Lecture #8

Chemical Reaction Engineering I

Youn-Woo Lee
School of Chemical and Biological Engineering
Seoul National University
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea ywlee@snu.ac.kr http://sfpl.snu.ac.kr
 Chapter 5
Isothermal Reactor Design: Conversion

Reaction Engineering I

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,
. ,

, .

. , CSTR PFR

.
.
 2
S2-1 .
, CSTR PFR
.

.
 4
4 .
(1) k
.
(2) k
CSTR .
(3) PFR
.
(4)
(PBR) .
20
.
 Objectives

Describe the algorithm that allows the reader to solve chemical

reaction engineering problems through logic rather than
memorization.
Size batch reactors, semibatch reactors, CSTRs, PFRs, and PBRs
for isothermal operation given the rate law and feed conditions.
Studying a liquid-phase batch reactor to determine the specific
reaction rate constant needed for the design of a CSTR.
Design of a tubular reactor for a gas-phase pyrolysis reaction.
Account for the effects of pressure drop on conversion in packed
bed tubular reactors and in packed bed spherical reactors.
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 Follow the Reaction Design Algorithm
Wizard of OZ
Follow the Yellow Brick Road
Isothermal Reaction
Design Algorithm
Isothermal Reaction
Design Algorithm
Isothermal Reaction
Design Algorithm
Isothermal Reaction
Design Algorithm
Isothermal Reaction
Design Algorithm
Isothermal Reaction
Design Algorithm
 Algorithm for isothermal reactor design

1. Mole balance and design equation

2. Rate law
3. Stoichiometry
4. Combine
5. Evaluate
We can solve the equations in the
combine step either
A. Graphically (Chapter 2)
B. Numerical (Appendix A4)
C. Analytical (Appendix A1)
D. Software packages (polymath)
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French Menu Analogy

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French Algorithm for isothermal reactors
Menu
Analogy Fig. 5-2

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 Scale-up of Liquid-Phase Batch Reactor
to the Design of a CSTR

PAST

Laboratory Pilot plant Full-scale

Experiment Operation Production

High cost of a pilot-plant leads to jump pilot plant operation

FUTURE

Microplant Full-scale
(Lab-bench-scale unit) Production

To make this jump successfully requires

a through understanding of the chemical kinetics and transport limitations.
 5.2 Batch Operation

For constant volume batch reactor, the mole balance can be written
in terms of concentration

1 dN A 1 dN A 1 dN A d (N A / V0 ) dC A
= rA = = = = rA
V dt V dt V0 dt dt dt

Generally, when analyzing laboratory experiments, it is best to

process the data in terms of the measured variable. Because
concentration is the measured variable for most liquid-phase
reactions, the general mole balance equation applied to reactions
in which there is no volume change becomes
dC A
= rA
dt
This is the form we will use in analyzing reaction rate data in Chap 7.
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 Reaction time in Batch Operation

Algorithm for isothermal reactor design A

B
1. Mole balance dX
N A0 = rAV0
& Design equation dt
2. Rate law rA = kC A2 irreversible, 2nd order in A

3. Stoichiometry C A = C A0 (1 X )

dX
4. Combination = kC A0 (1 X ) 2
dt 2nd order
Isothermal
Liquid-phase
dX
= kC A0 dt Batch reaction

(1 X ) 2

5. Analytical Evaluation
t X 1 X

1 dX
dt = t=
0 kC A0 0 (1 X ) 2 kC A0 1 X
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 Batch Reaction Times
Table 5-1

A
B
Mole balance dX rA
= V
dt N A0
First - order
First-order Second order
Second-order
Rate law
rA = kC A rA = kC A2
NA
Stoichiometry (V=V0) CA = = C A0 (1 X )
V0

dX dX
Combine = k (1 X ) = kC A0 (1 X ) 2
dt dt
1 1 X
Integration t = ln t=
k 1 X kC A0 (1 X )

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 Batch Reaction Times

1st - order (X = 0.9, k = 10 -4 s 1 ) 2nd order (X = 0.9, kC A0 = 10 3 s 1 )

1 1 X
t R = ln tR =
k 1 X kC A0 (1 X )
1 1 0.9
= ln =
k 1 0.9 kC A0 (1 0.9)
2.3 9
= =
k kC A0
2.3
= 4 1 =
9
10 s 10 3 s 1
= 23,000 sec = 9,000 sec
= 6.4hr = 2.5hr
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 Batch Reaction Times

Table 5-2
The order of magnitude of time
to achieve 90% conversion
For first- and second-order irreversible batch reactions

1st-order 2nd-order Reaction time

k (s-1) kCA0 (s-1) tR
6.4 hrs
10-4 10-3 Hours 2.5 hrs

10-2 10-1 Minutes

1 10 Seconds

1,000 10,000 Milliseconds

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 Reaction time in Batch Operation

Typical cycle times for a batch polymerization process

tt = tf + te + tR + tc
Activity Time (h)
1. Charge feed to the reactor and agitate, tf 0.5 - 2.0
2. Heat to reaction temperature, te 0.5 - 2.0
3. Carry out reaction, tR Varies
4. Empty and clean reactor, tc 1.5 - 3.0

Total cycle time excluding reaction 2.5 - 7.0

Batch polymerization reaction times may vary between 5 and 60 hours.

Decreasing the reaction time with a 60-h reaction is a critical problem. As the
reaction time is reduced (e.g. 2.5 h for a 2nd-order reaction with X=0.9 and
kCA0=10-3 s-1), it becomes important to use large lines and pumps to achieve
rapid transfer and to utilize efficient sequencing to minimize the cycle time.
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 Design a Reactor to Produce of ethylene glycol

Design a CSTR to produce 200 million pounds of ethylene glycol per year
by hydrolyzing ethylene oxide. However, before the design can be carried
out, it is necessary to perform and analyze a batch reactor experiment to
determine the specific reaction rate constant (kA). Since the reaction will be
carried out isothermally, kA will need to be determined only at the reaction
temperature of the CSTR. At high temperature there is a significant by-
product formation, while at temperature below 40oC the reaction does not
proceed at a significant rate; consequently, a temperature of 55oC has been
chosen. Since the water is usually present in excess, its concentration may
be considered constant during the course of the reaction. The reaction is
first-order in ethylene oxide.

O CH2-OH
H2SO4
CH2-CH2 + H2O CH2-OH
Catalyst
A + B C Seoul National University
 Example 5-1 Determining k from Batch Data

In the lab experiment, 500mL of a 2 M solution (2 kmol/m3) of EO in

water was mixed with 500mL of water containing 0.9 wt % sulfuric acid
catalyst. At T=55oC, the CEG was recorded with time. Determine the
specific reaction rate at 55oC.

Time Concentration of EG EO + H2O EG

(min) (kmol/m3) A + B C
0.0 0.000
0.5 0.145
1.0 0.270
1.5 0.376
2.0 0.467
3.0 0.610
4.0 0.715
6.0 0.848
10.0 0.957
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 Problem Solving Algorithm
Example 4-1 Determining k from Batch Data

A. Problem statement. Determine the kA D. Assumptions and approximations:

B. Sketch Assumptions
C. Identify 1. Well mixed
C1. Relevant theories A, B, C batch 2. All reactants enter at the same time
Rate law: rA = k AC A 3. No side reactions
4. Negligible filling and emptying time
dN A
Mole balance: = rAV 5. Isothermal operation
C2. Variables dt Approximations
Dependent: concentrations, Ci 1. Water in excess (CH2O~constant)
Independent: time, t CB~ CBO
C3. Knowns and unknowns E. Specification. The problem is neither
Knowns: CEG = f(time) overspecified nor underspecified.
Unknowns:
1. CEO = f(time) F. Related material. This problem uses the
2. kA mole balances developed in Chap. 1
3. Reactor volume for a batch reactor and the
C4. Inputs and outputs: reactant fed stoichiometry and rate laws developed
all at once a batch reactor in Chap. 3.
C5. Missing information: None G. Use an Algorithm.(figs 5-1 & 5-2)
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 Problem Solving Algorithm
Example 4-1 Determining k from Batch Data

1 dN A
1. MOLE BALANCE = rA Batch reactor that is well-mixed
V dt
Since water is present in such
excess, the concentration of water at
2. RATE LAW rA = kC A any time t is virtually the same as
the initial concentration and the rate
law is independent of the
concentration of H2O. (CB~CB0)
3. STOICHIOMETRY
A + B C
Species symbol Initial Change Remaining Concentration

CH2CH2O A NA0 - NA0X NA=NA0(1-X) CA=CA0(1-X)

H2O B BNA0 - NA0X NB=NA0(B-X) CB=CA0(B-X)
CB~ CA0 B = CB0

(CH2OH)2 C 0 NA0X NC =NA0X CC=CA0X

NT0 NT =NT0 - NA0X

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 Problem Solving Algorithm
Example 5-1 Determining k from Batch Data

1 dN A
= rA
V dt

dC A dC A
4. COMBINING = rA , rA = kC A = kC A
dt dt
Mole balance Rate law

5. EVALUATE

For isothermal operation, k is constant:

CA dC A t t C A0

C A0 CA
= kdt = k dt
0 0
ln
CA
= kt

C A = C A0 e kt
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 Problem Solving Algorithm
Example 5-1 Determining k from Batch Data

The concentration of EG at any time t can be obtained from the reaction stoichiometry

A+B C

N C = N A0 X = N A0 N A

NC NC
CC = = = C A0 C A = C A0 (1 e kt )
V V0

CC = C A0 (1 e kt )

C A0 C C
ln = kt
C A0
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 Example 5-1 Determining k from Batch Data

Rearranging and taking the logarithm

of both side yields rA = (0.311 min 1 )C A
C A0 C C
ln = kt The rate law can now be used in the design
C A0
of an industrial CSTR. Note that this rate
We see that a plot ln[(CA0-CC)/CA0] as law was obtained from the lab-scale batch
a function of t will be a straight line with reactor (1000 mL).
a slope k. 1

ln 10 2.3
k= = = 0.311 min 1 0.6
t 2 t1 8.95 1.55

(CA 0 -CC )/CA 0

t CC C A0 C C
(min) (kmol/m3) C A0
0.1
0.0 0.000 1.000
0.5 0.145 0.855 0.06
1.0 0.270 0.730
1.5 0.376 0.624
2.0 0.467 0.533
3.0 0.610 0.390 0.01
0 2 4 6 8 10 12
4.0 0.715 0.285
t ( min)
6.0 0.848 0.152 1.55 8.95
10.0 0.957 0.043 Seoul National University
 Example 5-1 Determining k from Batch Data

rA = (0.311 min 1 )C A
The rate law can now be used in the design of an industrial CSTR.
Note that this rate law was obtained from the lab-scale batch
reactor (1000 mL).

:
t C , CC
CRE .
( )
1 k t
CC .
 5.3 Design of CSTR

FA0 X
Mole balance V= Design Equation for a CSTR (5-6)
(rA ) exit

FA 0 = v 0 C A 0 v0C A0 X V C X
V= = = A0 the space time (5-7)
(rA ) exit v0 (rA ) exit

For a 1st-order irreversible reaction, the rate law is

Rate law rA = kC A Reactants

1 X C A0 X
Combine = =
k 1 X kC A

Rearranging Products

k
CSTR relationship X =
between
space time and conversion
1 + k (5-8)

for a 1st-order liquid-phase rxn

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 5.3.1 A single CSTR

We could also combine Eq (4-12) and (5-8) to find the exit

concentration of A, CA:

k k
C A = C A0 (1 X ) = C A0 1 X =
1 + k
1 + k
1 + k k C A0
= C A0 =
1 + k 1 + k
C A0
CA =
1 + k

C A0
exit concentration of A CA = (5-9)
1 + k

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 Reaction Damkhler number

rA0V Rate of Reaction at Entrance " a reaction rate"

Da = = =
FA0 Entering Flow Rate of A " a convection rate"

The Damkohler is a dimensionless number that can give us a quick

estimate of the degree of conversion that can be achieved in continuous-
flow reactor.
rA0V kC A0V
For 1st-order irreversible reaction Da = = = k
FA 0 v0 C A0

rA0V kC A2 0V
For 2nd-order irreversible reaction Da = = = kC A0
FA0 v0 C A0

RULE OF THUMB
Da 0.1 will usually give less than 10% conversion.
Da 10.0 will usually give greater than 90% conversion.
 Reaction Damkhler Number

=0 Batch CSTR PFR

1 X 1
1st order kt R = ln k = k = ln
1 X 1 X 1 X

X X
2nd order kt R C A0 =
X kC A0 = kC A0 =
1 X (1 X )2
1 X

0 Batch CSTR PFR

X (1 + X )
kt R = (1 + X )ln
1
k = (1 + X )ln
X k = 1
1st order X
1 X 1 X 1 X

kk R C A0 = 2 (1 + X )ln(1 X ) kC A0 = 2 (1 + X )ln(1 X )
X (1 + X )2
2nd order (1 + )2 X kC A0 =
+ 2
X+ (1 X )2 + 2X +
(1 + )2 X
1 X 1 X

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 5.3.1.2 A Second-Order Reaction in a CSTR

For a 2nd-order liquid-phase reaction We solve the above eq. for X:

being carried out in a CSTR, the
combination of the rate law and the
design equation yields (1 + 2kC A0 ) (1 + 2kC A0 )2 (2kC A0 )2
X =
2kC A0
V=
FA0 X FA0 X
= (5-10) (1 + 2kC A0 ) 1 + 4kC A0
=
rA kC A2 2kC A0
=
(1 + 2Da ) 1 + 4Da
For const density v=v0, FA0X=v0(CA0-CA) (5-12)
2Da
V C A0 C A
= =
v0 kC A2 The minus sign must be chosen in the
quadratic equation because X cannot
be greater than 1.
Using our definition of conversion, we
have
=
X
(5-11) X =
(1 + 2Da ) 1 + 4Da
kC A0 (1 X )
2
2Da
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 A Second-Order Reaction in a CSTR

X =
(1 + 2Da ) 1 + 4Da
2Da

rA0V
Da =
FA0

0.88
0.67

At high conversion, a 10-fold (6

60) increase in Da will
increase the conversion only to
88% due to lowest value of
reactant concentration in CSTR. 6 60
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 5.3.2 CSTRs in Series

CA0 CA1, X1
v0
CA2, X2

-rA1, V1 -rA2, V2

For 1st-order irreversible reaction with no volume change (v=v0) is carried out in
two CSTRs placed in series. The effluent concentration of A from reactor 1 is

C A0
C A1 =
1 + 1k1

From a mole balance on reactor 2,

FA1 FA2 v0 (C A1 C A2 )
V2 = =
rA2 k 2 C A2
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 CSTRs in Series

Solving for CA2, the concentration exiting the second reactor, we get

C A1 C A0 C A0
C A2 = = C A1 =
1 + 2 k 2 (1 + 2 k 2 )(1 + 1k1 )
(5-13) 1 + 1k1

If instead of two CSTRs in series we had n equal-sized CSTRs connected in

series (1 = 2 = = n = i = (Vi/v0)) operating at the same temperature (k1 =
k2 = = kn = k), the concentration leaving the last reactor would be

C A0 C A0
C An = = (5-14)
(1 + k )n
(1 + Da )n

The conversion and the rate of disappearance of A for these n tank reactors
in series would be

1 kC A0
X = 1 rAn = kC An =
(1 + k )
(5-15) (5-16)
(1 + k ) n n

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 Conversion as a function of reactors in series
for different Damkhler numbers for a first-order reaction

k=1

k=0.5

k=0.1

rA0V
Da =
FA0
Da 1, 90% conversion is achieved in two or three reactors;
thus the cost of adding subsequent reactors might not be justified
Da ~0.1, the conversion continues to increase significantly with each reactor added
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 CSTRs in Parallel

A balance on any reactor i, gives the individual

reactor volume
FA0 1
Xi
Vi = FA0i

rAi FA0 i
-rA1, V1

X1 = X 2 = = X n = X i

rA1 = rA2 = = rAn = rA

-rAi, Vi
The volume of each individual reactor, Vi, is
related to the total volume, V, of all the reactors,
and similar relationship exists for the total molar n
flow rate
V FA0
Vi = FA 0 i = -rAn, Vn
n n
 CSTRs in Parallel
Substituting these values into Eq (5-10) yields
F
FA0 i = A0
V n
Vi =
FA0 1
n Xi
Vi = FA0i

rAi FA0 i
-rA1, V1

i
V FA0 X i
=
n n rAi
-rAi, Vi
FA0 X i FA0 X
V= = n
rAi rA
The conversion achieved in any one of the reactors
in parallel is identical to what would be achieved if -rAn, Vn
the reactant were fed in one stream to one large
reactor of volume V!
 Example 5-2: Producing 200,000,000 lb/yr in a CSTR
~91 ton/yr
CA0=1 vA0=vB0
k
It is desired to produce 200 x 106 pounds per year
of EG. The reactor is to operated isothermally.
A 1 lb mol/ft3 solution of ethylene oxide (EO) in
water is fed to the reactor together with an equal
volumetric solution of water containing 0.9 wt%
of the catalyst H2SO4. The specific reaction rate
constant is 0.311 min-1 as determined in Ex 5-1.

(a) If 80% conversion is to be achieved, determine

the necessary CSTR volume.

(b) If two 800-gal reactors were arranged in parallel,

what is the corresponding conversion?

(c) If two 800-gal reactors were arranged in series,

what is the corresponding conversion?

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 M.W. of EG=62

M.W. of EO=58

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 v0 = vA0 + vB0

=1

3m 10

~2 gps 5
1.5m

5 gal~19.8L

1 gal ~3.78 L

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Seoul National University
Seoul National University
(E5-2.6)

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 (E5-2.7)

(5-15):

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Seoul National University
 Producing 200,000,000 lb/yr of EG in a CSTR

one CSTR two equal-sized CSTRs in parallel two equal-sized CSTRs in series

X=0.81
800gal

800gal 800gal
X=0.8
X=0.81 X1=0.68 X2=0.90
1480gal
800gal

Conversion in the series arrangement is greater than in parallel for CSTRs.

The two equal-sized CSTRs in series will give a higher conversion than
two CSTRs in parallel of the same size when the reaction order is greater than zero.
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: CSTR, 2 CSTR, 2 CSTR 1
-- CRE .
. 2 CSTR
, CSTR . 2
CSTR CSTR . 0
.

one CSTR two equal-sized CSTRs in parallel two equal-sized CSTRs in series

X=0.81
800gal

800gal 800gal
X=0.8
X=0.81 X1=0.68 X2=0.90
1480gal
800gal

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PEL (Permissible Exposure Limit)
 Lecture #9

Chemical Reaction Engineering I

Youn-Woo Lee
School of Chemical and Biological Engineering
Seoul National University
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea ywlee@snu.ac.kr http://sfpl.snu.ac.kr
 5.4 Tubular Reactors

-2nd-order liquid-phase rxn Rate law: rA = kC A

2

(A Products)
X

-Turbulent, dX
- No dispersion V = FA0
- No radial gradients in T, u, or C
0 kC A2
Stoichiometry for liq. phase rxn
PLUG-FLOW REACTOR T & P = constant

PFR mole balance C A = C A0 (1 X )

dX
FA 0 = rA Combination
dV
The differential form of PFR design F X 1 v0 X
equation must be used when there is a V = A20
kC A0 0 (1 X ) 2
dX =
kC A0 1 X
P or heat exchange between PFR &
the surrounds. In the absence of P or
heat exchange, the integral form of the kC A0 Da2
PFR design equation is used. X= =
1 + kC A0 1 + Da2
X

dX
V = FA0 Da2 is the Damkohler number
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0 rA for a second-order reaction
 5.4 Tubular Reactors

-2nd-order gas-phase rxn Rate law: rA = kC A2

(A Products)
-Turbulent,
- No dispersion X

dX
- No radial gradients in T, u, or C V = FA0
0 kC A2
PLUG-FLOW REACTOR

PFR mole balance Stoichiometry for gas phase rxn

dX T & P = constant
FA 0 = rA
dV FA FA0 (1 X ) (1 X )
The differential form of PFR design CA = = = C A0
v v0 (1 + X ) (1 + X )
equation must be used when there is a
P or heat exchange between PFR &
the surrounds. In the absence of P or Combination
heat exchange, the integral form of the
X (1 + X ) 2
PFR design equation is used.
V = FA0 dX
X 0 kC A0 (1 X )
2 2

dX
V = FA0
0 rA Seoul National University
 5.3 Tubular Reactors

X (1 + X ) 2
V = FA0 0 kC 2 (1
A0 X) 2
dX

CA0 is not function of X; k=constant (isothermal)

FA0 X (1 + X ) 2
V=
kC A2 0 0 (1 X ) 2
dX FA0 = C A0 v0

Integration yields (see Appendix A.1 Eq. (A-7) @ page1009)

v (1 + ) 2
X
V= 0 2(1 + ) ln(1 X ) + X +
2

kC A0 1 X

Reactor length will be

v0 (1 + ) 2
X V = Ac L
L= 2(1 + ) ln(1 X ) + X +
2

kC A0 Ac 1 X
Cross sectional area Seoul National University
Conversion as a function of distance down the reactor

1.2
A 0.5B (=-0.5)
1
A B (=0)
Conversion (X)

0.8 A 2B (=1)
A 3B (=2)
0.6

0.4
v0
0.2 = 2.0dm 3
kC A0
0
0 2 4 6 8 10 12 14
L (m)

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 The reaction that has a decrease in the total number of moles
will have the highest conversion for a fixed reactor length.
v = (1 0.5 X )v0
the reactant spends more time

v = (1 + 2 X )v0
the reactant spends less time

The volumetric flow rate decreases with increasing conversion,

and the reactant spends more time in the reactor
than reactants that produce no net change in the total number of moles.
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Change in Gas-Phase Volumetric Flow Rate Down the Reactor

v (1 + ) 2 X
v=vo(1+X) V= 0 2 (1 + ) ln(1 X ) + X +
2
(5-17)
kC A0 1 X
=1 : (A2B)
v = vo(1+X)

= 0 : (AB)
v = vo

=-0.5 : (2AB)
Complete
conversion v = vo(1-0.5X)

When there is a decrease in the number of moles in the gase phase,

the volumetric flow rate decreases with increasing conversion,
and the reactant spends more time in the reactor
than reactants that produce no net change in the total number of moles.
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 Example 5-3: Determination of a PFR Volume

Determine the PFR volume necessary to produce 300 million

pounds of ethylene a year from cracking a feed stream of pure
ethane. The reaction is irreversible and follows an elementary rate
law. We want to achieve 80% conversion of ethane, operating the
reactor isothermally at 1100K at a pressure of 6 atm.
k=0.072s-1@1000K ; E=82,000cal/mol.

C2H6 C2H4 + H2
A B +C
FB = 300x106 lb/year = 0.340 lb-mol/sec
FB = FAoX
FAo = FB/X = 0.340/0.8 = 0.425 lb-mol/sec
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 .2)

Ind. Eng. Chem. Process Des. Dev., 14, 218 (1975)

Ind. Eng. Chem., 59(5), 70 (1967)
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Seoul National University
Seoul National University
 EX 5-3

14

12
Reactor Volume (m3)

10

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
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Conversion (X)
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C2H6 C2H4 + H2
A B +C

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 5.5 Pressure Drop in Reactors

In liquid-phase reaction
- the concentration of reactants is insignificantly affected by even
relatively large change in the total pressure
- ignore the effect of pressure drop on the rate of reaction
when sizing liquid-phase chemical reactors
- that is, pressure drop is ignored for liquid-phase kinetics calculations

In gas-phase reaction
- the concentration of the reacting species is proportional to total pressure
- the effects of pressure drop on the reaction system are a key factor
in the success or failure of the reactor operation
- that is, pressure drop may be very important for gas-phase reactions
(Micro-reactors packed with solid catalyst)

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 Pressure drop and the rate law

for an ideal gas,

Fi FA0 ( i + vi X )
Ci = =
v v0 (1 + X )( P0 / P )(T / T0 ) .

For isothermal operation

+v X P
C i = C A0 i i i =
Fi 0
= y A0
1 + X P0 FA0
A = 1, B = b / a

- determine the ratio P/P0 as a function of V or W

- combine the concentration, rate law, and design equation
- the differential form of the mole balance (design equation) must be used
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 Pressure drop and the rate law

For example,
- the second order isomerization reaction in a packed-bed reactor
2A B + C
-the mole balance (differential form)
The differential form of
dX gmoles
FA 0 = rA PFR design equation
dW g catalyst min must be used when
there is a P
- rate law
rA = kC A2

- stoichiometry for gas-phase reactions

1 X P T0
C A = C A0
1 + X P0 T
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 Pressure drop and the rate law

Then, the rate law

2
1 X P T0
rA = k C A0 (5-20)
1 + X 0
P T

- the larger the pressure drop from frictional losses, the smaller the reaction rate

Combining with the mole balance (assuming isothermal operation: T=T0)

2
P
2
dX C A0 (1 X )
FA0 = k
+ P
dW 1 X 0
Dividing by FA0(=v0CA0)
2
1 X P
2
dX kC A0
=
1 + X P0
dW v0

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 Pressure drop and the rate law

2
1 X P
2
dX kC A0
=
dW v0 1 + X P0

-The right-hand side is a function of only conversion and pressure

dX (5-21)
= f ( X , P)
dW

-Another equation is needed to determine the conversion as a function of

catalyst weight: that is, we need to relate the pressure drop to the catalyst
weight dP
P = f (W ) We need
dW
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Flow through a packed bed

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 Flow through a packed bed dP
We need
dW

The majority of gas-phase reactions are catalyzed by passing the reactant

through a packed of catalyst particles

Ergun equation: to calculate pressure drop in a packed porous bed

dP G 1 150(1 )
= 3 + 1.75G (5-22)
dz g c D p Dp
laminar turbulent

G=u=superficial mass velocity [kg/m2s]; u=superficial velocity [m/s]; Dp=diameter of particle

in the bed [m]; =porosity=volume of void/total bed volume; 1- =volume of solid/total bed
volume, gc=1.0 [m/s2]; =viscosity [kg/ms]

The gas density () is the only parameter that varies with pressure on the right-
hand side. We are now going to calculate the pressure drop through the bed.
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 Flow through a packed bed

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 dP
Flow through a packed bed We need
dW

Equation of continuity
m 0 = m
0 v0 = v

- The reactor is operated at steady state, the mass flow rate at any point is equal to
the entering mass flow rate
Gas-phase volumetric flow rate

P T FT v0
v = v0 0
T

F
= 0
P 0 T0 v
Then,

v0 P T0 FT 0
= 0 = 0
v P0 T FT

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 Pressure drop in a packed bed reactor

then, Ergun equation

dP G (1 ) 150(1 ) P0 T FT
= + 1.75G
0 g c D p 3 T F
dz Dp P 0 T0

Simplifying dP P0 T FT
= 0 (5-24)
dz P T0 FT 0

G (1 ) 150(1 )
0 = + 1.75G (5-25)
We need
dP dP dP dz
=
0 g c D p
3
Dp
dW dW dz dW
Ac
The catalyst weight, W = (1 ) Ac z c z
Volume of Density of
solid solid catalyst

dW = c (1 ) Ac dz (5-26)
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 Pressure drop in a packed bed reactor

dz 1
dP 0 P0 T FT =
dW c (1 ) Ac
= dP dP dz
=
dW Ac (1 ) c P T0 FT 0 dW dz dW dP P T F
= 0 0 T
dz P T0 FT 0

dP T P0 FT
Simplifying = (5-27)
F
dW 2 T0 P / P0 T0

2 0
= (5-29)
Ac c (1 ) P0

F FT FA0
FT = FT 0 + FA0X = FT 0 1 + A0 X = 1 + X = y A0 =
FT 0 FT 0 FT 0

dP T P0
= (1 + X ) (5-30)
dW 2 T0 P / P0
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 Pressure drop in a packed bed reactor

dP T P0
= (1 + X ) (5-30)
dW 2 T0 P / P0

< 0, the pressure drop (P) will be less than = 0

> 0, the pressure drop (P) will be greater than = 0

For isothermal operation

dP dX
= f ( X , P) and = f ( X , P) (5-31)
dW dW

The two expressions are coupled ordinary differential equations.

We can solve them simultaneously using an ODE solver such as Polymath.
For the isothermal operation and = 0, we can obtain an analytical solution.
Polymath will combine the mole balance, rate law and stoichiometry
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 Pressure drop in a packed bed reactor
1 0
For the isothermal operation and = 0,

dP T P0
= (1 + X ) (4-30)
dW 2 T0 P / P0
Analytical Solution

If = 0 or X 1, we can obtain an analytical solution to Eq. (4-30) for isothermal

operation (i.e., T=T0). For isothermal operation with = 0, Eq. (4-30) becomes

Isothermal with dP P0
=
=0 dW 2 ( P / P0 )

Rearranging gives us

P d ( P / P0 ) d ( P / P0 ) 2
2
dW = =
P0 dW
Taking P/P0 inside
(4-32) the derivative
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 Pressure Drop in a Packed Bed Reactor

d ( P / P0 ) 2
=
dW
Integrating with P=P0 @ W=0

( P / P0 ) 2 = 1 W

P
=0 = 1 W (5-33)
T = T0 P0

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 Pressure drop in a packed bed reactor

If = 0 or X 1, we can obtain an analytical solution to Eq. (4-30) for isothermal

operation (i.e., T=T0). For isothermal operation with = 0, Eq. (4-30) becomes

P
Pressure ratio = 1 W (5-33)
only for = 0 P0
or X 1

2 0
=
Ac (1 ) c P0 2 0 z
W =
W = (1 ) Ac z c P0

G (1 ) 150(1 )
0 = + 1 . 75G
0 g c D p 3 Dp

Pressure as a P 2 z
function of = 1 0 (5-34)
P0 P0
reactor length, z
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 5.5.3 Pressure Drop in Pipes
Pressure drop for gases along the length of the pipe w/o packing

dP du 2 fG 2 u =G/
P dP 2 dP 2 fG 2
= G 0 G + =0
dL dL D = 0
P P0 dL PdL D
P0
Integrating with P=P0 at L=0, and assuming that f = constant
0
P02 P 2 P L P
= G2 0 2 f + ln 0
2 0 D P
Rearranging, we get
P 4 fG 2
y = 0 = 1 pV p =
P 0 P0 Ac D

Example 5-4: 1 schedule 40 x1000-ft L (p=0.018), P<10%

However, for high volumetric flow rates through microreactors,
the P may be significant. Seoul National University
 5-4

60 ft 1
40 .
104.4 lbm/h . 260C
. 45%,
. 10 atm.

Pipe size Sch OD (in.) ID (in.) t (in.)

1-1/2 40 1.900 1.610 0.145
10 1.900 1.682 0.109
5 1.900 1.770 0.065
 5-4
 5-4
 5-4

= 3.3+160.7
 5-4
 5-4
 5-4

10

8
P (atm)

2

.
0
0 10 20 30 40 50 60

z (ft)
E5-4.1 z = W/(Acc(1 - ))
 5-4
E5-4.1 z = W/(Acc(1 - ))
1000

800
.
v (ft3/h)

600

400

200

0
0 10 20 30 40 50 60

z (ft)
 Lecture #10

Chemical Reaction Engineering I

Youn-Woo Lee
School of Chemical and Biological Engineering
Seoul National University
155-741, 599 Gwanangro, Gwanak-gu, Seoul, Korea ywlee@snu.ac.kr http://sfpl.snu.ac.kr
 5.5.4 Analytical Solution for Reaction with Pressure Drop

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.

5-8
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 Reaction with Pressure Drop
Conversion as a function of catalyst weight
2nd-order isothermal reaction

A B Combining

Mole balance:
dX
dX
dW
=
kC A2 0
FA0
[
(1 X ) 2 (1 W )1/ 2 ]2

F A0 = rA
dW
Separating variable and Integrating
Rate law:

rA = kC A2
= (1 W )dW
(5-19) FA0 dX
kC A2 0 (1 X ) 2

Stoichiometry: Gas-phase isothermal with =0

at X = 0, W = 0 and FA0 = C A0 v0
P
C A = C A0 (1 X ) (5-37)
P0 v0 X W
= W 1
P kC A0 1 X 2
= 1 W (5-33)
P0

C A = C A0 (1 X )(1 W )1/ 2
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 Reaction with Pressure Drop
Conversion as a function of catalyst weight

Conversion for 2nd-order isothermal reaction in PFR with P

kC A0W W
1
v0 2
X = (5-38)
kC W W
1 + A 0 1
v0 2

Catalyst weight for 2nd-order isothermal reaction in PFR with P

1 {1 [(2v0 ) / kC A0 ][X /(1 X )]}1/ 2 (5-39)

W =

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 5-5
 5-5
 5-5
 5-5
 5-5
 5-5
 5-5
 5-5
: .

. 10 DVD-ROM 12
,
.


( 10-5 ).
k1/Dp [DVD-ROM 12 (12-35) ],
( 10-9).

k ,
.
, k
.

. E5-5.1 .
 The Optimum Catalyst Particle Diameter

Pressure drop
dominant Internal diffusion
Conversion inside catalyst k ~ 1/Dp
dominant
X

Dp, opt
Particle Diameter, Dp

Why not pack the catalyst Problems with large diameter tubes:
into a large diameter (1) Bypassing or Channeling
to reduce P? (2) Little efficient of heat transfer rate
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(Diffusion) (Reaction)

(Diffusion) (Reaction)
 5-5

, G
P
?

(1)
(Channeling) (Bypassing)
.

(2) ()


 5-6 X
85 . 2010 0.53,
40 . 60% .
(30%), (30%), (10%) (5%) .
60%
. .

rA = kPA1 / 3 PB2 / 3 mol / kgcat s

mol
k = 0.00392 @ 260 o C
atm kgcat s

260C .
10 atm(1013 kPa) 136.21 mol/s . 100 1
40 , 10
. 0.1362 mol/s.
. 1925 kg/m3, 0.45,
16 kg/m3. , , , , ,
E5-4 . , . ?
0 . 5-4
0 =25.8 atm/m, =0.0367 kg-1 .

Ag
C2H4+ O2 C2H4O
C2H4
X=0.6 3 136.21 mol/s
5
4 Air
W=? X=0.6 260oC, 10atm
 5-6 X
 5-6 X
 5-6 X
 5-6 X
 5-6 X
60% 27kg .
Wf =27 kg
W=0 X=0, y=1.0. Wf=27kg.
60%
, 27kg . 60%
.

(, ODE ) .
.
(E5-6.9) (E5-6.10) [ (5-6.11) (5-6.14)]

E5-6.1 E5-6.2 . (E5-
6.9) (E5-6.10) ,
.
.
 5-6 X
(W) Wf=27kg

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 5-6 X
 5-6 X

( ) , .
 5-6 X
.
(4-23) ,

f=/0

. .
 5-6 X

rA . 0
,
.
 5-6 X
 5.6 Synthesizing a Chemical Plant

,
4 2 2
.

The profit from a chemical plant will be the difference between income
from sales and the cost to produce the chemical

Profit = value of products cost of reactants

operating costs separation costs

The operating cost: energy, labor, overhead, and depreciation of

equipment

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 Example 4-6 Production of ethylene glycol

H2, C2H4
402 million
lbC2H6 /yr
1 C2H6 C2H4 + H2 2
separator
V=81 ft3, X=0.8 C2H6
O2, C2H4, N2, C2H4O
rA = kPA1/ 3 PB2 / 3 k = 0.0141
lbmol
@ 260o C
Ag atm lb cat h
C2H4+ O2 C2H4O C2H4
3
6 5 260oC, 10bar
4 Air
separator
W=45,440 lb, X=0.6
H2O C2H4O
7 8 H2O, 0.9wt% H2SO4

C2H4O(aq)
200 million
9
lb EG/yr
V=197 ft3, X=0.8
absorber
CH2OH
C2H4O + H2O Cat.

CH2OH Seoul National University
 Production of ethylene glycol

H2, C2H4
402 million
lbC2H6 /yr
1 C2H6 C2H4 + H2 2
separator
V=81 ft3, X=0.8 C2H6
O2, C2H4, N2, C2H4O
Ag
C2H4+ O2 C2H4O C2H4
3
6 5
4 Air
separator
W=45,440 lb, X=0.6
H2O C2H4O
7 8 H2O, 0.9wt% H2SO4

C2H4O(aq)
200 million
9
lb EG/yr
V=197 ft3, X=0.8
absorber
CH2OH
C2H4O + H2O Cat.

CH2OH Seoul National University
 Production of ethylene glycol

lb mol
M.W. bp(oC) 1 2 3 4 5 6 7 8 9 $/lb
s
C2H6 0.425 0.040
C2H4
H2
O2
N2
EO
EG 0.102 0.380
H2SO4 - 0.043
H2O
Total 0.425 0.102
 Synthesizing a Chemical Plant

Ethylene glycol = $0.69/lb (2x108 lb/yr)

Ethane = $0.17/lb (4x108 lb/yr)
Sulfuric acid = $0.15/lb (2.26x106 lb/yr)
Operating cost = $1.2x107/yr

Profit = $138MM $68MM - $0.34MM - $12MM

= $57.7 MM

How the profit will be affected by conversion, separation, recycle

stream, and operating costs?

2006 , $0.17, $0.15 $0.69.

www.chemweek.com . Seoul National University
Lotte Chemical to Make US$3 Billion Joint Investment to Build Ethane Cracker, EG Plants in USA

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Fig. 5-1
Isothermal
Reaction
Design
Algorithm
for Conversion

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 .

, batch, CSTR, PFR, PBF,

.

Evaluation

Combine

Stoichiometry

Rate Law

Mole Balance

, PBR
,
. .
, 30
[P5-11B P5-15B ]
[P5-8B ]. Seoul National University
Homework #6

P5-1A

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