Reactor Design II- Fourth Year

Dr.Ali N.Khalaf

University of Basrah
College of Engineering
Chemical Engineering Department
Fourth Year
First Semester
Reactor design II

Chapter Two
Multiple Reactions

1 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

1-Introduction:
In the preceding chapters on single reactions showed that the performance (size) of a
reactor was influenced by the pattern of flow within the vessel. In this chapter, we
extend the discussion to multiple reactions and show that for these, both the size
requirement and the distribution of reaction products are affected by the pattern of
flow within the vessel. We may recall at this point that the distinction between a single
reaction and multiple reactions is that the single reaction requires only one rate
expression to describe its kinetic behavior whereas multiple reactions require more
than one rate expression.

Since multiple reactions are so varied in type and seem to have so little in common, we
may despair of finding general guiding principles for design. Fortunately, this is not so
because many multiple reactions can be considered to be combinations of two primary
types: parallel reactions and series reactions.

Let us consider the general approach and nomenclature. First of all, we find it more
convenient to deal with concentrations rather than conversions. Second, in examining
product distribution the procedure is to eliminate the time variable by dividing one
rate equation by another. We end up then with equations relating the rates of change
of certain components with respect to other components of the systems. Such
relationships are relatively easy to treat.

The two requirements, small reactor size and maximization of desired product, may
run counter to each other. In such a situation an economic analysis will yield the best
compromise. In general, however, product distribution controls; consequently, this
chapter concerns primarily optimization with respect to product distribution, a factor
which plays no role in single reactions.

Finally, we ignore expansion effects in this chapter; thus, we take ε= 0 throughout.

This means that we may use the terms mean residence time, reactor holding time,
space time, and reciprocal space velocity interchangeably.

2-Classification of Multiple Reactions:

First, we describe the four basic types of multiple reactions:

• Series
• Parallel
• Independent
• Complex

2 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

3 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

3 – Selectivity and Yield:

 instantaneous rate selectivity, SD/U

rate of formation of D rD
SD U  
rate of formation of U rU
 overall rate selectivity S0 D /U
ND Final moles of desired product
S0 D /U = = For batch reactor
N U Final moles of undesired product

FD Final molar flow rate of desired product

S0 D /U = = For Flow reactor s
F U Final molar flow rate of undesired product

 instantaneous yield, YD (at any point or time in reactor)

rate of formation of D r
YD   D
rate of consumption of A  rA
 overall yield Y o, D

FD
Y o D= For flow reactors(CSTR+ PFR )
F Ao−F A
ND
Y o D= For batch reactor
N Ao−N A

Maximize selectivity / yield to maximize production of desired product

4- Parallel Reactions: Maximizing Selectivity:

4 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

Maximizing SD/U for Parallel Reactions: Temperature Control

What reactor conditions and configuration maximizes the selectivity?

Start with temperature (affects k):

Specific rate of desired reaction kD increases more rapidly with increasing T

Use higher temperature to favor desired

b)product
If ED <formation.
EU
5 Chemical Engineering Department- University of Basrah
 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

Specific rate of desired reaction kD increases less rapidly with increasing T

Use lower T to favor desired product formation

(not so low that the reaction rate is tiny)
Maximizing SD/U for Parallel Reactions: Concentration Control

What reactor conditions and configuration maximizes the selectivity?

How do these concentration requirements affect reactor selection?

Example 1:
Maximize SD/U for Parallel Reactions using Temperature

What reactor temperature maximizes the selectivity if?

ED = 20 kcal/mol, EU = 10 kcal/mol,
T = 25 ◦C (298K) or 100 ◦C (373K)

6 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

Example 2:
What reactor/reactors scheme and conditions would you use to maximize the selectivity
parameters for the following parallel reaction?

To maximize the production of the desired product, the temperature should be as high as
possible (without decomposing the reactant or product)
To maximize the production of the desired product, CA should be as low as possible (but
not so low the rate = 0)
However, high CC will increase the reaction rate and offset the slow reaction rate that is
caused by low CA (that’s a good thing)

7 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

8 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

Example 3:
What reactor/reactors scheme and conditions would you use to maximize the
selectivity parameters for the following parallel reaction?

 Since ED>EU1, kD increases faster than kU1 as the temperature increases

 Operate at a high temperature to maximize CD with respect to CU1
 αD<αU1, keep CA low to maximize CD with respect to CU1
 rD and rU1 are 1st order in CC, so changing CC does not influence selectivity
 However, high CC will increase the reaction rate and offset the slow reaction
rate that is caused by low CA (that’s a good thing)

9 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

Example 4:
How does the selection of reactor/reactors scheme and conditions change if D can
react with C and form another undesired product?

Solution:

10 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

Consider relative magnitude of SD/U1 and SD/U2 as a function of position in PFR

PFR w/ side streams feeding low CA

11 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

5-Series (Consecutive) Reactions:

12 Chemical Engineering Department- University of Basrah

 Reactor Design II- Fourth Year
Dr.Ali N.Khalaf

For series (i.e., consecutive) reactions, the most important variable are time: space-
time for a flow reactor and real-time for a batch reactor. To illustrate the importance of
the time factor, we consider the sequence A→B→C in which species B is the desired
product.
If the first reaction is slow and the second reaction is fast, it will be extremely difficult
to produce species B. If the first reaction (formation of B) is fast and the reaction to
form C is slow, a large yield of B can be achieved.
However, if the reaction is allowed to proceed for a long time in a batch reactor, or if
the tubular flow reactor is too long, the desired product B will be converted to the
undesired product C. In no other type of reaction is exactness in the calculation of the
time needed to carry out the reaction more important than in series reactions.
5.1: Series Reactions in a Batch Reactor:
The elementary liquid phase series reaction is carried out in a batch reactor. The
reaction is heated very rapidly to the reaction temperature where it is held at this
temperature until the time it is quenched.
(a) Plot and analyze the concentrations of species A, B, and C as a function of time.
(b) Calculate the time to quench the reaction when the concentration of B will be a
maximum.
(c) What are the overall selectivity and yields at this quench time?
Additional Information:

13 Chemical Engineering Department- University of Basrah