Chemical Reaction

Engineering
Reactor Design for
Multiple Reactions
Dr Veluri VPS Murthy, Professor
Phone: +606 7989 271 (preferred)
Mobile: +601116672959
e-mail: vvpsnm@gmail.com

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 L9-2

Reactor Design for

Multiple Reactions
Usually, more than one reaction occurs within a chemical reactor
Minimization of undesired side reactions that occur with the desired
reaction contributes to the economic success of a chemical plant
Goal: determine the reactor conditions and configuration that
maximizes product formation
Reactor design for multiple reactions
Parallel reactions
Series reactions
Independent reactions
More complex reactions
Use of selectivity factor to select the proper reactor that minimizes
unwanted side reactions

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 Multiple Reactions
Types of multiple reactions
Reaction Rates of Single &
Multiple Reactions
Maximizing Selectivity and Yield for
Parallel Reactions:

Single reactant systems

Two reactant systems

Series Reactions

Series-Parallel Reactions

Algorithm for Multiple Reactions

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 Types of Multiple Reactions
. Series Reactions A k1 B k2 C
E.g. Ethylene oxide + NH3 Mono Di- Tri-ethanolamine
. Parallel Reactions A e.g.
k BEthanol Ethylene
1

A k2
Ethanol CAcetaldehyde
. Complex Reactions: Series and Parallel
Products of above reactions A1 B
k
A k1 B C

Ethylene +Acetaldehyde Ak2 COR

Butadiene AC D
k2
B Ck3 D
. Independent i.e. feedstock has many reactants
A k1 C e.g. Cracking of crude oil to gasoline
B D
k2

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Parallel reactions

Series reactions

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Parallel or Competitive Reactions:
Example
Ethylene Oxide Synthesis

CH2=CH2 + 3O22CO2 + 2H2O (undesired)

O

CH2=CH2 + O2CH2-CH2(desired)
Series-Parallel reactions

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 Parallel Reactions Economics
What should be the criterion for designing reactor system ?
Economic success of a plant depends on minimization of
undesired side reactions. D
How to maximize desired product and minimize
undesired product?

Separator
Reactor D
A System U
Cost

Reactor Cost
U
Separator Cost

Efficiency
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 Parallel Reactions - Parameters
Desired Reaction A kD
D
Example : oxidation of ethylene to ethylene oxide

Undesired Reaction A kU
U
Example : complete oxidation of ethylene
rD
Selectivity Local S DU
rU
ND
Batch YD
Yield Overall Reactor NAo NA
rD
Local YD Yield Flow YD
FD
rA Reactor FAo FA

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 Selectivity and Yield
There are two types of selectivity and yield:
Instantaneous and Overall.

Instantaneous Overall
Selectivity rD ~ F
S DU S DU D
rU FU

Yield rD ~ FD
YD YD
rA FA0 FA

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 Maximizing Selectivity (Local)
for Parallel Reactions
By the selection of reactors and their operational
strategies
Localvs. Overall Selectivity
Local Selectivity: rD
SDU
Overall Selectivity: rU
Batch systems: S
DU = ND/NU = Moles of D at
the end/ Moles of U at the end
Flow systems: SDU = FD/FU = Exit molar flow
rate of D/ Exit molar flow rate of U.
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 Selectivity in Parallel Reactions:
Single Reactant Systems
Desired Reaction: DA D
kD
rD k DCAD
Undesired Reaction: UA U
kU
rU k UCAU

What is the selectivity ?

D
rD k DC A k D ( D U )
S DU U
CA
rU kU C A kU
Let us examine some reactor operating
scenarios to maximize selectivity.
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 Selectivity for Single Reactant Systems
Case1:DU>0 rD k D ( D U )
SDU C A
rU k U
High CA favors D
How can we accomplish this?
Forgas phase reactions, maintain high pressures
For liquid-phase reactions, keep diluents to a
minimum
Batch or Plug Flow Reactors should be used.
CSTR should NOT be chosen.

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 Selectivity for Single Reactant Systems
rD kD
Case2:DU<0 SDU
rU k UC(AU D )
Low CA favors D

How can we accomplish this? CA0

For gas phase reactions, CA

operate at low pressures.
For liquid-phase reactions, CA

dilute the feed

CSTR is the preferred Reactant concentration
maintained at low level
reactor.
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 Selectivity for Single Reactant Systems
Case3: D U=0
Concentration has no effect on selectivity!
Then, how to maximize selectivity?
By choosing the most suitable temperature.

rD kD A D exp [ ED / RT ] AD
SDU exp [ (ED EU ) / RT ]
rU kU A U exp [ EU / RT ] AU

(a) If ED > EU

Operate reactor at the highest possible temperature

(b) If EU > ED
Operate reactor at the lowest possible temperature
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 L9-16

Maximizing SD/U for Parallel

Reactions: Temperature Control
ED EU
SD U
AD
AU
e RT
C A12 CB 1 2

What reactor conditions and configuration maximizes the selectivity?

Start with temperature (affects k):
a) If ED > EU b) If ED < EU
ED EU
ED EU ED EU
ED EU 0 e RT 1
0 e RT 1 RT
RT
Specific rate of desired reaction kD
Specific rate of desired reaction
increases less rapidly with
kD increases more rapidly with
increasing T
increasing T
Use lower T to favor desired
Use higher temperature to favor product formation (not so low that
desired product formation the reaction rate is tiny)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-17

Maximize SD/U for Parallel Reactions

using Temperature
kD D
ED EU
A AD
SD U e RT CA12
AU
U kU
What reactor temperature maximizes the selectivity?
ED = 20 kcal/mol, EU = 10 kcal/mol, T = 25 C (298K) or 100 C (373K)
T = 25 C
20,000
cal
10,000
cal a) ED > EU

(298K): mol mol
cal
1.987 298K

A A
SD U D e molK C A12 SD U D 4.6 10 8 C A1 2
AU AU
cal cal
T = 100 C 20,000 10,000 kD/U
(373K): mol mol
cal
1.987 373K

AD A
SD U e mol
K CA1 2
SD U D 1.4 10 6 C A1 2
AU AU
SD/U is greater at 373K, higher temperature to favors desired product formation
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 Selectivity in Parallel Reactions:
Two Reactant Systems
Desired Reaction: 1A 1B kD D rD k D CA1 CB1
Undesired Reaction: A B kU U rU k U CA2 CB2
2 2

rD k D ( 1 2 ) (1 2 )
SDU C A CB
rU k U

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 Selectivity for Two Reactant Systems

Case 1: 1>2; 1 > 2 Let, a = 1-2; b = 1 - 2

Example: 2A + 2B D A+BU
rD k D a b
SDU C A CB
rU k U
For high SDU, maintain both A & B as high as
possible
How can we accomplish this?
Use a Batch reactor
Or a Plug Flow reactor for continuous production.
Use high pressure for gaseous systems.
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 Selectivity for Two Reactant Systems
Case 2: 1>2; 1 < 2 Let, a = 1-2; b = 2 - 1
Example: 2A + B D A + 2B U
For high SDU, maintain
rD k D CaA
SDU concentration of A high
rU k U CbB
and of B low
How can we accomplish this?
Use a semi-batch reactor where B is fed slowly.
Use Tubular reactor with side streams of B
being fed continuously.
Use series of small CSTRs with A fed only to the first
and small amounts of B to each reactor.
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 Selectivity for Two Reactant Systems

Case 3: 1<2; 1 < 2 Let, a = 2-1; b = 2 - 1

Example: A + B D 2A + 2B U

rD k D For high SDU, maintain

SDU both concentration of A
rU k U CaA CbB
and B low.
How can we accomplish this?
Use a CSTR.
Use a Tubular reactor with large recycle ratio.
Use diluted feed
Use low pressure for gaseous reactions.
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 Selectivity for Two Reactant Systems
Case 4: 1<2; 1 > 2 Let, a = 2-1; b = 1 - 2

Example: A + 2B D 2A + B U
b For high SDU, maintain
rD k D C
SDU B
a concentration of B high
rU k U C
A and of A low
How can we accomplish this?
Use a semi-batch reactor where A is fed slowly
Use Tubular reactor with side streams of A
being fed continuously
Use series of small CSTR with B fed only to first
and A to each reactor.
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Contacting patterns for batch operation:

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Contacting patterns for continuous operation:

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 L9-25

Maximizing SD/U for Parallel Reactions:

Concentration
Desired Reaction: 1A 1B kD D ED EU
Undesired Reaction 2 A 2B kU U SD U
AD
AU
e RT CA12 CB12
What reactor conditions and configuration maximizes the selectivity?
Now evaluate concentration:
a) 1 2 1 2 0 b) 1 2 1 2 0

CA1 2 CA1 2
Use large CA Use small CA

c) 1 2 1 2 0 d) 1 2 1 2 0

CB 1 2 CB 1 2
Use large CB Use small CB
How do these concentration requirements affect reactor selection?
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L9-26

Concentration Requirements &

Reactor
k
Selection D
D How do concentration requirements play
A+B into reactor selection?
kU
U CA00 CA0
CB00 CB0
CSTR:
PFR concentration is
PFR (or PBR): concentration is always at its
high at the inlet & progressively lowest value
drops to the outlet (that at outlet)
concentration
Semi-batch: concentration
Batch: CB0
of one reactant (A as
concentration is shown) is high at t=0 &
CA(t)
high at t=0 & progressively drops with
CB(t)
progressively drops increasing time, whereas
with increasing time CA concentration of B can be
kept low at all times
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 kD L9-27
D High C favors desired High CA favors undesired
A+B A
product formation product formation
kU
U (keep CA low)
Batch reactor
PFR/PBR
Side streams feed low CA
High CB CA
When CA & CB are low (end time Semi-batch
favors or position), all rxns will be slow reactor slowly feed High CB
desired A to large amt of B
product PFR/PBR CA CA CA
formation High P for gas-phase rxn, do not CSTRs in
add inert gas (dilutes reactants) series
CA00 CA0
CB00 CB
CSTR
PFR/PBR w/ side streams feeding
High CB low CB CB
favors Semi-batch
undesired reactor, slowly High CA PFR/PBR
product feed B to large amount of A PFR/PBR w/ high
formation CB CB CB recycle
CSTRs in Dilute feed with inerts that are
(keep CB series
easily separated from product
low) B consumed
Slides courtesy of Prof before&leaving
M L Kraft, Chemical CSTR
Biomolecular Engr Low P if gas phaseUrbana-Champaign.
n Dept, University of Illinois,
 L9-28

Different Types of Selectivity

rate of formation of D rD
instantaneous rate selectivity, SD/U SD U
rate of formation of U rU
overall rate selectivity,S% DU

F Exit molar flow rate of desired product

S%D U D
FU Exit molar flow rate of undesired product

N Final moles of desired product

S%D U D
NU Final moles of undesired product

instantaneous yield, YD rate of formation of D r

YD D
(at any point or time in reactor) rate of consumption of A rA
%
overall yield, YD

% FD ND
batch Y%
Evaluated Evaluated
Y
flow D F F D
A0 A at outlet NA0 NA at tfinal
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
More Yields for Parallel Reactions
Point (relative) yield: Point (relative) yield
measures the ratio of the production rate of
a desired product P and the rate of
disappearance of the key reactant A.

Point yield is a function of composition and

this varies
along a PFR reactor, varies in time in a
batch reactor, and is a constant number in a
CSTR.
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 Overall (relative) yield
Overall (relative) yield: Overall (relative)
yield gives the ratio of the overall product
P produced and the total consumption of
reactant A.
In a CSTR the overall and point yield
are identical.
In a PFR the overall yield is the integral
average of the point yield:

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 Overall operational yield
defined as the number of moles of the
desired product produced per mole of key
reactant fed to the system. The relationship
to overall relative yield is obvious

where xA is the overall conversion of A.

None of the above yields has been
normalized, i.e., their maximum theoretical
value may be more or less than one as
dictated by stoichiometric coefficients.

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 Normalized yield

A normalized yield can be introduced

by
Where, y (P/A) max is obtained by
assuming that only the reactions
leading from A to P occur.

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 CSTR Vs. PFR for yield: General Rule

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