Solid catalysts reactants

There are many different kinds of catalysts. Heterogeneous catalysts are solid materials, usually with a high specific surface area. The heterogeneous catalysts that are used in various industrial processes have specific surface areas that range from about 10 to 1000 m /g. One or more fluid phases are in contact with the solid catalyst. Reactant molecules in the fluid phase adsorb on the surface of the solid catalyst, rearrange or react with another adsorbed molecule, and then the product(s) desorb back into the fluid(s). Chapter 9 treats the subject of heterogeneous catalysis in much greater detail. 

Macroscopic properties often influence tlie perfoniiance of solid catalysts, which are used in reactors tliat may simply be tubes packed witli catalyst in tlie fonii of particles—chosen because gases or liquids flow tlirough a bed of tliem (usually continuously) witli little resistance (little pressure drop). Catalysts in tlie fonii of honeycombs (monolitlis) are used in automobile exliaust systems so tliat a stream of reactant gases flows witli little resistance tlirough tlie channels and heat from tlie exotlieniiic reactions (e.g., CO oxidation to CO,) is rapidly removed. 

Separability. One of the greatest advantages of a solid catalyst is that it can be separated easily from the products of reaction. To do this successfully requires careful control of the process conditions so that exposure of the catalyst to nonreactant liquids capable of affecting or dissolving either the catalytic material or the support is prevented or rninimi2ed. Solid catalysts typically are used in axial or radial flow beds and multitubular reactors. Many successful commercial processes maintain the reactants and products in the gas phase while in contact with the catalyst to avoid catalyst degradation problems. 

Consider a gaseous reactant flowing through a bed of solid catalyst pellets. The physical steps involved are the transfer of the component... 

Figure 4-8 shows a continuous reactor used for bubbling gaseous reactants through a liquid catalyst. This reactor allows for close temperature control. The fixed-bed (packed-bed) reactor is a tubular reactor that is packed with solid catalyst particles. The catalyst of the reactor may be placed in one or more fixed beds (i.e., layers across the reactor) or may be distributed in a series of parallel long tubes. The latter type of fixed-bed reactor is widely used in industry (e.g., ammonia synthesis) and offers several advantages over other forms of fixed beds. 

The effect of physical processes on reactor performance is more complex than for two-phase systems because both gas-liquid and liquid-solid interphase transport effects may be coupled with the intrinsic rate. The most common types of three-phase reactors are the slurry and trickle-bed reactors. These have found wide applications in the petroleum industry. A slurry reactor is a multi-phase flow reactor in which the reactant gas is bubbled through a solution containing solid catalyst particles. The reactor may operate continuously as a steady flow system with respect to both gas and liquid phases. Alternatively, a fixed charge of liquid is initially added to the stirred vessel, and the gas is continuously added such that the reactor is batch with respect to the liquid phase. This method is used in some hydrogenation reactions such as hydrogenation of oils in a slurry of nickel catalyst particles. Figure 4-15 shows a slurry-type reactor used for polymerization of ethylene in a sluiTy of solid catalyst particles in a solvent of cyclohexane. 

Measurements of the true reaction times are sometimes difficult to determine due to the two-phase nature of the fluid reactants in contact with the solid phase. Adsorption of reactants on the catalyst surface can result in catalyst-reactant contact times that are different from the fluid dynamic residence times. Additionally, different velocities between the vapor, liquid, and solid phases must be considered when measuring reaction times. Various laboratory reactors and their limitations for industrial use are reviewed below. 

A similar nonlinear equation for heterogeneous catalytic systems was developed empirically by Olaf Hougen and Kenneth Watson and derived on a more scientific basis by Irving Langmuir and Cyril Hmshelwood. WTien applied to fluid reactants and solid catalysts, the nonlinear equation m its simplest form becomes... 

If the three-parameter Michaelis-Menten equation is divided by C i, it becomes the same as the three-parameter Langmuir-I linshelwood equation where 1/Cm = Ka. Both these rate equations can become quite complex when more than one species is competing with the reactant(s) for the enzyme or active sites on the solid catalyst. 

From a theoretical point of view the study of the kinetics of coupled catalytic reactions makes it possible to investigate mutual influencing of single reactions and the occurrence of some phenomena unknown in the kinetics of complex reactions in the homogeneous phase. This approach can yield additional information about interactions between the reactants and the surface of the solid catalyst. 

As a final example of the application of gas-liquid-particle operation to a process involving a gaseous reactant and a solid catalyst, the possibility of polymerizing ethylene in, for example, a slurry operation employing a metal or metal oxide catalyst can be cited. It has been suggested that the good control of reaction conditions obtained in a slurry-type operation may be of importance in the production of certain types of polyethylene (Rl). 

The catalytic converter on a car uses a precious-metal-based, solid catalyst, usually in the form of a monolith, to convert unburned hydrocarbons and carbon monoxide to carbon dioxide. Many different reactants are converted to two products CO2 and water. 

The carbon removal reaction supposedly takes place at two-phase boundary of a solid catalyst, a solid reactantfcarbon particulate) and gaseous reactants(02, NO). Because of the experimental difficulty to supply a solid carbon continuously to reaction system, the reaction have been exclusively investigated by the temperature programmed reaction(TPR) technique in which the mixture of a catalyst and a soot is heated in gaseous reactants. 

Figure 1.2. Potential energy diagram of a heterogeneous catalytic reaction, with gaseous reactants and products and a solid catalyst. Note that the uncatalyzed reaction has to overcome a substantial energy barrier, whereas the barriers in the catalytic route are much lower.

Adsorption of reactants on the surface of the catalyst is the first step in every reaction of heterogeneous catalysis. Flere we focus on gases reacting on solid catalysts. Although we will deal with the adsorption of gases in a separate chapter, we need to discuss the relationship between the coverage of a particular gas and its partial pressure above the surface. Such relations are called isotherms, and they form the basis of the kinetics of catalytic reactions. 

For a catalytic reaction of a reactant from a single fluid phase (either gas or liquid) to take place on a solid catalyst, diffusion processes also play a role, so in the complete process the following steps can be distinguished ... 

The flow pattern of fluids in gas-liquid-solid (catalyst) reactors is often far from ideal. Special care must be taken to avoid by-passing of the catalyst particles near the reactor walls, where the packing density of the catalyst pellets is lower than in the centre of the bed. By-passing becomes negligible if the ratio of reactor to particles diameter is larger than 10 a ratio of 20 is recommended. Flow maldistributions might be serious in the case of shallow beds. Special devices must be used to equalize the velocity over the cross-section of the reactor before reactants are introduced onto the catalyst bed. 

Considering the specific application of chemical synthesis, the presence of solid catalyst (particles/salts in a typical concentration range of 1-10% by weight of the reactants optimization is recommended in majority of the cases using laboratory... 

Slurry Reactors. Slurry reactors are commonly used in situations where it is necessary to contact a liquid reactant or a solution containing the reactant with a solid catalyst. To facilitate mass transfer and effective catalyst utilization, the catalyst is usually suspended in powdered or in granular form. This type of reactor has been used where one of the reactants is normally a gas at the reaction conditions and the second reactant is a liquid, e.g., in the hydrogenation of various oils. The reactant gas is bubbled through the liquid, dissolves, and then diffuses to the catalyst surface. Obviously mass transfer limitations can be quite significant in those instances where three phases (the solid catalyst, and the liquid and gaseous reactants) are present and necessary to proceed rapidly from reactants to products. 

Although not all facets of the reactions in which complexes function as catalysts are fully understood, some of the processes are formulated in terms of a sequence of steps that represent well-known reactions. The actual process may not be identical with the collection of proposed steps, but the steps represent chemistry that is well understood. It is interesting to note that developing kinetic models for reactions of substances that are adsorbed on the surface of a solid catalyst leads to rate laws that have exactly the same form as those that describe reactions of substrates bound to enzymes. In a very general way, some of the catalytic processes involving coordination compounds require the reactant(s) to be bound to the metal by coordinate bonds, so there is some similarity in kinetic behavior of all of these processes. Before the catalytic processes are considered, we will describe some of the types of reactions that constitute the individual steps of the reaction sequences. 

Figure 12.4 Some modes of operation of semicontinuous reactors (a) gas-liquid reaction (b) gas-solid (catalyst or reactant) reaction (c) cyclic operation (reaction)-) and regeneration)- -)) for deactivating catalyst...

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