Steady State operation

• Analysis of following
• The molar flow rates, Fi and Fi0
• The molar enthalpies, Hi , Hi0[Hi = Hi (T), and Hi0 = Hi (T0)]

Reaction Scheme
 Heat of reaction at temperature T and is designated HRx(T)

All enthalpies (e.g., HA, HB) are evaluated at the Temperature at the outlet of the system volume and
• Adiabatic Reactor –

• With Heat Exchange – Exothermic/Endothermic reaction

• Steady State Flow reactor – PFR/PBR, CSTR

• Unsteady state – Batch reactor

Adiabatic Reactor

• Consider a system with no work, Ws = 0,

adiabatic operation Q = 0, letting Ti0 = T0

Applies to a CSTR, PFR, or PBR, and also to a BR

• Adiabatic Tubular Reactor

Obtain the temperature, conversion, and concentration profiles along the length of
the reactor by solving for PBRs and PFRs operated adiabatically
Algorithm for Tubular reactor
• The elementary reversible gas-phase reaction is carried out in a PFR in
which pressure drop is neglected

1. Take mole balance

2. Rate law
3. Stoichiometry

4. Combine

5. Energy Balance: To relate temperature and conversion, apply the

energy balance to an adiabatic PFR/PBR. All species enter at the same
temperature Ti0 = T0. For adiabatic reactor Q = 0 and Ws = 0 to obtain T as
a function of conversion yields
If CP = 0
Solution Procedure PFR/PBR
• Numerical Technique – Integrating mole and energy balance
1. Set X.
2. Calculate T
3. Calculate k
4. Calculate Kc
5. Calculate T0/T (gas phase)
6. Calculate –rA
7. Calculate FA0/-rA.
8. If X is less than the exit conversion specified, increase X, go to Step 2.
9. Prepare table of X vs FA0/-rA.
10. Numerical integration
Problem
• N-Butane, C4H10, is to be isomerized to i-butane in a plug-flow reactor. This elementary reversible
reaction is to be carried out adiabatically in the liquid phase under high pressure using essentially
trace amounts of a liquid catalyst that gives a specific reaction rate of 31.1 h–1 at 360 K. The feed
enters at 330 K.
a) Calculate the PFR volume necessary to process 163 kmol/h at 70% conversion of a mixture 90
mol % n-butane and 10 mol % i-pentane,which is considered an inert.
b) Plot and analyze X, Xe, T, and –rA down the length of the reactor.
c) Calculate the CSTR volume for 40% conversion
1. Mole Balance:

2. Rate Law:

3. Stoichiometry (liquid phase, v = v0):

4. Combine:
5. Energy Balance:

5. Parameter Estimation

At equilibrium –rA = 0
 X T(K) k(h-1) KC Xe -rA FA0/-rA
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7

Get Volume by calculating area under curve

• For CSTR

• From the energy balance → T = 330 + 43.4X get T for 40%

Adiabatic Equilibrium Conversion
• For a first-order reaction, the equilibrium conversion

• For exothermic reactions, the equilibrium conversion decreases

with increasing temperature.
 • The shape of the Xe versus T curve is similar for reactions other than
first order as well
• To determine the maximum conversion that can be achieved in an
exothermic reaction carried out adiabatically, find the intersection of
the equilibrium conversion as a function of temperature with
temperature–conversion relationships from the energy balance

The adiabatic equilibrium conversion and

temperature for an entering temperature T0
Problem
• For the elementary liquid-phase reaction AB Determine the adiabatic
equilibrium temperature and conversion when pure A is fed to the reactor at a
temperature of 300 K. What is the CSTR volume to achieve 90% of the adiabatic
equilibrium conversion for v0 = 5dm3/min?
• The adiabatic equilibrium conversion, Xe, is one of the first things to determine
when carrying out an analysis involving reversible reactions. It is the maximum
conversion one can achieve for a given entering temperature, T0, and feed
composition.
• If Xe is too low to be economical, try lowering the feed temperature and/or
adding inerts.
• It can be observed that changing the flow rate has no effect on the equilibrium
conversion.
• For exothermic reactions, the adiabatic conversion decreases with increasing
entering temperature T0, and for endothermic reactions the conversion increases
with increasing entering T0.

• If adding inert or lowering the entering temperature is not feasible, then one
should consider reactor staging
Adiabatic Reactor Staging
• Conversions higher than those shown can be achieved for adiabatic
operations by connecting reactors in series with inter-stage cooling

Exothermic Reaction
• For Endothermic Reactions – Inter-stage heating can be provided
• The equilibrium conversion increases with increasing temperature. A
typical equilibrium curve and temperature conversion trajectory for
the reactor sequence
Optimum Feed Temperature
• Consider an adiabatic reactor of fixed size or catalyst weight and the
reaction is reversible and exothermic
• What happens as the feed temperature is varied.

L
• It is apparent that with conversions are very
low for both high and low feed
temperatures
• There must be an optimum feed
temperature that maximizes conversion.
• Feed temperature is increased from a very
low value, the specific reaction rate will
increase, as will the conversion.
• The conversion will continue to increase
with increasing feed temperature until the
equilibrium conversion is approached in the
reaction.
• Further increases in feed temperature for
this exothermic reaction will only decrease
the conversion due to the decreasing
equilibrium conversion.
• This is optimum inlet temperature