CE3102 (Reaction Engineering II) Coursework

1. (a) Identify the three main processes that can lead to loss of catalytic activity. The main processes which cause deactivation / loss of catalytic activity: 1. Mechanism : Poisoning o Type : Chemical o Brief Description : Strong chemisorption of species on catalytic sites, thereby blocking active sites for catalytic reaction 2. Mechanism : Fouling o Type : Mechanical o Brief description : Physical deposition of species from uid phase onto the catalytic surface and in catalyst pores blocking active sites 3. Mechanism : Sintering o Brief Description : Thermally induced loss of catalytic surface area, support area, and active phasesupport reactions 1 (b) For each of the processes identified in (a), discuss how catalyst deactivation occurs and suggest how to minimise loss of activity. 1. Catalyst Deactivation: Catalyst poisoning refers to the effect that a catalyst can be poisoned if it reacts with another compound that bonds chemically to its active surface sites. This effectively reduces the usefulness of the catalyst. Poisoned sites can no longer accelerate the reaction with which the catalyst was supposed to catalyse and may cause changes in the surface morphology of the catalyst either by surface reconstruction or modification of the bond between the metal catalyst and the support. 1. Minimise loss of activity: Physical separation or by chemical treatment. Poisoned catalyst can hardly be regenerated, and therefore the best method to reduce poisoning is to decrease to acceptable levels the poison content of the feed. This is generally achieved by appropriate treatments of the feed, adsorption over appropriate beds of solids to remove trace amounts of poisons (e.g. ZnO for H2S or alkalinized alumina for HCl). In several processes, e.g. low-temperature , guard-beds are installed before the principal catalyst bed and effectively reduce the poisoning of the catalyst bed. 2. Catalyst Deactivation: The deposit of unwanted materials on a surface is defined as fouling, and affects how a chemical process proceeds. Fouling adds a layer of organic, inorganic or even living organisms to the surface which affects the properties of the catalyst and the mechanism of the process. Coke formation is one of the most prominent types of catalytic fouling and is chiefly involved in the deactivation of a catalyst. This coke formation forms a fouled layer on the surface of a catalyst which reduces how much of the surface area of the catalyst is available to the surroundings. With less surface area exposed, a catalyst is less effective.

2. Minimise loss of activity : Chemical fouling inhibitors can reduce fouling in many systems, mainly by interfering with the crystallization, attachment, or consolidation steps of the fouling process. On the component design level, fouling can often be minimized by maintaining a relatively high uniform fluid velocity throughout the component and so eliminating stagnant regions. Low-fouling surfaces (for example, very smooth, implanted with ions, or of low surface energy like Teflon) are an option for some applications. Chemical or mechanical cleaning processes for the removal of deposits and scales are recommended when fouling reaches the point of impacting the system performance. To minimize coking for example the reactor may be operated at short residence times / hydrogen may be added to the process stream to convert gas phase carbon into methane or by minimizing the temperature upstream of the catalyst bed. 3. Catalyst Deactivation: Catalyst Sintering degrades catalyst performance due to the loss of active surface area. A decrease in surface area of the catalyst results and consequently and irreversible reduction in catalyst sites. Generally occurs if the local temperature of the catalyst exceeds approximately 1/3 to of its melting temperature. 3. Minimise loss of activity : To prevent sintering, catalysts may be doped with stabilizers which may have a high melting point. An example of a stabilizer is Alumina.

1 (c) Compare the design equation for a Packed Bed Reactor (PBR) with that of a Plug Flow Reactor (PFR) and explain briefly how the rate terms, -rA, are related in the two equations.

The design equation for a Plug flow reactor is:

The design equation for a Packed bed reactor is:

The PFR design allows for the reactor to be sized by finding the volume of the reactor (V), whereas the PBR design equation uses the weight of the catalyst (W) to size the reactor. When calculating the rate constant for the PBR you need to take into account the adsorption of the reactant onto the catalyst surface, the chemical reaction on the surface and also the desorption of the products from the surface. The rate terms are related by the equation : ( ) ( ) where is the density

) is in volume units ( mol A m3 s-1 ) whereas in the PBR the rate is In the PFR equation the rate ( in mass units ( mol A ( kg cat ) -1 s -1 ).