4.

ALGORITHM FOR ISOTHERMAL REACTOR DESIGN

Topics

Part 1: Mole Balances in Terms of Conversion

1. Algorithm for Isothermal Reactor Design
2. Applications/Examples of CRE Algorithm
3. Reversible Reactions
4. ODE (Polymath) Solutions to CRE Problems
5. General Guidelines for California Problems
6. PBR with Pressure Drop
7. Engineering Analysis

Part 2: Measures Other Than Conversion

1. Measures Other Than Conversion
2. Membrane Reactors
3. Semibatch Reactors

Part 1: Mole Balances in Terms of Conversion

1. Algorithm for Isothermal Reactor Design

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French Menu
Analogy
4.1 The reaction (2A+B-->C)
carried out in a CSTR, PFR and a Batch
Reactor.
4.2 Labratory Experiment
4.3 Semilog plot to find reaction
rate constant
to a closed ended PFR/CSTR
example.
CHEMKIN Reactor Models

Example: The elementary liquid phase

reaction
is carried out isothermally in a CSTR. Pure A
enters at a volumetric flow rate of 25 dm3/s
and at a concentration of 0.2 mol/dm3.
What CSTR volume is necessary to achieve a
90% conversion when k = 10 dm3/(mol*s)?

Mole Balance

Rate Law

Stoichiometry

liquid phase (v = vo)

Combine

Evaluate

at X = 0.9,

V = 1125 dm3

Space Time

Here are some links to example problems.

You could also use these problems as self
tests.
CSTR Type 1 Home Problem
CSTR Type 2 Home Problem
CSTR Type 3 Home Problem
Critical Thinking Questions for
CSTR
The following movies were made by the
students of Professor Alan Lane's chemical
reaction engineering class at the University of
Alabama Tuscaloosa

2. Applications/Examples of the CRE Algorithm

Gas Phase
Elementary Reaction

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Additional
Information
only A fed

P0 = 8.2 atm

T0 = 500 K

CA0 = 0.2
mol/dm3

k = 0.5
dm3/mol-s

vo = 2.5
dm3/s

Solve for X = 0.9

Applying the algorithm to the above reaction
occurring in a Batch, CSTR, and PFR.
Batch

CSTR

PFR

Gas: T =T0, P =P0

Gas: T = T0, P = P0

Per Mole of A:

Per Mole of A:

Mole
Balance:
Rate Law:
Gas: V = V0
Stoichiometr
(e.g., constant volume
y:
steel container)

Combine:

Integrate

Evaluate

For X = 0.9:

V = 680.6 dm3

V = 90.7 dm3

Visual Encyclopedia of Reaction

Engineering Equipment
4.4 Gas Phase Reaction Example
CSTR and PFR Example
4.1 Calculate V for a Zero-Order
Reaction

3. Reversible Reactions

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To determine the conversion or reactor

volume for reversible reactions, one
must first calculate the maximum conversion
that can be achieved at the isothermal
reaction temperature, which is the equilibrium
conversion. (See Example 3-8 in the text for
additional coverage of equilibrium conversion
in isothermal reactor design.)
Equilibrium Conversion, Xe
From Appendix C:

4.5 Calculate Equilibrium

Conversion (Xe) for a Constant Volume
System

Example: Determine Xe for a PFR with no

pressure drop, P = P0

Given that the system is gas phase and

isothermal, determine the reactor volume
when X = 0.8 Xe.
Reaction

Additional Information
CA0 = 0.2 mol/dm3
KC = 100 dm3/mol

k = 2 dm3/mol-min
FA0 = 5 mol/min

First calculate Xe:

Xe = 0.89
X = 0.8Xe = 0.711

One could then use Polymath to

determine the volume of the PFR. The
corresponding Polymath program is shown
below.

4. ODE (Polymath) Solutions to CRE Problems

Algorithm Steps

Polymath Equations

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Mole Balance

d(X)/d(V) = -rA/FA0

Rate Law

rA = -k*((CA**2)-(CB/KC))

Stoichiometry

CA = (CA0*(1-X))/(1+eps*X)
CB = (CA0*X)/(2*(1+eps*X))

Parameter Evaluation

Initial and Final Values

eps = -0.5

CA0 = 0.2

FA0 = 5

KC = 100

X0 = 0

V0 = 0

k=2

Vf = 500

Polymath Screen Shots

Equations
Plot of X vs. V
Results in Tabular Form
A volume of 94 dm3 (rounding up from
slightly more than 93 dm3) appears to be our
answer.

4.6 Batch Reactor With a

Reversible Reaction
5. General Guidelines for California Problems

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Every state has an examination engineers

must pass to become a registered
professional engineer. In the past there have

typically been six problems in a three hour

segment of the California Professional
Engineers Exam. Consequently one should be
able to work each problem in 30 minutes or
less. Many of these problems involve an
intermediate calculation to determine the final
answer.
Some Hints:
1. group unknown parameters/values on the same side of the equation
example:
[unknowns] = [knowns]
2. look for a Case 1 and a Case 2 (usually two data points) to make intermediate
calculations
3. take ratios of Case 1 and Case 2 to cancel as many unknowns as possible
4. carry all symbols to the end of the manipulation before evaluating, UNLESS THEY
ARE ZERO

California Professional Engineers

Registration Problem
4.7 Batch Reactor Optimization
6. PBR with Pressure Drop

Note: Pressure drop does NOT affect liquid

phase reactions

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Sample Question:
Analyze the following second order gas phase
reaction that occurs isothermally in a PBR:

Mole Balance

Must use the differential form of the mole

balance to separate variables
Rate Law
Second order in A and irreversible:
Stoichiometry

Isothermal, T = T0

Combine

Need to find (P/P0) as a function of W (or V if

you have a PFR).
Pressure Drop in Packed Bed Reactors
Ergun Equation

Variable Gas Density

let

Catalyst Weight

where

let

then

EnglishEspanolSvenskaWe will use this form for multiple reactions:

We will use this form for single reactions:

Isothermal
Operation

recall that

notice that

The two expressions are coupled ordinary differential equations. We can

solve them simultaneously using an ODE solver such as Polymath. For the
special case of isothermal operation and epsilon = 0, we can obtain an
analytical solution.
Polymath will combine the mole balance, rate law and stoichiometry.

Analytical Solution

, [e], PFR with

CAUTION: Never use this form if

Combine

Solve

Could now solve for X given W, or for W given

X.
For gas phase reactions, as the pressure drop
increases, the concentration decreases,
resulting in a decreased rate of reaction,
hence a lower conversion when compared to
a reactor without a pressure drop.

4.2 Pressure Drop in a Packed

Bed Reactor
4.3 Pressure and Reaction Orders
4.8 Formation of Ethyl Acetate
Here are some links to example problems
dealing with packed bed reactors. You could
also use these problems as self tests.
PBR Type 1 Home Problem
PBR Type 2 Home Problem
PBR Type 3 Home Problem
POLYMATH

Consider the following gas phase reaction

carried out isothermally in a packed bed
reactor. Pure A is fed at a rate of 2.5 moles/s
and with
, and = 0.0002 kg-1.
2A B
Mole Balance

Rate Law
Elementary
Stoichiometry
Gas with T = T0
A B/2

POLYMATH will combine everything - You do

not need the combine step. Thank you
POLYMATH

Profiles
4.4 "What Four Things are Wrong
with this Solution?"
Optimum Paritcle Diameter

Laminar Flow, Fix P0, 0,

0 = P0(MW)/RT0
0P0P02

Increasing the particle diameter descreases

the pressure drop and increases the rate and
conversion.

However, there is a competing effect. The

specific reaction rate decreases as the particle
size increases, therefore so deos the
conversion.
k 1/Dp

DP1 > DP2

k1 > k2
Higher k, higher conversion

The larger the particle, the more time it takes

the reactant to get in and out of the catalyst
particle. For a given catalyst weight, there is
a greater external surgace area for smaller
particles than larger particles. Therefore,
there are more entry ways into the catalyst
particle.

In CD-ROM chapter 12, we will learn that

effectiveness factor decreases as the particle
size increases
7. Engineering Analysis - Critical Thinking and Creative Thinking

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We want to learn how the various parameters

(particle diameter, porosity, etc.) affect the
pressure drop and hence conversion. We need
to know how to respond to "What if"
questions, such as:
"If we double the particle size, decrease the
porosity by a factor of 3, and double the pipe
size, what will happen to D P and X?"
(See Critical Thinking in Preface page xx.
e.g., Questions the probe consenquences)
To answer these questions we need to see
how a varies with these parameters.

Turbulent Flow

Compare Case 1 and Case 2:

For example, Case 1 might be our current
situation and Case 2 might be the parameters
we want to change to.

For constant mass flow through the system =

constant

Laminar Flow

4.5 Effect of Reducing Particle

Size on Conversion in a PBR

Here are more links to example problems

dealing with packed bed reactors. Again, you
could also use these problems as self tests.
PBR Type 5 Home Problem
PBR Type 7 Home Problem
PBR Type 8 Home Problem

Part 2: Measures Other Than Conversion

1. Measures Other Than Conversion

Uses:
A. Membrane reactors
B. Multiple reaction
Liquids: Use concentrations, I.E. CA

1. For the elementary liquid phase

reaction
carried out in a CSTR, where V,
vo, CAo, k, and Kc are given and the feed is

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pure A, the combined mole balance, rate

laws, and stoichiometry are:

There are two equations, two unknowns,

CA and CB
Gases: Use Molar Flow Rates, I.E. FI

2. If the above reaction,

,carried out in
the gas phase in a PFR, where V, vo,CAo,k, and
Kc are given and the feed is pure A, the
combined mole balance, rate laws, and

stoichiometry yield, for isothermal operation

(T=To) and no pressure drop (P=0) are:

Use Polymath to plot FA and FB down the

length of the reactor.
4.9 Stoichiometry for Measures
Other than Conversion
4.6 Gas Phase PFR
4.7 Liquid Phase CSTR
Use Creative and then Critical
Thinking
4.8 What Four Things are Wrong
With this solution?
Microreactors

For isothermal microreactors, we use the

same equations as a PFR as long as the flow

is not laminar. If the flow is laminar, we must

use the techniques discussed in chapter 13.
See example 4.8 of the text.

University of Washington Transport

Effects in Microreactors site
Institut fr Mikrotechnik Mainz

GmbH
2. Membrane Reactors

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Membrane reactors can be used to achieve

conversions greater than the original
equilibrium value. These higher conversions
are the result of Le Chatelier's Principle; you
can remove one of the reaction products and
drive the reaction to the right. To accomplish
this, a membrane that is permeable to that
reaction product, but is impermeable to all
other species, is placed around the reacting
mixture.
Example: The following reaction is to be
carried out isothermally in a membrane
reactor with no pressure drop. The membrane
is permeable to Product C, but it is
impermeable to all other species.

For membrane reactors, we cannot use

conversion. We have to work in terms of the
molar flow rates FA, FB, FC.
Polymath Program
Mole Balances

Rate Laws

Stoichiometry
Isothermal, no pressure drop

Combine

Polymath will combine for you-- Thanks Polymath...you rock!

Parameters

Solve

Polymath

4.9 "What four things are wrong

with this membrane reactor solution?"
Here are links to example problems dealing
with membrane reactors. You could also use
these problems as self tests.
Membrane
(Heterogeneous)
Membrane
(Homogeneous)
Membrane
Membrane

Type 4 Home Problem

Type 4 Home Problem
Type 7 Home Problem
Type 8 Home Problem

3. Semibatch Reactors p. 190

Semibatch reactors can be very effective in

maximizing selectivity in liquid phase
reactions.

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to Selectivity
The reactant that starts in the reactor is
always the limiting reactant.

Three Forms of the Mole Balance Applied to Semibatch Reactors:

1. Molar Basis

2. Concentration Basis

3. Conversion

For constant molar feed:

For constant density:

Use the algorithm to solve the remainder of

the problem.

Example: Elementary Irreversible Reaction

Consider the following irreversible elementary
reaction:
-rA = kCACB
The combined mole balance, rate law, and
stoichiometry may be written in terms of
number of moles, conversion, and/or
concentration:
Conversion

Concentration

Number of Moles

Polymath Equations:
Conversion

Concentration

Moles

d(X)/d(t) = -ra*V/Nao

d(Ca)/d(t) = ra - (Ca*vo)/V

d(Na)/d(t) = ra*V

ra = -k*Ca*Cb

d(Cb)/d(t) = rb + ((CboCb)*vo)/V

d(Nb)/d(t) = rb*V +
Fbo

Ca = Nao*(1 - X)/V

ra = -k*Ca*Cb

ra = -k*Ca*Cb

Cb = (Nbi + Fbo*t Nao*X)/V

rb = ra

rb = ra

V = Vo + vo*t

V = Vo + vo*t

V = Vo + vo*t

Vo = 100

Vo = 100

Vo = 100

vo = 2

vo = 2

vo = 2

Nao = 100

Fbo = 5

Fbo = 5

Fbo = 5

Nao = 100

Ca = Na/V

Nbi = 0

Cbo = Fbo/vo

Cb = Nb/V

k = 0.1

k = 0.01

k = 0.01

Na = Ca*V

X = (Nao-Na)/Nao

Polymath Screenshots:
Conversion

Concentration

Polymath Equations

Polymath Equations

SummaryTable

Summary Table

Conversion vs.Time

Conversion vs.Time

Concentration vs.Time

Concentration vs.Time

Volume vs.Time

Volume vs.Time

Critical Thinking Questions

Equilibrium Conversion in Semibatch Reactors with Reversible
Reactions

Consider the following reversible reaction:

Everything is the same as for the irreversible
case, except for the rate law:

Where:

At equilibrium, -rA=0, then

4.10 Semibatch: A B Acid

Catalyzed
See Also:
Web Module on Reactive Distillation
Web Module on Wetlands
You Rate Some Wetlands Critical
Thinking Questions
Object Assessment of Chapter 4

All chapter references are for the 4th Edition

of the text Elements of Chemical Reaction
Engineering .
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Fogler & Gurmen
2007 University of Michigan

CHAPTER 4 EXAMPLE
Elementary gas phase reaction in different reactor types.
CSTR

The elementary gas phase reaction

takes place in a CSTR at constant
temperature (500 K) and constant pressure
(16.4 atm). The feed is equal molar in A and
B.
Mole Balance
Rate Law
Stoichiometry

gas phase, isothermal (T = T0), no pressure drop (P = P0)

Why do you suppose CB is a constant, when B is being consumed?

Combine

Evaluate

PFR and Batch Reactors

Elementary Gas Phase Reaction:

PFR
Mole Balance

Rate Law
Stoichiometry

gas phase, isothermal (T = T0), no pressure drop (P = P0),

CAo=CBo (=1), v=vo(1+X)

Combine

Parameter
Evaluation

CAo=0.2, v=vo=25 dm3/s, k=10 dm6/mol2 s, =-0.5, X=0.9

V=227 dm3

Batch Reactor Constant Volume, V=V and the

pressure changes.
o

Mole Balance

Rate Law
Stoichiometry

Combine

Parameter Evaluation

CAo=0.2, k=10 dm6/mol2 s,

Back to Chapter 4

Example Algorithm for Steps in Solving Closed-Ended Problems

1. Statement
The elementary, liquid-phase, irreversible reaction

is to be carried out in a flow reactor. Two reactors are available, an 800

dm3 PFR that can only be operated at 300 K and a 200 dm3 CSTR that can be
operated at 350 K. The two feed streams to the reactor mix to form a single fee
d stream that is equal molar in A and B, with a total volumetric flowrate of 10
dm3/min. Which of the two reactors will give us the highest conversion?
Additional Information:

2. Real Problem

at 300 K, k = 0.07 dm3/mol-min

E = 85000 J/mol-K
CA0B = CB0B = 2 mol/dm 3
vA0 = vB0 = 0.5*v0 = 5 dm3/min

We have two choices, a PFR operated at 300 K and a CSTR operated at 350 K.
Which one do we choose?

3. Sketch

4. Identify and Name

A. Relevant Theories and Equations
Arrhenius Equation:
The higher the temperature, the faster the reaction rate.
B.
Rate Law:
Mole Balances:

D. Systems
Volume of CSTR
Volume of PFR
E. Dependent and Independent Variables
Independent: V, FA0, T
Dependent: X
F. Knowns and Unknowns
Knowns: k0, E, V, 0, CA0B, CB0B
Unknowns: X
G. Inputs and Outputs
In: FA0 = FB0, so B = 1
Out: FA = FA0(1-X), FB = FA0(1-X), FC = FA0X
H. What color should we paint the reactor?
Not an issue.
5.
6. Assumptions
Isothermal, no pressure drop. The CSTR is well mixed. There are no radial
variations in the PFR.

7. Specifications
There is neither too much redundant information, nor is there too little
information given. Therefore, the problem is neither over-specified, nor underspecified.

8. Similar or Related Example Problems

This problem has a solution procedure in common with Examples 4-2 and 4-4
in the text.

9. Algorithm
CSTR

PFR

10.
A. Mole Balance

B. Rate Law

C. Stoichiometry - liquid, v = vo; equal molar B = 1

CA = CA0(1-X)
CB = CA0(1-X)
D. Combine

(eqn 1)

(eqn 2)
E. Evaluate
v A0 = 5 dm3/min
Before mixing

CA0B = 2 mol/dm3
FA0 = CA0B* vA0
FA0 = (5 dm3/min)(2 mol/dm3) = 10 mol/min
After mixing
v0 = vA0 + vB0 = 5 dm3/min + 5 dm3/min = 10 dm3/min
CA0 = 1 mol/dm3

at 350 K,
k = 8.447 dm3/mol-min

11. Manipulate
A. CSTR @ 350 K
the combined CSTR equation (eqn 1) can be arranged as

B. PFR @ 300 K

12.Choose the CSTR, because it gives the highest conversion.

13.
14.Units Check
X is dimensionless

15.Is it reasonable?
This is a reasonable conversion.
This the end of the PFR/CSTR example. A sample registration exam problem is also
available.

CHAPTER 4 EXAMPLE
Deriving The Equilibrium Constant (KC) and Equilibrium
Conversion(Xe) for a Constant Volume System:

You are given the reversible reaction:

which takes place in a constant volume batch reactor. The equilibrium constant, KC, for
this reaction is:

where CAe and CBe are:

Substituting for CAe and CBe gives us:

Substituting known values (CA0 = 0.2 mol/dm3 and KC = 100 dm3/mol):

Solving for the equilibrium conversion, Xe, yields:

Xe = 0.83