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Real Life Reactors.

Real Life reactors are normally complex and their design is based on coupled effect of kinetics and hydrodynamics.

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Kinetics & Hydrodynamics ?

CRE deals with relating output to input for various reaction kinetics and flow-pattern / hydrodynamics

HETROGENEOUS REACTIONS
Most of the real life reaction systems involve heterogeneous catalyst . For any heterogeneous systems phase boundaries are inherent and need to be delt-with for heat and mass transfer along with reaction kinetics Thus physical processes affect the reactor design in more than that for homogeneous reaction systems However the starting point for both type of systems is to write mass and energy balance. This could be more involved for Heterogeneous reaction as these equations may have to be developed for each Phase

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GLOBAL RATE
Mass balance as starting point to develop performance equation for a reactor system include a kinetic term using reaction rate as moles / second / volume of the reactor. For Heterogeneous systems involving reaction fluid and solid catalyst particle, the proper rate to use in MB equation will include the effects of mass and energy transfer processes from fluid to solid surface and with in the solid particle. Such rates are called Global Rate

Packed Bed Gas Solid Reactor

CAout

Global Rate Based on C A-in, CA-out, Catalyst Weight and Flow rate

CAin

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GLOBAL RATE TO INCLUDE

Global rate in terms of bulk properties should include different steps contributing to the global rate. Following is the Sequence of Steps for converting reactants to products
1. 2. 3. 4. 5. 6. 7.

Transfer of Reactants from bulk to fluid-solid interface Intra-particle Transport of reactants in to catalyst particle (if Porous Catalyst) Adsorption of reactants at interior site Chemical Reaction of Adsorbed reactant to adsorbed product Desorption of adsorbed Product Transport of products from the interior sites to outer surface of the catalyst Transport of products from fluid-solid interface to bulk

Schematics follows..

Steps Involved . (Contd.):

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Typical Catalyst
Catalyst Structure
Catalyst Support (earth oxide, alumina, silica...) Metal finely deposited on the support responsible for the hydrogenation activity and the selectivity of the catalyst

The selected catalyst metal takes into account impurities related to the nature of the feedstock

Intra-catalyst Transfer
External surface of the catalyst grain

Micropores

Gas or liquid phase containing the reactives

Macropores

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Adsorption Reaction Desorption

Catalysis Mechanism
Adsorption of reactant on specific active site Chemical reaction on catalysts surface Product desorption

Pore inside the catalyst grain

Chemical reaction

Active site

Global Rate (Contd..)

Global Rate can be developed using the measurements at Steady State. At Steady State the rates of all above defined seven steps are equal. Thus for a simplified situation, Global rates can be defined using Bulk inlet and outlet concentration at bulk temperature of the fluid.

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Concept of Global Rate

As already indicated various steps are involved and should be considered to define GLOBAL REACTION RATE. Let us consider a irreversible reaction A(g) B(g) on solid Catalyst at constant Temperature Let for the sake of simplicity the Catalyst is non-porous so that intra catalyst transport does not take place and steps 2 and 6 above are absent. The problem is to formulate the rate of reaction per unit Volume of the bed (rv) in terms of bulk concentrations and temperature. Note that Reaction rates per unit mass of the catalyst (rp ) are related to (rv ) using catalyst bulk density

Concept Global Rate Contd.

For non porous catalyst steps involved are 1, 3,4,5, and 7 Supposing that steps 3, 4 and 5 can be represented by single first order reaction, the over all raction can be described in three steps
Gas A transported from Bulk to Catalyst Surface 2. Reaction Occurs at catalyst Surface 3. Finally Product B is transferred from Catalyst Surface to Bulk.
1.

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Concept Global Rate Contd.

Since for irreversible reaction Presence of B does not influence the rate the disappearance of A can be represented by first 2 steps only e.g.
Rate of Transfer of A from bulk to the catalyst surface

rp = k m am (Cb Cs )
Or Rate of reaction at the surface

rp = k C s
km is the mass transfer rate per unit area and am is the transfer area per unit catalyst wt. k is the reaction rate per unit mass of catalyst At steady state both the rates are the same

Concept Global Rate Contd.

Because Cs < Cb to facilitate transfer of A Actual rate is lower than that it would be for Cb . Therefore Mass Transfer resistance is reducing the overall reaction rate

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Cs and Cb variation with resistance

Reaction Control Cb Intermediate Cs Diffusion Control

Global Rate in terms of Cb

At steady state both mass transfer and reaction rates are equal i.e.

rp = k m a m (C b C s ) = k C or C
s

kmam Cb kmam + k ng for C s we have Cb 1 1 1 + k kmam

or substituti rp =

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Global Rate contd

This is the expression for the Global rates. Of course it is subjected to many simplifications as stated in the previous slides, however fully demonstrates the concept of a Global Rate. Subsequent modules addresses the less simplified situations to describe Global Rate.

Coupled effect of Mass and Heat transfer

Above hypothetical example considers resistances to mass transfer (1/km am) as well as Chemical Reaction (1/k). Incase of exo- or endothermic reactions, resistance to heat transfer is also important. There are examples that Higher temperature at the reaction site on the catalyst in case of exothermic reaction, there could be an offset of 350% in the estimated of reaction rate, if estimated using intrinsic kinetics. Therefore methodical analysis is important for heterogeneous reaction systems

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Types of Heterogeneous Reactions

Types of Heterogeneous Reaction systems can be classified depending on the types of phases invoved.. Gas Solid heterogeneous reaction systems are commonly encountered and could be Catalytic and Non-Catalytic. Non-Catalytic Heterogeneous reactions involves reaction of Gas phase with at least one solid reactant. Hydro fluorination of Uranium di-oxide or Smelting of ores (ZnS to ZnO) are such examples.

Contd
Example Non-Catalytic G-S reactions are
Hydroflorination of Uranium Di Oxide UO2 (s) + 4HF(g) UF4 (s) + 2 H2O(g) Smelting of Ores ZnS(S) + 3/2 O2(g) ZnO (s) + SO2 (g) Making HCl in Transport Reactor 2NaCl(s) + SO3(g) + H2O(g) Na2SO4(s)+2HCl(g)

Of course Non Catalytic gas-solid reactions are dynamic in nature due to consumption of solid reactant which is not the case with Solid catalyst based Gas-Solid Heterogeneous reaction Systems.

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Contd
Gas Liquid Heterogeneous systems present the example of Steady State Non-Catalytic Heterogeneous systems where reactant from gas phase are absorbed and continuously react with Liquid Phase Component. Bubble Column Reactors fall in this category which can operate co-current or Counter current manner. Chlorination of Para-cresol is one of the examples Co2 Absorption fro gas using Amine solution is another example

Contd
Liquid-Solid Reactions where solid is a catalyst are often encountered in Petroleum industry. Examples are: 1. Alkylation with AlCl3 Such systems are not simple to analyze and component of empiricism increases to have a design model. Three Phase (G-L-S - Slurry Reactors) systems are also employed in Petroleum industry for example Residue up-gradation through hydro Cracking.

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Contd
Liquid-Solid Reactions where solid is a catalyst are often encountered in Petroleum industry. Examples are: 1. Alkylation with AlCl3 Such systems are not simple to analyze and component of empiricism increases to have a design model. Three Phase (G-L-S - Slurry Reactors) systems are also employed in Petroleum industry for example Residue up-gradation through hydro Cracking.

Contd
Gas-Liquid -Solid reaction systems as packed bed in the form of Trickle bed reactors are also employed extensively for large scale hydro-treatments in Petroleum refining. Liquid Liquid multiphase reactors are also encountered. Alkylation of Hydrocarbons with Sulfuric Acids or HF is an example. Solid Solid non catalytic reactions are relevant for ceramics industry. However, diffusion process/ resistance are difficult to define and little is known about these.

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