale production was achieved the same year. A solution of acrylonitrile ia water was passed over a fixed bed of copper catalyst at 85°C, which produced a solution of acrylamide ia water with very high conversions and selectivities to acrylamide. 

Steps 1 through 9 constitute a model for heterogeneous catalysis in a fixed-bed reactor. There are many variations, particularly for Steps 4 through 6. For example, the Eley-Rideal mechanism described in Problem 10.4 envisions an adsorbed molecule reacting directly with a molecule in the gas phase. Other models contemplate a mixture of surface sites that can have different catalytic activity. For example, the platinum and the alumina used for hydrocarbon reforming may catalyze different reactions. Alternative models lead to rate expressions that differ in the details, but the functional forms for the rate expressions are usually similar. 

The authors would like to acknowledge the contributions of several individuals for their insight and hard work in achieving the data included in this report J. Scott McCracken (TAP reactor), Kevin S. Slusser (fixed bed reactor), and Tom Borecki (catalysis synthesis). The authors would also like to thank DuPont s vinyl acetate business and manufacturing teams for allowing this work to be published. 

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. 

O Shea, V. A. D., Alvarez-Galvan, M. C., Campos-Martin, J. M., and Fierro, J. L. G. 2007. Fischer-Tropsch synthesis on mono- and bimetallic Co and Fe catalysts in fixed-bed and slurry reactors. Applied Catalysis A General 326 65-73. 

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. 

The structure of this review is as follows. Section II focuses on the basic principles of MRI techniques, and then more advanced techniques which have been used to study catalytic reactors will be introduced in Section III. To illustrate the use of these techniques examples will be given from the field of catalysis, although not necessarily at the scale of the reactor and, in some cases, data for model systems will be shown. Section IV describes methods used to achieve chemical mapping. Section V focuses exclusively on previous research which has used MRI techniques to spatially resolve chemical composition in fixed-bed reactors. 

Skeletal catalysts are usually employed in slurry-phase reactors or fixed-bed reactors. Hydrogenation of cottonseed oil, oxidative dehydrogenation of alcohols, and several other reactions are performed in sluny phase, where the catalysts are charged into the liquid and optionally stirred (often by action of the gases involved) to achieve intimate mixing. Fixed-bed designs suit methanol synthesis from syngas and catalysis of the water gas shift reaction, and are usually preferred because they obviate the need to separate product from catalyst and are simple in terms of a continuous process. 

Catalysts have been bonded to insoluble polymers to allow, in principle, an appreciable simplification of PTC the catalyst represents a third insoluble phase which can be easily recovered at the end of the reaction by filtration, thus avoiding tedious processes of distillation, chromatographic separation and so on. This is of potential interest mainly from the industrial point of view, due to the possibility of carrying on both discontinuous processes with a dispersed catalyst and continuous processes with the catalyst on a fixed bed. This technique was named "triphase catalysis" by Regen (13,33,34). 

There are reports of numerous examples of dendritic transition metal catalysts incorporating various dendritic backbones functionalized at various locations. Dendritic effects in catalysis include increased or decreased activity, selectivity, and stability. It is clear from the contributions of many research groups that dendrimers are suitable supports for recyclable transition metal catalysts. Separation and/or recycle of the catalysts are possible with these functionalized dendrimers for example, separation results from precipitation of the dendrimer from the product liquid two-phase catalysis allows separation and recycle of the catalyst when the products and catalyst are concentrated in two immiscible liquid phases and immobilization of the dendrimer in an insoluble support (such as crosslinked polystyrene or silica) allows use of a fixed-bed reactor holding the catalyst and excluding it from the product stream. Furthermore, the large size and the globular structure of the dendrimers enable efficient separation by nanofiltration techniques. Nanofiltration can be performed either batch wise or in a continuous-flow membrane reactor (CFMR). 

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. 

Fixed- or packed-bed reactors refer to two-phase systems in which the reacting fluid flows through a tube filled with stationary catalyst particles or pellets (Smith, 1981). As in the case of ion-exchange and adsorption processes, fixed bed is the most frequently used operation for catalysis (Froment and Bischoff, 1990 Schmidt, 2005). Some examples in the chemical industry are steam reforming, the synthesis of sulfuric acid, ammonia, and methanol, and petroleum refining processes such as catalytic reforming, isomerization, and hydrocracking (Froment and Bischoff, 1990). 

The energy balance (3.301) is applicable for catalysis, adsorption, and ion exchange. More specifically, in catalysis, where the steady-state condition exists, frequently the accumulation term is zero. In contrast, adsorption and ion exchange operate under unsteady-state condition. The analysis of the energy balance equation for catalytic fixed beds is presented in detail in Section 5.3.4. 

More or less, the comments above concerning the scale-up of the processes of adsorption and ion exchange in fixed beds can be also applied to catalysis. However, there are some points that should be emphasized in catalytic processes. 

In connection with the engineering content of the book, a large number of reactors is analyzed two- and three-phase (slurry) agitated reactors (batch and continuous flow), two-and three-phase fixed beds (fixed beds, trickle beds, and packed bubble beds), three-phase (slurry) bubble columns, and two-phase fluidized beds. All these reactors are applicable to catalysis two-phase fixed and fluidized beds and agitated tank reactors concern adsorption and ion exchange as well. 

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. 

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