Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Unit 5:
Reactor Design for Multiple
Reactions

Prof Ning Yan, 2023/2024 Sem 2

 2

Learning Objectives (Unit 5)

• Definitions of instantaneous and overall selectivities
• Product distributions in parallel, series and series-parallel reactions for different
reactor types
• Importance of contacting scheme
 3

Parallel Reactions of a Single Reactant

• Consider parallel reactions:
• A→ R k1 (desired reaction)
• A→ S k2 (unwanted reaction)
• For constant density batch reactors and PFRs:

• If α1 > α2, can be increased by increasing cA, and vice versa.

• can be varied by changing the temperature. If Ea1 > E a2, increases with
increasing temperature, and vice versa.
• can also be changed by using a suitable catalyst, which may modify not only
the rate constants, but possibly also the rate laws.
 4

Parallel Reactions of More than One Reactant

• Consider parallel reactions:
• A+ B→ R k1 (desired reaction)
• A+ B→ S k2 (unwanted reaction)

• For constant density batch reactors and PFR:

• In addition to the methods outlined for parallel reactions of a single reactant, cB

can also be utilised to manipulate the value of . If β1 > β2, can be increased
by increasing cB, and vice versa.
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Parallel Reactions of More than One Reactant

• Contacting patterns for batch reactors:

• Contacting patterns for flow reactors:

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Reversible Parallel Reactions

• The product concentration may go through a maximum:

(irreversible)

Self-study
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Multiple Reactions: Conversion, Selectivity & Yield

Note: ×
 8

Opening Question 1
A company uses A to produce R in a first order reaction. There are two side
reactions, A to S (zeroth order) and A to T (second order), respectively:
A→S rS = k0
A → R (desired) rR = k1cA
A→T rT = k2cA2
Scenario 1: A is expensive, and recovery of unreacted A is relatively easy.
Scenario 2: A is cheap, while recovery of A is cost prohibitive.
−rA
What flow reactor (CSTR or PFR) and at what conversion of A→T
A would you design in each scenario?
A→ R

A→S
t or xA
 9

Overall Selectivity
• Consider parallel reactions:
• A→ R k1 (desired reaction)
• A→ S k2 (unwanted reaction)

• The overall selectivity is obtained from the mole balance of the reactor. If no R
is present initially:
/ (batch reactors)
−

/ (flow reactors)
−

• For a constant density system, the above expressions become:

/ (batch reactors)
( − ) −

/ (flow reactors)
( − ) −
 10

Instantaneous Selectivity
• The instantaneous selectivity is defined as:
/

• For constant density batch reactors and PFRs, where rates are the
concentration gradients (with respect to time and position, respectively):
/

• Function f, which depends on the rate law, describes the shape of the plot of
φR/A against cA.

• φ R/A and Φ R/A determine the effectiveness of the reactor in producing the
desired product R. Therefore, their values should be as high as possible.
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Relating Instantaneous and Overall Selectivities

• Integrating the φR/A expression for constant density systems gives:

/
0

• Substitute into the ΦR/A expression for constant density systems:

/
/ /

• where / is the mean value of φR/A in the interval between cA and cA0.

• For a given conversion of A, maximising ΦR/A is equivalent to maximising the

integral / .
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Instantaneous and Overall Selectivities for CSTR

• For a CSTR, the value of φR/A is equal to / :
/ /

where is the value of φ evaluated at the outlet concentration .

• For multiple CSTRs in series:
( )
/

φ φ
cR cR

Note: / /
−

cA cA0 cA
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Instantaneous and Overall Selectivities for PFR

• For a PFR:
φ
cR
/ /

The integral is equal to the AUC between cA and cA0.

• For multiple PFR in series:

cA
( )

/ φ cR
It is identical to the expression for a single PFR.

cA
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Revisit: Opening Question 1

A→S rS = k 0 −rA
A→T
A → R (desired) rR = k 1 c A
A→T rT = k2cA2
A→R
/
A→S
t or xA
Maximum value of / is achieved at
/
Scenario 1: A is expensive, and recovery of unreacted A is relatively
easy.
Should maximise the overall selectivity of R, / .

Use CSTR with such that / /

Scenario 2: A is cheap, while recovery of A is cost prohibitive.

Should maximise the yield of R, . More on next slide… /
 15

Revisit: Opening Question 1

For Scenario 2, the engineer proposed four types of operations:
(1) Single CSTR (outlet concentration = )
(2) Single PFR (outlet concentration = )
(3) CSTR (outlet concentration = ) then PFR (outlet concentration = )

(4) PFR (outlet concentration = ) then CSTR (outlet concentration = )

(1) (2) (3) (4)

/ / / /

/
/ /
/
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Quiz 1
1. Is the overall selectivity in a series of CSTR always larger than that in a single
CSTR?

2. For a series of PFRs, is Φ equal to the average of the overall selectivities of

each reactor?
 17

Recap

A→R Maximize cA for positive

order reaction (PFR or
Design purpose: minimize reactor volume → maximize –rA → CSTR in series)
Minimize cA for negative
order reaction (CSTR)
A → R (desired)
A→T
Design purpose:
minimize reactor volume;
or
maximize selectivity /
or
maximize yield
 18

A → R (desired) r R = k 1c A
A→T rT = k2cA2

If the target is to achieve 90% conversion of A with the smallest possible

reactor volume, should PRF or CSTR be considered? PFR!

If the target is to achieve 90% conversion of A with the highest possible yield
of R, should PRF or CSTR be considered? CSTR!

Yield = conversion x selectivity a lower reactor volume -> higher conc -> lower selectivity
and vice versa

/ /

Low concentration of CA is good for high selectivity, CSTR should be used

 19

Opening Question 2
A company uses A to produce R in a liquid phase reaction. R further reacts to
basically a single reaction A->S unless R is wanted
form S. Both reactions are first order:
A→R→S ,
Which reactor should be used, PFR or CSTR, to maximise concentration of R in
the outlet? if R is final product, just have to increase conversion of A->R

when conc R is max, conc A = conc R

 20

Series Reactions
• Consider series reactions with first order kinetics for each step:
k k
A →1 R →2 S
• For a constant density batch reactor:

only variable is CR

• This first order ODE can be solved using the integrating factor:
( )

( − )
 21

Series Reactions
• When t = 0, cR = 0 :

cR = cS = 0

• Based on the stoichiometric table, cA + cR + cS = cA0 (if no R and S initially):

Case 1: k1 >> k2 (A is much more reactive than R)

− −

RDS: R → S
 22

Series Reactions
Case 2: k1 << k2 (R is much more reactive than A)

− −

RDS: A → R
In rough estimation, cR ≈ 0.

A: correct since R is intermediate product

B: yes based on graph
C:
 23

Series Reactions
Case 3: k1 ~ k2
• cR goes through a maximum at tmax.

• To determine tmax, differentiate the expression for cR

and equate the derivative to zero:

−
 24

Series Reactions
Product distribution of first order reactions in PFRs
• Essentially the same as the batch reactor:

−
These equations will be used to solve HW,
to enhance your understanding.
 25

Series Reactions
Product distribution of first order reactions in batch reactors and PFRs
Example:
A→R→S how much
A is left
and

Identify cA, cR and cS.

cS

how much R

dashed line: max concentration of R at any conversion

 26

Series Reactions
Product distribution of first order reactions in batch reactors and PFRs (cont’d)

• cRmax increases with decreasing k2.

• At low conversions (small τ), cS is negligible.
A: correct since R is intermediate product
• At high conversions
B: yes based on graph (large τ), cS approaches that of a single first order reaction
with rate constant k2.
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Quiz 2
For series reactions A to R to S (both first order), we hope to maximize the
selectivity of R. Which of the following is not correct?
k1 k 2
A→R→S

A. If a batch reactor is used, we can maximise R by changing reaction time.

B. If a PFR is used, we can maximise R by changing molar flow rate (or τ).
C. If a batch reactor and a PFR are both used, after respective optimisation at
the same temperature, the two would offer different selectivities towards R.
D. We may improve selectivity of R by changing the reaction temperature.
E. We may improve selectivity of R by using a catalyst that enhance k1.
yes, since that is the point of batch
yes based on graph
no different optimization parameters but should arrive at the same answer
yes, k1 increases when T increases, increasing rate
yes k1 increases, k2 decreases
 28

Series Reactions
Product distribution of first order reactions in CSTRs no need integration

A→R→S FA0, v0, cA0 F A , F R , FS , v 0

FR0 = FS0 = 0 V, τ cA, cR, cS
• Mole balance for A: Recall unit 3

• Mole balance for R:

 29

Series Reactions
Product distribution of first order reactions in CSTRs (cont’d)
• Based on the stoichiometric table:

• To determine τmax such that cR is maximum, differentiate the expression for cR

and equate the derivative to zero:

Check appendix for details

 30

Series Reactions
Product distribution of first order reactions in CSTRs (cont’d)

CSTR
 31

Revisit: Opening Question 2

A→ R → S ,
Which reactor should be used, PFR or CSTR, to maximize concentration of R in the outlet?
Solution 1 (Equation method):
smaller size

( )
( )

( )
( ) − 1
1−10

higher conc

( ) ( ) Under optimised condition, PFR is smaller in size.

( ) ( ) Under optimised condition, PFR produces higher concentration of R.

In fact, it can be deduced that τmax(PFR) < τmax(CSTR) (unless k1 = k2, in which case both τmax’s are equal
1
to ).
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Revisit: Opening Question 2

Solution 2 (Graphical method):
1. Compare cRmax

Therefore, PFR produces higher concentration of R.

 33

Revisit: Opening Question 2

2. Compare reactor size

PFR CSTR

k1τmaxPFR = 2.6 k1τmaxCSTR = 3.1

τmaxPFR < τmaxCSTR PFR is smaller
 34

Series Reactions
Higher order reactions
• Consider series reactions:
k k
A →1 R →2 S

• If α > ρ, can be increased by increasing cA0, and vice versa.

Self-study
 35

Reversible Series Reactions

• The concentration of the intermediate may not go through a maximum:

(irreversible)

Self-study
 36

Quiz 3
1. In a CSTR, what happens to cRmax as k2 increases? decreases

2. For high conversions, does the difference in the ΦR/A between PFR and CSTR
become larger or smaller as k2 increases?
 37

Opening Question 3
Consider the following reactions in the liquid phase:
A+B→R rR = k1cAcB
R+B→S rS = k2cRcB
1 mole of A and 3 moles of B are rapidly mixed. The reaction is slow, allowing analysis of
composition at various times. When 2.2 moles of B remain unreacted, 0.2 mole of S is present in
the mixture. What should be the composition of the mixture when the amount of S present is
0.6 mole?
Species t = 0 Δ t>0 From the question setting, Species t = 0 Δ t>0
A 1 −α 1−α 3 − α − β = 2.2 A 1 −0.6 0.4
β = 0.2
B 3 −α − β 3 − α − β B 3 −0.6 − 0.2 2.2
α = 0.6
R 0 α−β α−β R 0 0.6 − 0.2 0.4
S 0 β β S 0 0.2 0.2
Total 4 4−α−β Total 4 3.2
 38

Series-Parallel Reactions
• Consider series-parallel reactions:
• A+ B→ R
• R+B→S
• The reactions are series with respect A, and parallel with respect to B.
• Example:
+ Cl2 + HCl + Cl2 + HCl

• For a constant density batch reactor:

 39

Series-Parallel Reactions
• If R is the desired product:
• Since R is the intermediate product in the series reactions A → R → S, PFR is the
preferred flow reactor, while in semi-batch operation, B is added to A.
• R is a product in the parallel reactions B → R, B → S, and both reactions have the
same reaction order with respect to B in this case. Therefore, it does not matter
how B is introduced to the reaction.
 40

Series-Parallel Reactions
Product distribution in batch reactors and PFRs
• In constant density batch reactor and PFRs:

∫− 𝑑
• This first order ODE can be solved using the integrating factor
ln
:
 41

Series-Parallel Reactions
Product distribution in batch reactors and PFRs (cont’d)
• For k1 ≠ k2:

• When cA = cA0, cR = cR0:

 42

Series-Parallel Reactions
Product distribution in batch reactors and PFRs (cont’d)
• For k1 = k2:

• When cA = cA0, cR = cR0:

 43

Series-Parallel Reactions
Product distribution in batch reactors and PFRs (cont’d) A+ B → R
• Based on material balance, cA + cR + cS = cA0 + cR0 + cS0: R+B→S

• Express concentrations in terms of extents of reaction:

• Summing up to eliminate and :

• Combine the equations for and to eliminate cS and cS0:

 44

Series-Parallel Reactions
Product distribution in batch reactors and PFRs (cont’d)
• For a given conversion of A, , , and can be calculated
using the above equations:

Recall series reaction chart

 45

Series-Parallel Reactions
Product distribution in CSTRs
• Mole balance around the reactor:

• Combining the above equations gives:

 46

Series-Parallel Reactions
Product distribution in CSTRs (cont’d)
• This equation is used together with earlier equations for and to calculate
the concentrations:
CSTR
 47

Revisit: Opening Question 3

Consider the following reactions in the liquid phase:
A+ B →R rR = k1cAcB
R+B→S rS = k2cRcB
1 mole of A and 3 moles of B are rapidly mixed. The reaction is slow, allowing analysis of
composition at various times. When 2.2 moles of B remain unreacted, 0.2 mole of S is present in
the mixture. What should be the composition of the mixture when the amount of S present is
0.6 mole?

Species t = 0 Δ t>0 Analysis:

A 1 −0.6 0.4 1
(1)
B 3 −0.8 2.2 1−

R 0 0.4 0.4 (2)

S 0 0.2 0.2 Need to find , then combine (1) and (2) to find cR and cA at
Total 4 3.2
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Revisit: Opening Question 3

Solution 1:
1
For series-parallel reactions in batch or PFR: (1)
1−

(2)

Substitute values:
Substitute experimental values:

1 .
1−0.8
(1)

(2)
 49

Revisit: Opening Question 3

Solution 2:
−Δ
Using , operation point is along
blue line.

0.8 mol of B participated in both reactions.

0.2 mol of B participated in Reaction 2.
0.6
0.6 mol of B participated in Reaction 1,
consuming 0.6 mol A.
xA = 0.60 Operation point is along red line. X

Intersection of blue and red lines locates Y

operating point X.

For the same reaction, remains the same.

Move along this line to to locate
the new operating point Y.
Here, , and
 50

Quiz 4 (Series-Parallel Reactions)

1. For a given , does a PFR or CSTR give a higher cR?

2. To achieve the maximum c R for a given , is the conversion required for a

PFR higher or lower than that for a CSTR?
 51
Appendix: Quotient rule and how to use it to find in CSTR
𝑓(𝑥)
𝑓(𝑥) 𝑑𝑦 𝑑ℎ(𝑥) 𝑑
𝑔(𝑥)
If 𝑔(𝑥)
, we have 𝑑𝑥 𝑑𝑥
.
𝑑𝑥

For series reactions in CSTR, we have:

Differentiate the expression for cR:

Equate the derivative to zero: