Reactor Designing Mathematical Models

Chemical reactors are vessels designed to contain chemical reactions. The design of
a chemical reactor deals with multiple aspects of chemical engineering including
mathematical modeling.
A model of a reaction process is a set of data and equation that is believed to
represent the performance of a specific vessel configuration (mixed, plug flow,
laminar, dispersed, etc.).
Chemical engineers, design reactors to maximize net present value for the given
reaction. Designers ensure that the reaction proceeds with the highest efficiency
towards the desired output product, producing the highest yield of product.
The equations used in mathematical modeling include the stoichiometric relations,
rate equations, heat and material balances and auxiliary relations such as those of
mass transfer, pressure variation, residence time distribution, etc.

Basic Elements of Reactor Designing

Reactions are carried out as batches or with continuous streams through a vessel. There
are two main basic vessel types, viz.;
Tank Reactor a tank

Tubular Reactor a pipe or tube

Most commonly, reactors are run at a steady-state, but can also be operated in a transient
state. Transient state is a state in which the key process variables like residence time,
volume, temperature, pressure or concentration of chemical species, etc., change with time.
Such a situation generally arises when either the reactor is purchased new or is brought
back in operation after maintenance or inoperation. Chemical reactors may be designed
keeping in view the various process variables. Key process variables include:
Residence Time Distribution ()

Volume (v)

Temperature (T)

Pressure (P)

Concentrations of chemical species (C1, C2 ------C4) Heat transfer coefficients (h, U)

Flow reactors are distinguished by the degree of mixing of successive inputs. The ideal
situations are
1) Complete mixing :- For example Continuous Stirred Tank Reactor (CSTR), and
2) No axial mixing For example, Plug Flow Reactor (PFR)
Real reactors deviate more or less from these ideal behaviours. Deviations may be
detected with RTDs obtained with the aid of tracer tests. The commonest models are
combinations of CSTRs and PFRs in series and/or parallel. Thus, a stirred tank may be
assumed completely mixed in the vicinity of the impeller or a plug flow near outlet.

Reactor Batch
Ideal Batch Reactor: It is a closed system. The mass balance for a substance A
becomes
IN + PROD = OUT + ACC
0 + rAV = dnA/dt + 0
where rA denote the rate at which substance A is produced, V is the volume (which
may be constant or not), nA the number of moles (n) of substance A.

In a fed-batch reactor some reactants/ingredients are added continuously or in pulses.

Batch reactors are used in batch processes.

Batch processes are suited to small production rates, to long reaction times, or to
reactions, where they may have superior selectivity, as in some polymerizations.
They are conducted in tanks with stirring of the contents by internal impellers, gas
bubbles or pump around. Control of temperature is done with the help of jackets,
reflux condensers or pump around through an exchanger.
Batch processes are currently used in the chemical and food process industries.
Their automation and optimization pose difficult issues mainly because it is
necessary to operate concurrently with countinous (algebric or differential
equations) and discrete (state machines) models. Andreu et al14, have tried to
analyse how techniques developed in the field of discrete manufacturing systems
(DMS) can be extended to batch systems.

Semi-batch reactors operate much like batch reactors in that they take place in a
single stirred tank with similar equipment . It modified allow reactant addition and/or
product removal in time. A semi-batch reactor, however, allows partial filling of
reactants with the flexibility of adding more as time progresses. Semi-batch reactors
are used primarily for liquid-phase reactions , two-phase reactions in which a gas
usually is bubbled continuously through the liquid , and also for biological and
polymerization reaction.
A semi-batch reactor is operated with both continuous and batch inputs and outputs.
A fermentor, for example, is loaded with a batch which constantly produces carbon
dioxide, which has to be removed continuously. Similarly, in a reaction like
chlorination, where one of the reactant is gas (chlorine), if it is introduced
continuously, most of it bubbles off, therefore a continuous feed of gas is injected into
the batch of a liquid.

(Adapted from H. S. Fogler, Elements ofChemical Reaction Engineering, 3rd ed.,

Prentice Hall, Upper Saddle River, NJ, 1999.) Pure butanol is fed into a semibatch
reactor containing pure ethyl acetate to produce butyl acetate and ethanol in the reversible
reaction:
CH3COOC2H5 + C4H9OH < CH3COOC4H9 + C2H5OH
The reaction rate can be expressed in the Guldberg-Waage form. The reaction is carried
out isothermally at 300 K. At this temperature, the equilibrium constant is 1.08 and the
forward rate constant is 9.0 X 10-5 L (mol s)-I. Initially, there are 200 L ofethyl acetate in
the reactor and butanol is fed at a rate of 0.050 L / s . The feed and initial concentrations
of butanol and ethyl acetate are 10.93 mol / L and 7.72 mol / L, respectively.
(a) Plot the equilibrium conversion of ethyl acetate as a function of time.
(b) Plot the conversion of ethylacetate, the rate of reaction, and the concentration of
butanol as a function of time.

Continuous-Stirred Tank
Reactor CSTR

Kinds of Phases
Usage
Present
1. Gas phase
1. When
2. Liquid phase agitation is
required
3. Liquid Solid
2. Series
configurations
for different
concentration
streams

Advantages

Disadvantages

1. Continuous operation

1. Lowest conversion
per unit volume, very
large reactors are
necessary to obtain
high conversions
2. By-passing and
channeling possible
with poor agitation

2. Good temperature control

3. Easily adapts to two phase
runs
4. Simplicity of construction
5. Low operating (labor) cost
6. Easy to clean

Characteristics Continuous-Stirred Tank Reactor CSTR

Run at steady state ,the flow rate in must equal the mass flow rate out, otherwise
the tank will overflow or go empty transient state).
The feed assumes a uniform composition throughout the reactor, exit stream has
the same composition as in the tank.
The reaction rate associated with the final (output) concentration
Reactor equipped with an impeller to ensure proper mixing
Dividing the volume of the tank by the average volumetric flow rate through the
tank gives the residence time or the average amount of time a discrete quantity of
reagent spends inside the tank

Some important aspects of the CSTR:

It is economically beneficial to operate several CSTRs in series. This
allows, for example, the first CSTR to operate at a higher reagent
concentration and therefore a higher reaction rate. In these cases, the sizes
of the reactors may be varied in order to minimize the total capital
investment required to implement the process.

Figure (3) Flow sheet for the manufacture of

nitrobenzene from benzene using a cascade of CSTR

Tubular Reactor
(PFR)

Kinds of
Phases
Present
1. Primarily
Gas
Phase

Usage
1. Large Scale
2. Fast Reactions
3. Homogeneous Reactions
4. Heterogeneous Reactions
5. Continuous Production
6. High Temperature

Advantages

Disadvantages

1. High Conversion
per Unit Volume
2. Low operating
(labor) cost)
3. Good heat
transfer

1. Undesired thermal
gradients may exist
2. Difficult temperature
control
3. Shutdown and
cleaning may be
expensive
4. Hot spot occur for
exothermic reaction

Characteristics Tubular Reactor PFR

Consists of long cylindrical tube or many short reactors in a
tuve
Operated at steady state.
The rate is very high at the inlet to the PFR
No radial variation in reaction rate (concentration) and the
reactor is referred to as a plug-fiow rcactor (PFR).
Concentration changes with length down the reactor
As the concentrations of the reagents decrease and the
concentration of the product(s) increases the reaction rate
slows.
A PFR typically has a higher efficiency than a CSTR of the
same volume. That is, given the same space-time, a reaction
will proceed to a higher percentage completion in a PFR
than in a CSTR.

Packed bed Reactor

(fixed-bed,PBR)
Is essentially a tubular
reactor that is packed with
solid catalyst particles.

Kinds of Phases
Present
1. Gas-Soli phase
2. Liquid-Solid
phase
3. Gas-Liquid Solid

Usage
Heterogeneous
reaction

Advantages

Disadvantages

Most reaction gives the 1. Difficulties with temperature control

highest conversion per
2. Catalyst is usually troublesome to
weight of catalyst of
replace
any catalytic reactor.
3. Channeling of the gas or liquid flow
occurs, resulting in ineffective use of
part of the reactor bed

Fluidized-bed Reactor
Is analogous to the CSTR in that its
contents. Heterogeneous reactor, are
well mixed.

Kinds of Phases
Usage
Advantages
Disadvantages
Present
1. Gas-Solid phase 1. Heterogeneous
3. Good mixing temperature is 6. Bed-fluid mechanics
reaction
relatively uniform throughout not well known
2. Liquid-Solid
phase
2. Rreactor can handle 4. Catalyst can be continuously 7. Severe agitation can
3. Gas-Liquid
large amounts of
regenerated with the use of an result in catalyst
Solid phase
feed and solids
auxiliary loop
destruction and dust
formation
5. Good temperature control
8. Uncertain scale-up