KKKR3523 REACTION

ENGINEERING II

Prof Ir Dr Zahira Yaakob

 CHAP 8: Steady-State Nonisothermal
Reactor Design
Objectives

• Algorithm for CSTRs, PFRs, and PBRs that are not

operated isothermally.
• Size adiabatic and nonadiabatic CSTRs, PFRs, and
PBRs.
• Use reactor staging to obtain high conversions for highly
exothermic reversible reactions.
• Analyze multiple reactions carried out in CSTRs, PFRs,
and PBRs which are not operated isothermally in order
to determine the concentrations and temperature as a
function of position (PFR/PBR) and operating variables.
 Steady-State Non-Isothermal Reactor
Design

Topics
• Energy Balances
• Reversible Reactions
• Adiabatic Reactions
• Applications of the PFR/PBR User Friendly Energy
Balance Equations
• Interstage Cooling/Heating
• Evaluating the Heat Exchanger Term
• Multiple Steady States
• Multiple Reactions with Heat Effects
 EFFECT OF TEMPERATURE
• In reaction engineering 1, we have
considered how reactor type and size
influence the conversion and product
distribution
• For reaction engineering 2, we will study
how temperature and catalyst influence
the progress and rate of reaction.
• At the end, we will also look at nonideal
reactor
 3 steps procedure
• 1- How equilibrium composition, rate of reaction, and
product distribution affected by changes in operating
temperature. Determine optimum temperature
progression
• 2- Chemical reaction usually accompanied by heat
effects, how these will change the temperature of the
reacting mixture. Propose a number of favourable
reactor and heat exchange systems
• 3- Economic consideration will select the best systems
 Collision Theory
• Some reaction proceeds very rapidly,
while others proceed very slowly that the
rate is not detectable
• Metal when exposed to weather will
undergo reactions with oxygen and water
which results in corrosion
• 2 theories, Transition state theory and
collision theory
 Collision theory
Consider A + B -> Products

•In order for A and B to react, they must collide together

•However, not every collision of A and B will results in formation of
products
•A and B collide with certain amount of energy called activation energy
•If temperature is increased, kinetics energy of A and be are increased,
more collision per time, rate increased
 Single reaction
• Concerned on conversion level and
reactor stability
• Thermodynamics – give information on
heat liberated or absorbed and maximum
possible conversion
 Heat of reaction from
thermodynamics
• Heat liberated or absorbed at temperature
T2 depends on nature of the reacting
system, the amount of material reacting
and the T and P of the reacting system.
• Heat can be calculated from heat of
reaction
• Can use handbooks to estimate from heat
of formation and heat of combustion
 Equilibrium Conversion
• Equilibrium composition governed by
equilibrium constant, change with
temperature

• Equilibrium constant is not affected by

pressure, presence or absence of inerts,
or by the kinetics of the reaction
 Equilibrium Constant
• K > 1 indicates practically complete
conversion possible and the reaction can
be considered irreversible
• K<1, reaction will not proceed to any
appreciable extent
• Conversion increase for endothermic
reaction and decrease for exothermic
reaction if T increase
 Example
• Nitrogen triiodide is unstable, and reacts exothermically
when agitated

Let's calculate the volume necessary to achieve a conversion, X, in

a PFR for a first-order, exothermic reaction carried out adiabatically.
For an adiabatic, exothermic reaction the temperature profile might
look something like this:
The combined mole balance, rate law, and
stoichiometry yield:
Solve equation. Relate X and T. Use Energy
Balance. E.g. for an adiabatic reaction,

the energy balance

set X, then calculate T, can plot vs. X

Typical profile look like this.
.
 User Friendly Energy Balance Equations
Adiabatic CSTR, PFR, Batch, PBR achieve this:
 Energy Balance Equations
CSTR with heat exchanger, UA(Ta-T)
and large coolant flow rate.
 Energy Balance Equations

PFR/PBR with heat exchange

In terms of conversion, X
 Energy Balance Equations

PFR/PBR with heat exchange

In terms of molar flow rates, Fi

 Energy Balance Equations

For Multiple Reactions

Coolant Balance

These equations are derived in the text.

These are the equations that we will use to solve
reaction engineering problems with heat effects.
 Energy Balance

Typical units for each term are J/s; i.e.

Watts
Energy Balance

(1)
 Steps
• Replace Ei by Ei = Hi - PVi
• Express Hi in terms of enthalpies of formation
and heat capacities
• Express Fi in terms of either conversion or rates
of reaction
• Define ΔHRX
• Define ΔCP
• Manipulate so that the overall energy balance is
either in terms of the User Friendly Equations
depending on the application
 Step 1
Substitute , ,

and

into equation (1) General Energy Balance:

 Cont’
For steady state operation:

Relate X and T in order to size reactors.

Write the molar flow rates in terms of conversion
the enthalpies as a function of temperature .
• Flow Rates, Fi
For the generalized reaction:

In general,
• Enthalpies, Hi
• Assuming no phase change:
• Mean heat capacities:
 Heats of Reaction
• Calculate , , for the
reaction

• There are inerts I present in the system.

Additional information
 Solution

Note: The inerts NEVER enter into these calculations

Energy Balance :

For constant or mean heat capacities:

Adiabatic Energy Balance:
• Adiabatic Energy Balance for variable heat
capacities:

For constant heat capacities:

 Reversible Reactions

Elementary rate law.

Ke is the concentration equilibrium constant.

Le Chatlier's Law ; if the reaction is exothermic,
Ke will decrease as the temperature is increased and the
reaction will be shifted back to the left. If the reaction is endothermic
and the temperature is increased, Ke will increase and the reaction
will shift to the right.
For the special case of :
Adiabatic Reactions
plot vs. X. Find V
• CSTR+PFR

The best arrangement is a CSTR with a

40% conversion followed by a PFR up to 70% conversion.
 PFR/PBR Energy Balance Equations

Heat exchange for a PFR:

a = heat exchange area per unit volume of reactor;
tubular reactor, a = 4/D

Heat exchange for a PBR:

Steady State Energy Balance (with no work):

in Terms of Conversion:

in terms of Molar Flow Rates

 Effect of pressure drop

Note: the pressure drop will be greater for exothermic adiabatic

reactions than it will be for isothermal reactions
 Balance on Heat Exchanger Coolant

Solve simultaneously using an ODE solver (Polymath/MatLab).

If the coolant temperature Ta is not constant, then we must add an
additional energy balance on the coolant fluid:

with Ta = Tao at W = 0
 For an exothermic reaction:

Counter current flow - Trial and Error to find exit X and T

Eg : Exothermic rxn,coolant stream enters at reactor end at T a0 = 300 K.

Assume: Coolant temp. at reactor entrance (X = 0, V = 0) T a2 =340 K.

Calculate X, T, and Ta as a function of V.

Trial 1 : Ta2 of 340 K → coolant temperature of 310 K (not

match actual entering coolant temperature 300 K)

Trial 2 : Ta2 of 330 K → coolant temperature of 300 K (OK)

Sketch the ambient temperature as a function of V

Sketch Ta vs. V for a high and low coolant rate, m a.

Solution High coolant rate, Ta is constant

Low coolant rate

a) Exothermic reaction

b) Endothermic reaction
 Elementary Liquid Phase Reaction

Eg : Liquid phase reaction in PFR, elementary rate law

a) Write the CRE algorithm, sketch T(X) for an adiabatic

endothermic and exothermic reaction

b) Write the adiabatic energy balance.

c) Find the adiabatic equilibrium conversion and T

for both an exothermic and endothermic reaction

d) Sketch the adiabatic equilibrium conversion, X and T,

Show how they vary along the length of the reactor.
Solution

a) PFR Algorithm
Exothermic

Endothermic
Adiabatic Energy Balance

Exothermic Endothermic

Adiabatic Equilibrium
Interstage Cooling:
 Example:Interstage Cooling

Elementary Exothermic Reversible Reaction:

 Endothermic Reaction

Endothermic reaction in an interstage reactor system.

Inerts are injected between the reactors to increase T

Inert I is injected at the points shown below:

Sketch the X - T trajectory for the reaction system.

 Solution

Endothermic reaction, XEB increases with increasing T. For

From the energy balance we know the temperature decreases
with increasing conversion. (The endothermic heat of
reaction is positive.)
Final profile. Look at the derivation in the text book
 CSTR Algorithm

Example : Adiabatic Second Order Reaction Liquid

Phase in A CSTR
 Second order in A. The feed, equimolar in a solvent
(which contains the catalyst) and A, enters the reactor
at a total volumetric flow rate of 10 dm 3 /min.Concentration
of A = 4M. The entering T = 300 K.

(a) What CSTR reactor volume for 80% conversion?

(b) What conversion if VCSTR = 1000 dm3? What is the new exit T?

(c) How would your answers to part (b) change, if the entering T
of the feed were 280 K?

Additional Information:
 Solution Adiabatic Liquid Phase in A CSTR

a)
1. CSTR Design Equation:

2. Rate Law:

3. Stoichiometry:

4. Combine:
Given conversion (X), determine the reaction T, then calculate V

5. Determine T: From the adiabatic energy balance:

6. Solve for the Rate Constant (k) at T = 380 K:
b) CSTR Design Equation

liquid
Solve the Energy Balance for XEB as a function of T

Solve the Mole Balance for XMB as a function of T

plot XEB and XMB as functions of T to find the intersection
X = 0.87 and T = 387 K
c) initial T= 280 K. All other equations remain unchanged.

Plot X EB and X MB :
X = 0.75 at T = 355 K
 Evaluating the Heat Exchanger Term

Energy transferred between the reactor and the coolant:

At high coolant flow rates

 Multiple Steady States (MSS)

Factor FA0 CP0 and then divide by FA0

For a CSTR: FA0X = -rAV
 Example : Finding when R(T) = G(T)

a) For an entering temperature of 340 K and an ambient

temperature of 310, find the reactor temperature
and conversion.
b) Find X and T when the flow rate is increased by
a factor of 4.
Now we need to find X. We do this by combining the mole
balance, rate law, Arrhenius Equation, and stoichiometry

Consider first-order, irreversible reaction A --> B, we have :

At steady state:
The following curve gives the G(T) for the reaction.
a) For an entering temperature of 340 K and an ambient
temperature of 310, find the reactor temperature and conversion.

The heat removal curve is

The intercept T = TC is
This line is shown on the figure below. We see that

K
From the intersection of R(T) and G(T), we find that the
steady state reactor temperature is 333 K. To find the
conversion: G(T) = X(- ΔHRx) @ Intersection of G(T) and R(T),
G(T) = R(T) = 800

The conversion is 80%

b) We now consider another situation where the flow rate
is increased by a factor of 4 and the inlet temperature
is 330K and the ambient temperature is 300K.

The heat removal line is now

the intercept is
We see that at two points, consequently there
are two possible steady states for the temperatures
inside the reactor, one at 320K and one at 340K.
The corresponding conversions are

and
 Finding MSS for an Endothermic Reaction
Can there be multiple steady states (MSS) for a
irreversible first order endothermic reaction?
Solution

For an endothermic reaction HRX is positive

(e.g., HRX=+100 kJ/mole).

There are no multiple steady states for an endothermic,
irreversible first order reactor. The steady state
reactor temperature is TS
 Multiple Reactions with Heat Effects
To account for heat effects in multiple reactions, replace
the term (-ΔHRX) (-rA) in equations for PFR/PBR and CSTR by:

PFR/PBR

CSTR

These equations are coupled with the mole balances

and rate law equations discussed in Chapter 6.
Complex Reactions

Consider the following gas phase reactions

Combined Mole Balance, Rate Law, Stoichiometry, and Energy Balance:
substitute the various parameter
values into equations (1)-(13)
solve simultaneously using Polymath