Chapter 4

Isothermal Reactor Design

Chemical Reaction Engineering 1

반응공학 1
 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.

• The principles of unsteady operation and semibatch reactor.

 Content
 Part I
Analysis of Batch reactor, CSTRs, and PFRs
by mole balances in terms of conversion, X

 Part II
Analysis of Membrane reactors, startup of a CSTR,
and semibatch reactors by mole balances in terms of
concentration, Ci, and molar flow rates, Fi
 Content
 Part I
4.1 Design Structure for Isothermal Reactor
4.2 Scale-up of Liquid-Phase Batch Reactor Data to the Design of a CSTR
4.3 Design of Continuous Stirred Tank Reactors (CSTRs)
4.4 Tubular Reactors
4.5 Pressure Drop in Reactors
4.6 Synthesizing the Design of a Chemical Plant

 Part II
4.7 Mole balances on CSTRs, PFRs, PBRs, and Batch
4.8 Microreactors
4.9 Membrane Reactors
4.10 Unsteady-State Operation of Stirred Reactors
4.11 The Practical Side
Fig. 4-1
Isothermal
Reaction
Design
Algorithm
for Conversion
 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)
French Menu Analogy
Algorithm for isothermal reactors
 4.2 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.
 4.2.1 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 5.
 Reaction time in Batch Operation

Algorithm for isothermal reactor design A

→ B
dX
= − rAV0
1. Mole balance
N A0
& 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 
 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 1.5-3.0
2. Heat to reaction temperature, te 0.2-2.0
3. Carry out reaction, tR Varies
4. Empty and clean reactor, tc 0.5-1.0

Total cycle time excluding reaction 3.0-6.0

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 kCA0=103 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.
 Batch Reaction Times
A
→ B
dX −r
Mole balance = AV
dt N A0
First - 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 )
 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
 Batch Reaction Times
Table 4-3
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

10-4 10-3 Hours

10-2 10-1 Minutes

1 10 Seconds

1,000 10,000 Milliseconds

 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
 Example 4-1 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
 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(t) overspecified nor underspecified.
Unknowns:
1. CEO = f(t) 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 4-1 & 4-2)
 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 any time t is virtually
2. RATE LAW −rA = kC A the same as the initial concentration and the rate
law is independent of the concentration of H2O.
(CB~CB0)

3. STOICHIOMETRY

Species symbol Initial Change Remaining Concentration

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

H2O B ΘBNA0 - NA0X NB=NA0(ΘB-X) CB=CA0(ΘB-X)
CB~ CA0 ΘB = CB0

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

NT0 NT =NT0 - NA0X

 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
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
 Example 4-1 Determining k from Batch Data

ln 10 2.3
Rearranging and taking the logarithm k= = = 0.311 min −1
of both side yields t 2 − t1 8.95 − 1.55

C A0 − C C
ln = − kt
C A0 − rA = (0.311 min −1 )C A
We see that a plot ln[(CA0-CC)/CA0] as
1
a function of t will be a straight line with
a slope –k. 0.6

Time C A0 − C C

(CA 0 -CC )/CA 0

(min) C A0
0.0 1.000
0.1
0.5 0.855
1.0 0.730 0.06
1.5 0.624
2.0 0.533
3.0 0.390
4.0 0.285 0.01
6.0 0.152 0 2 4 6 8 10 12

10.0 0.043 1.55 t ( min) 8.95

 Example 4-1 Determining k from Batch Data

−1
− rA = (0.311 min )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).
 4.3 Design of CSTR
Design Equation for a CSTR
FA 0 X
Mole balance V=
(−rA ) exit

FA 0 = v 0 C A 0 v0 C A0 X V C A0 X
V= τ= = the space time
− rA v0 − rA

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

Rate law − rA = kC A

1  X  C A0 X
Combine τ=  =
k  1 − X  kC A

Rearranging

τk CSTR relationship
X = between space time and
1 + τk conversion for a 1st-order
liquid-phase rxn
 4.3.1 A single CSTR
We could also combine Eq (3-29) and (4-8) to find the exit
concentration of A, CA:

 τk  τk
C A = C A0 (1 − X ) = C A0 1 −  X =
1 + τk
 1 + τk 
 1 + τk − τk  C A0
= C A0  =
 1 + τk  1 + τk
C A0
CA =
1 + τk

C A0
exit concentration of A CA =
1 + τk
 Reaction Damköhler number

− rA0V Rate of Reaction at Entrance " a reaction rate"

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

The Damköhler 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 = = = τk
FA 0 v0 C A0

− rA0V kC A2 0V
For 2nd-order irreversible reaction Da = = = τkC 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.
 4.3.2 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 + τ1k1

From a mole balance on reactor 2,

FA1 − FA2 v0 (C A1 − C A2 )
V2 = =
− rA2 k 2 C A2
 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 + τ 2 k 2 (1 + τ 2 k 2 )(1 + τ1k1 )
1 + τ1k1

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

series (τ1 = τ2 = … = τn = τi = (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 = =
(1 + τk )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 + τk ) n
(1 + τk )n
 Conversion as a function of reactors in series
for different Damköhler numbers for a first-order reaction

τk=1

τk=0.5

τk=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
 4.3.3 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
 4.3.3 CSTRs in Parallel
Substituting these values into Eq (4-12) yields
F
FA 0 i = A0
V n
Vi =
FA0 1
n  Xi 
Vi = FA0i  

 − rAi  FA0 i
-rA1, V1

i
V FA 0  X i 
=  
n n  − rAi 
 -rAi, Vi
FA 0 X i FA 0 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!
 4.3.4 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 + 2τkC A0 ) − (1 + 2τkC A0 )2 − (2τkC A0 )2
X =
2τkC A0
V=
FA 0 X FA0 X
= (4-14) (1 + 2τkC A0 ) − 1 + 4τkC A0
=
− rA kC A2 2τkC A0
=
(1 + 2Da ) − 1 + 4Da
For const density v=v0, FA0X=v0(CA0-CA) (4-16)
2Da
V C A0 − C A
τ= =
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
τ=
X
(4-15) X =
(1 + 2Da ) − 1 + 4Da
kC A0 (1 − X )
2
2Da
 A Second-Order Reaction in a CSTR

−rA0V
Da =
FA0

0.88
0.67
At high conversion, a 10-fold
increase in Da will increase the
conversion only to 88% due to
lowest value of reactant
concentration in CSTR.
6 60
 Example 4-2: Producing 200,000,000 lb/yr in a CSTR
~91 ton/yr
CA0=1 vA0=vB0
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 4-1.

(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?
M.W. of EG=62

M.W. of EO=58
 v0 = vA0 + vB0

=1

3m 10’

~2 gps 5’
1.5m

5 gal~19.8L

1 gal ~3.78 L
 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.
PEL (Permissible Exposure Limit)
 4.4 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 τkC A0 Da2
PFR design equation is used. X= =
1 + τkC A0 1 + Da2
X
∫
dX
V = FA0 Da2 is the Damkohler number
0 − rA for a second-order reaction
 4.4 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 + εX ) (1 + εX )
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 + εX ) 2
PFR design equation is used.
V = FA0 ∫ dX
X 0 kC A0 (1 − X )
2 2

∫
dX
V = FA0
0 − rA
 4.3 Tubular Reactors
X (1 + εX ) 2
V = FA0 ∫ 0 kC 2 (1 −
A0 X) 2
dX

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

FA0 X (1 + εX ) 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 + ε ) 2
X
V= 0 2ε(1 + ε) ln(1 − X ) + ε X +
2

kC A0  1 − X 

Reactor length will be

v0  (1 + ε ) 2
X V = Ac L
L= 2ε(1 + ε) ln(1 − X ) + ε X +
2

kC A0 Ac  1 − X 
Cross sectional area
Conversion as a function of distance down the reactor

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

0.8 A  2B (ε=1)
A  3B (ε=2)
0.6

0.4
v0
0.2 = 2.0dm 3
kC A0
0
0 2 4 6 8 10 12 14
L (m)
 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.
Change in Gas-Phase Volumetric Flow Rate Down the Reactor

v  (1 + ε ) 2 X 
v=vo(1+εX) V= 0 2ε (1 + ε ) ln(1 − X ) + ε X +
2

kC A0  1 − X 
ε=1 : (A→2B)
v = vo(1+X)

ε = 0 : (A→B)
v = vo

ε =0.5 : (2A→B)
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.
 Example 4-3: 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.

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
 .2)

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

Ind. Eng. Chem., 59(5), 70 (1967)
C2H6 → C2H4 + H2
 4.5 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)
 Pressure drop and the rate law
기상반응에서는 반응 성분
• for an ideal gas, 의 농도가 반응압력에 비례
Fi FA0 (Θ i + vi X ) 하므로 압력강하에 대한
Ci = = 고려가 필수적이다.
v v0 (1 + εX )( P0 / P )(T / T0 )

• For isothermal operation

Θ +v X  P
C i = C A0  i i  Θi =
Fi 0
ε = y A0δ
 1 + εX  P0 FA0
ν A = −1, ν 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
 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 + εX  P0 T
 Pressure drop and the rate law
• Then, the rate law
2
  1− X  P T0 
− rA′ = k C A0    (4-20)
  1 + εX  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 ) 
FA 0 = k   
+ ε P 
dW  1 X   0 
• Dividing by FA0(=v0CA0)
2
 1 − X   P 
2
dX kC A0
=    
 1 + εX   P0 
dW v0 
 Pressure drop and the rate law

2
 1 − X   P 
2
dX kC A0
=    
dW v0  1 + εX   P0 

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

dX (4-21)
= 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
Flow through a packed bed
 dP
Flow through a packed bed 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 − Φ  150(1 − Φ )µ 
=−  3  + 1.75G  (4-22)
dz ρρg c D p  Φ   Dp 
laminar turbulent

G=ρu=superficial mass velocity [kg/m2s]; u=superficial velocity [m/s]; Dp=diameter of particle

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

• The gas density (ρ) 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.
 Flow through a packed bed

1−φ
 dP
Flow through a packed bed We need
dW

• Equation of continuity
m 0 = m
ρ 0 v0 = ρv

- 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
ρ = ρ0
P  0  T0 v
• Then,

v0 P  T0  FT 0
ρ = ρ0 = ρ0  
v P0  T  FT
 Pressure drop in a packed bed reactor
• then, Ergun equation

dP G (1 − Φ ) 150(1 − Φ )µ  P0 T  FT
=−  + 1.75G   
ρ0 g c D p Φ 3 T F
dz  Dp  P  0  T0

• Simplifying dP P0  T  FT
= −β 0   (4-24)
dz P  T0  FT 0

G (1 − Φ ) 150(1 − Φ )µ 
β0 =  + 1.75G  (4-25)
We need
dP dP dP dz
=
ρ 0 g c D p Φ 
3
Dp 
dW dW dz dW
Ac
• The catalyst weight, W = (1 − Φ ) Ac z × ρ c z
Volume of Density of
solid solid catalyst

dW = ρ c (1 − Φ ) Ac dz (4-26)
 Pressure drop in a packed bed reactor
dz 1
dP β0 P0  T  FT =
dW ρ c (1 − Φ ) Ac
=−   dP dP dz
=
dW Ac (1 − Φ )ρ c P  T0  FT 0 dW dz dW dP P T  F
= −β 0 0   T
dz P  T0  FT 0

dP α T P0  FT 
• Simplifying =−   (4-28)
 
dW 2 T0 P / P0  FT 0 

2β 0
α= (4-29)
Ac ρ c (1 − Φ ) P0

 F  FT FA0
FT = FT 0 + FA0δX = FT 0 1 + A0 δX  = 1 + εX ε = y A0 δ = δ
 FT 0  FT 0 FT 0

dP α T P0
=− (1 + εX ) (4-30)
dW 2 T0 P / P0
 Pressure drop in a packed bed reactor
dP α T P0
=− (1 + εX ) (4-30)
dW 2 T0 P / P0

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

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

• For isothermal operation

dP dX
= f ( X , P) and = f ( X , P) (4-31)
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 ε = 0, we can obtain an analytical solution.
• Polymath will combine the mole balance, rate law and stoichiometry
 Pressure drop in a packed bed reactor
1 0
For the isothermal operation and ε = 0,

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

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

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

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

Rearranging gives us

 P  d ( P / P0 ) d ( P / P0 ) 2
2 
 dW = −α = −α
 P0  dW
Taking P/P0 inside
(4-32) the derivative
Pressure Drop in a Packed Bed Reactor

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

( P / P0 ) 2 = 1 − αW

P
ε=0 = 1 − αW (4-33)
T = T0 P0
 Pressure drop in a packed bed reactor

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

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

P
Pressure ratio = 1 − αW (4-33)
only for ε = 0 P0

2β 0
α=
Ac (1 − Φ )ρ c P0 2β 0 z
αW =
W = (1 − Φ ) Ac z × ρ c P0

G (1 − Φ ) 150(1 − Φ )µ 
β0 =  + 1 . 75G 
ρ 0 g c D p Φ 3  Dp 

Pressure as a P 2β z
function of = 1− 0 (4-34)
P0 P0
reactor length, z
 4.5.3 Pressure Drop in Pipes
Pressure drop for gases along the length of the pipe w/o packing

dP du 2 fG 2 u =G/ρ
P dP 2 dP 2 fG 2
= −G − ρ0 −G + =0
dL dL ρD ρ = ρ0
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 ρ0  D P
Rearranging, we get
P0 4 fG 2
= 1 − α pV αp =
P ρ 0 P0 Ac D

Example 4-4: 1½” schedule 40 x1000-ft L (αp=0.018), ∆P<10%

However, for high volumetric flow rates through microreactors,
the ∆P may be significant. Example 4-4
 4.5.4 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.
 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 − αW )1/ 2 ]
2

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

− rA′ = kC A2
= (1 − αW )dW
FA0 dX
kC A2 0 (1 − X ) 2

Stoichiometry: Gas-phase isothermal with ε=0

at X = 0, W = 0 and FA0 = C A0 v0
P
C A = C A0 (1 − X )
P0 v0  X   αW 
  = W 1 − 
P kC A0  1 − X   2 
= 1 − αW
P0

C A = C A0 (1 − X )(1 − αW )1/ 2 (4-37)

 Reaction with Pressure Drop
Conversion as a function of catalyst weight

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

kC A0W  αW 
1 − 
v0  2 
X = (4-38)
kC W  αW 
1 + A 0 1 − 
v0  2 

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

1 − {1 − [(2v0 α) / kC A0 ][X /(1 − X )]}1/ 2 (4-39)

W =
α
 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
 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+ ½ 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
Example 4-6 Calculating X in a Reactor with Pressure Drop

dX k′  1− X 
=  y
dW FA0  1 + εX 

dy α (1 + εX )
=−
dW 2y
Example 4-6 Calculating X in a Reactor with Pressure Drop
Example 4-6 Calculating X in a Reactor with Pressure Drop
Example 4-6 Calculating X in a Reactor with Pressure Drop
Example 4-6 Calculating X in a Reactor with Pressure Drop
 4.5.5 Spherical Packed-Bed Reactors
Spherical Ultraformer Reactor (Amoco) for dehydrogenation reaction such as

Paraffin aromatic + 3 H2

 Spherical reactor
- minimize pressure drop
- inexpensive
- the most economical shape for high pressure
Coordinate system and variables
used with a spherical reactor
 Spherical reactor
Assume that the fluid moves down through the reactor in plug flow

 then, the increase in cross-sectional area Ac as the fluid enters the

sphere, the superficial velocity G will decrease ( G = m Ac )

 From the Ergun equation

dP G (1 − Φ ) 150(1 − Φ )µ  P0 T  FT
=−  + 1.75G   
ρ0 g c D p Φ 3 T F
dz  Dp  P  0  T0

 by decreasing G, the pressure drop will be reduced significantly,

resulting in higher conversion
 Dehydration Reaction in a Spherical Reactor

paraffin  olefin + H2 Rate law:

rA = −kC A = −k ′C Aρ C (1 − Φ )

FA Stoichiometry: Gas isothermal (T=T0)

z
∆z
z+∆z  1− X  P
C A = C A0  y ε = 1, y=
FA  1 + εX  P0
dy β
− rA′ = k ′C A = − 0 (1 + εX )
dz P0 z
− rA = ρ B (−rA′ ) = ρ C (1 − Φ )(−rA′ )
G (1 − Φ ) 150(1 − Φ )µ 
β0 =  + 1.75G 
= ρ C (1 − Φ )k ′C A ρ 0 g c D p Φ 
3
Dp 
Mole balance: m m
FA z − FA z + ∆z
+ rA Ac ∆z = 0
G= =
[
Ac π R 2 − ( z − L) 2 ]
dX − rA Ac  1 1 
= W = ρ c (1 − Φ )π R 2 z − ( z − L) 3 − L3 
dz FA0  3 3 
 Negligible Pressure Drop in Pipes
Pressure drop along the length of the pipe

dP dµ 2 fG 2 P dP 2 dP 2 fG 2
= −G − ρ0 −G + =0
dL dL ρD P0 dL PdL D
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 ρ0  D P

Rearranging, we get
P0 4 fG 2
= 1 − α pV αp =
P ρ 0 P0 Ac D

Example 4-4: 1½” sch. 40 x1000-ft L (αp=0.018), ∆P<10%

 4.6 Synthesizing a Chemical Plant

 Always challenge the assumptions, constraints, and

boundaries of the problem
 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
 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+ ½ 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
 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 = $0.38/lb (2x108 lb/yr)

Ethane = $0.04/lb (4x106 lb/yr)
Sulfuric acid = $0.043/lb (2.26x108 lb/yr)
Operating cost = $8x106/yr

 Profit = $0.38/lb x 2x108 lb/yr - $0.04/lb x 4x108 lb/yr

-$0.043/lb x 2.26x106 lb/yr - $8x106/yr
= $52 million

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

stream, and operating costs?
Example 4-7 Gas-Phase Reaction in a Microreactor
Fig. 4-1
Isothermal
Reaction
Design
Algorithm
for Conversion
 Homework

P4-5 (a) (b) (c) (d) (e) (f)

P4-6 (a) (b) (c) (d) (e)

Due on April 22
 Part 2
Mole balance written in terms of
CA (liquid) and FA (gas)
 Using CA (liquid) and FA (gas)
in the mole balance and rate laws

 There are many instances when it is much more convenient to

work in terms of the number of moles (NA, NB) or molar flow rates (FA,
FB, etc) rather than conversion.

 Membrane reactors and multiple reactions taking place in the

gas phase are two such cases where molar flow rates are preferred
rather than conversion.

 We now modify our algorithm by using concentration for liquids

and molar flow rates for gases as our dependent variables.

 The main difference between the conversion algorithm and the

molar flow rate/concentration algorithm is that, in the conversion
algorithm, we needed to write a mole balance on only one species,
whereas in the molar flow rate and concentration algorithm, we must
write a mole balance on each and every species.
 Fig. 4-11 Isothermal reaction design algorithm for mole balances

A + 2B  C Stoichiometry

(4) (a) Write the concentrations in terms of molar flow rates

Mole for isothermal gas-phase reaction
balance (1) Write mole balance on each species
FA P F P
각 성분에 대해서… dFA dFB dF C A = CT 0 C B = CT 0 B
= rA ; = rB ; C = rC FT P0 FT P0
dV dV dV with FT = FA + FB + FC
(b) For liquid-phase reaction use concentration, CA, CB

Rate law (2) Write rate law in terms of concentration ∆P

 C 
− rA = k A  C AC B2 − C  (5) Write the gas-phase pressure drop
in terms of molar flow rate
 KC 
dy α FT P
=− with y=
dW 2 y FT 0 P0
Stoichiometry

(3) Relate the rates of rxn of each species to one another

combine

rB = 2rA , rC = −rA
(6) Use an ODE solver or a nonlinear equation solver
to combine Steps (1) through (5) to solve for,
for example, the profiles of molar flow rates,
concentration and pressure.
 4.7.1 Liquid phase
b c d
A+ B → C+ D
a a a
 For constant-volume liquid-phase reaction  concentration is preferred variable
 We have only to specify the parameter values for the system (CA0, v0, etc.)
and for the rate law (kA, α, β) to solve the coupled ordinary differential equations
for either PFR, PBR, or batch reactors or to solve the coupled algebraic
equations for a CSTR.

Table 4-5. Mole balance for liquid-phase reactions

4.7 Mole balances on CSTRs, PFRs, PBRs, and Batch Reactors
Gas-phase rxn Liquid-phase rxn
Moles or molar flow rates concentration

dN A dC A
Batch = rAV = rA
dt dt
FA0 − FA v0 (C A0 − C A )
CSTR V= V=
− rA − rA

dFA dC A
PFR − = − rA v0 = rA
dV dV

dFA dC A
PBR = rA' v0 = rA'
dW dW
 4.7.2 Gas phase
 For gas phase reactions
 need to be expressed in terms of the molar flow rates
dF j
Mole balance
= rj
dV
Rate law − rA = k AC Aα C Bβ y
 Fj  P  T0 
Stoichiometry
C j = CT 0    
 P  T
 FT  0  

dy α FT
 Pressure drop : =− (4-28)
dW 2 y FT 0
n
 Total molar flow rate: FT = ∑F j =1
j = FA + FB + FC + FD + FI

We now combine all the preceding information as shown in Table 4-6.

 Table 4.6 Algorithm for Gas phase reaction

aA + bB 
→ cC + dD
1. Mole balances:
Batch CSTR PFR

dN A F − FA dFA
= rAV V = A0 = rA
dt − rA dV
dN B F − FB dFB
= rBV V = B0 = rB
dt − rB dV
dN C
= rCV F − FC dFC
= rC
V = C0
dt − rC dV
dN D F − FD dFD
= rDV V = D0 = rD
dt − rD dV
 Algorithm for Gas phase reaction

2. Rate law: − rA = k AC αA C Bβ

3. Stoichiometry:
rA r r r
Relative rate of reaction: = B = C = D
−a −b c d
b c d
rB = rA rC = − rA rD = − rA y
a a a
FA P T0 FB P T0
Concentration: C A = CT 0 C B = CT 0
FT P0 T FT P0 T
FC P T0 FD P T0
CC = CT 0 C D = CT 0
FT P0 T FT P0 T
Total molar flow rate: FT = FA + FB + FC + FD
dy − α FA T P
= , y=
dW 2 y FT 0 T0 P0
 Algorithm for Gas phase reaction

4. Combine: For an isothermal operation of a PFR with no ∆P

α β α β
dFA α + β  FA   FB  dFB b α + β  FA   FB 
= − k ACT 0     = − k ACT 0    
dV  FT   FT  dV a  FT   FT 
α β α β
dFC c α + β  FA   FB  dFD d α + β  FA   FB 
= k ACT 0     = k ACT 0    
dV a  FT   FT  dV a  FT   FT 
 Specify the parameter values: kA, CT0, α, β, T0, a, b, c, d
 Specify the entering number: FA0, FB0, FC0, FD0, and final value: Vfinal

5. use an ODE solver:

 4.8 Microreactors

 Microreactors are emerging as a new technology in CRE.

 Microreactors are characterized by high surface area-to

volume ratio. A typical channel width might be 100 µm with a
length of 20,000 µm. The resulting high surface area-to-
volume ratio (ca. 10,000 m2/m3) reduces or even eliminates
heat and mass transfer resistances often found in larger reactor.

 Consequently, surface catalyzed reactions can be greatly

facilitated, hot spots in highly exothermic reactions can be
carried out isothermally.
 4.8 Microreactors

 These features provide the opportunity for microreactors to

be used to study the intrinsic kinetics of reaction.

 Another advantage of microreactor is their use in the

production of toxic or explosive intermediates where a leak or
microexplosion for a single unit will do minimal damage
because of the small quantities of material involved.

 Other advantages include shorter residence times and

narrower residence time distribution.

 Microreactors are also used for the production of special

chemicals, combinatorial chemical screening, lab-on-a-chip,
and chemical sensors.
 Microreactor and Lab-on-Chip

Microreactor made of silicon Lab-on-Chip made of glass and polymer

anodically bonded with glass for DNA amplification and detection

Rutherford Appleton Laboratory (RAL) in the UK

 Microreactor for DNA analysis
10 nano g / µ

± 0.1°C

50 nano liter

(50h X 500 w µm)

 Microreactor and Microplant

Microreactor with heat exchanger Microplant with reactor, valves, mixers

Ehrfeld, Hessel, and Lowe,

Microreactors: New Technology for Modern Chemistry (Wiley-VCH, 2000)
 4.8 Microreactors

 Production in microreactor systems can be increased

simply by adding more units in parallel. For example, the
catalyzed reaction

R-CH2OH + ½O2 Ag
R-CHO + H2O

Required only 32 microreaction systems in parallel to

produce 2000 tons/yr of acetate!

2g/s per a microreaction system

 Example 4-7: Gas-Phase Reaction in a Microreactor

The gas phase reaction

2NOCl → 2NO + Cl2

− rA = kC A2

is carried out at 425oC and 1641 kPa (16.2 atm). Pure NOCl is to be fed,
and the reaction follows an elementary rate law. It is desired to produce 20
tons of NO per year in a microreactor system using a bank of ten
microreactors in parallel. Each microreactor has 100 channels with each
channel 0.2 mm square and 250 mm in length.

Plot the molar flow rates as a function of volume down the length of the
reactor. The volume of each channel is 10-5 dm3.

Rate constant and activation energy (given): k = 0.29 dm3/mol-sec at 500K

with E = 24 kcal/mol. To produce 20 tons/year of NO at 85% conversion
would require a feed rate of 0.0226 mol/s of NOCl or 2.26x10-5 mol/s per
channel.
Solution For one channel

FAo = 22.6 µmol/s FB = 19.2 µmol/s, X=0.85, V=?

= 22.6 x 0.85

2NOCl → 2NO + Cl2

2A → 2B + C
A → B + ½C
Although this particular problem could be solved using conversion, we shall illustrate
how it can also be solved using molar flow rates as the variable in the mole balance.

1. Mole balances on species A, B, and C: 2. Rate law:

dFA
= rA − rA = kC A2
dV
dFB
= rB dm 3
dV k = 0.29 @500K, E=24 kcal/mol
dFC mol ⋅ s
= rC
dV J.B. Butt, Reaction Kinetics and Reactor Design,
2nd ed. New York, Marcel Dekker, 2001, p153
 FT T  FT
3. Stoichiometry: Gas phase with T=To and P=Po, then v = v0
P0
v = v0  
T F
FT 0 P  0  T0

3-1. Relative rate A → B + ½C

rA rB rC
= = rC = − 1 2 rA
−1 1 1
2
rB = − rA

3-2. Concentration: by applying Equation (3-42)

FA FB FC
C A = CT 0 , C B = CT 0 , CC = CT 0
FT FT FT
with FT = FA + FB + FC FA P T0 FB P T0
C A = CT 0 C B = CT 0
FT P0 T FT P0 T
FC P T0 FD P T0
CC = CT 0 C D = CT 0
FT P0 T FT P0 T
Equation (3-42)
4. Combine 5. Evaluate

P0
2 CT 0 =
F  RT0
− rA = k ACT20  A 
 FT 
=
(1641kPa )
 kPa ⋅ dm 3 
 8.314 (698 K )
2
 mol ⋅ K 
dFA 2  FA 
= − k ACT 0  
dV  FT 
mol
= 0.286
2 dm 3
dFB 2  FA 
= k ACT 0   Use Polymath to solve three ODEs
dV  FT 
2
dFC 1 F  When using Polymath or another ODE solver,
= 2 k ACT20  A  one does not have to actually combine
dV  FT  the mole balances, rate laws, and stoichiometry
as was done in the combine step in previous examples
in this chapter. The ODE solver will do that for you.

Thanks, ODE solver!

Profiles of microreactor molar flow rates

25

Flow rates in micro-mol/s

20
Flow rates [µmol/s]

FA FB
15

10 FC

0
0 2.0e-6 4.0e-6 6.0e-6 8.0e-6 1.0e-5
V [dm3]
 4.9 Membrane reactors

 Membrane reactors can be used to increase conversion

when the reaction is thermodynamically limited as well as to
increase the selectivity when multiple reactions are occurring.
 Thermodynamically limited reactions are reactions where
the equilibrium lie far to the left (i.e., reaction side) and there is
little conversion.
 If the reaction is exothermic, increasing the temperature will
only drive the reaction further to the left, and decreasing the
temperature will result in a reaction rate so slow that there is
very little conversion.
 If the reaction is endothermic, increasing the temperature
will move the reaction to the right to favor a higher conversion;
however, for many reactions these higher temperatures cause
the catalyst to become deactivated.
 4.9 Membrane reactors

 The term membrane reactor describe a number of different

types of reactor configurations that contain a membrane. The
membrane can either provide a barrier to certain components
while being permeable to others.
 Like reactive distillation, the membrane reactor is another
technique for driving reversible reactions to the right toward
completion in order to achieve very high conversion.
 These high conversion can achieve by having one of the
reaction products diffuse out of a semipermeable membrane
surrounding the reacting mixture.
 As a result, the reversible reaction will not be able to take
place, and the reaction will continue to proceed to the right
toward completion.
 What kinds of membrane reactors are available?

Membrane reactors are most commonly used when a reaction involves

some form of catalyst, and there are two main types of these membrane
reactors: the inert membrance reactor and the catalytic membrane reactor.
 The inert membrane reactor allows catalyst pellets to flow with the
reactants on the feed side (usually the inside of the membrane). It is
known as an IMRCF, which stands for Inert Membrane Reactor with
Catalyst on the Feed side. In this kind of membrane reactor, the
membrane does not participate in the reaction directly; it simply acts as a
barrier to the reactants and some products.
 A catalytic membrane reactor (CMR) has a membrane that has either
been coated with or is made of a material that contains catalyst, which
means that the membrane itself participates in the reaction. Some of the
reaction products (those that are small enough) pass through the
membrane and exit the reactor on the permeate side.
 Membrane reactors

 Inert membrane reactor with catalyst pellets on the feed side (IMRCF)

C6H12  3H2 + C6H6

A  3B + C

H2 molecule is small enough to diffuse through the small pore of the

membrane while C6H12 and C6H6 cannot.
 Membrane reactors

 Catalytic membrane reactor (CMR)

C6H12  3H2 + C6H6

A  3B + C

Membrane reactors are commonly used in dehydrogenation reactions,

where only one of the products (molecular hydrogen) is small enough to
pass through the membrane. This raises the conversion for the reaction,
making the process more economical.
 H2 diffuses through the membrane
while C6H6 does not
Inert sweep
Gas
H2 (B)
C6H12 (A)

C6H6 (C)
Inert sweep
Gas
Sweep Gas

membrane
Reactants

C6H12
H2
 Analyzing membrane reactors

 We shall choose the reactor volume rather than catalyst weight as our
independent variable for this example. The catalyst weight, W, and reactor
volume, V, are easily related through the bulk catalyst density, ρb (i.e.
W=ρbV).
 The mole balances on the chemical species that stay within the reactor,
namely A and C, are shown in Fig. 4-11 and also in Table 4-6.

dFA
= rA (1-11)
dV
 The mole balances on C is carried out in an identical manner to A,
dFC
= rC (4-40)
dV
 Analyzing membrane reactors

 However, the mole balance on B (H2) must be modified because

hydrogen leaves through both the side of the reactor and end of the reactor.
 First, we shall perform mole balances on the volume ∆V shown in Fig. 4-
12(d). The mole balances on hydrogen (B) is over a differential volume ∆V
shown in Fig. 4-12(d) and it yields

RB
∆V
membrane

FA FA
FB FB
FC FC
membrane

V V+∆V
Fig. 4-12(d) RB
 Analyzing membrane reactors
RB RB: Molar rate of B leaving through the sides the
reactor per unit volume of reactor (mol/dm3·s)
membrane

FA FA
FB FB
FC membrane FC
V V+∆V
RB
Balance on B in the catalytic bed:
In Out Out
by flow – by flow – by diffusion + Generation = Accumulation

FB − FB − RB ∆V + rB ∆V = 0
V V + ∆V

Dividing by ∆V and taking the limit as ∆V → 0 gives

dFB
= rB − RB (4-41)
dV
 Analyzing membrane reactors

CBS

B CB

RB = WB a = kC′ a (C B − C BS ) RB = kC C B

WB = kC′ (C B − C BS ) (4-41) kC = kC′ a and C BS ≈ 0

Area πDL 4
a= = =
Volume πD 2
D
L
4
RB = Molar rate of B leaving through the sides the reactor per unit volume of reactor (mol/m3·s)
WB =The molar flux of B (mol/m2·s)
k’C= the overall mass transfer coefficient (m/s)
a = the surface area per unit volume of reactor (m-1)
kc = a transport coefficient (s-1)
 Example 4-8 Membrane reactor for Dehydrogenation reactions

 According to The DOE, an energy saving of 10 trillion Btu/yr could result

from the use of catalytic membrane reactors as replacements for
conventional reactors for dehydrogenation reactions:
such as the.

A  B +C

CH2CH3 CH=CH

Dehydrogenation of
ethylbenzene to styrene + H2

Dehydrogenation of
butane to butylene C4H10  C4H8 + H2
Dehydrogenation of
propane to propylene C3H8  C3H6 + H2
The basic algorithm for solving reaction in the membrane reactor

RB=kcCB ∆V A  B +C
Equilibrium constant
FA
P=8.2 atm KC=0.05 mol @227oC
FA A  B +C FB
T=227oC
F FC
FA0=10mol/min B
membrane

RB=kcCB V+∆V There are

two “OUT”
1. Mole balance: A, B & C terms

for a differential mole balance on A for a differential mole balance on B

in the catalytic bed at steady state in the catalytic bed at steady state

FA V − FA V + ∆V + rA ∆V = 0 FB V
− FB V + ∆V
− RB ∆V + rB ∆V = 0
dFA dFB
= rA = rB − RB
dV dV

for a differential mole balance on C dFC

in the catalytic bed at steady state
= rC
dV
The basic algorithm for solving reaction in the membrane reactor

2. Rate law:
 C C 
− rA = k  C A − B C ;
 rB = − rA ; rC = − rA
 KC 
3. Transport out the sides of the reactor: CBS~0

RB = k C C B

kc is a transport coefficient. kc=f(membrane & fluid properties, tube diameter…)  constant

4. Stoichiometry: P & T = const

FA F F
C A = CT 0 ; C B = CT 0 B ; CC = CT 0 C
FT FT FT
FT = FA + FB + FC FA P T0 FB P T0
C A = CT 0 C B = CT 0
− rA = rB = rC FT P0 T FT P0 T
FC P T0 FD P T0
CC = CT 0 C D = CT 0
FT P0 T FT P0 T
The basic algorithm for solving reaction in the membrane reactor

5. Combining and Summarizing:

dFA dFB  FB  dFC

= rA ; = − rA − k c CT 0  ; = − rA
dV dV  FT  dV

 FA  CT 0  FB  FC 
− rA = k c CT 0   −   
 FT  KC  FT  FT 
FT = FA + FB + FC

6. Parameter evaluation:
CT0=0.2 mol/L, k=0.7 min-1, KC=0.05 mol/L, kc=0.2 min-1
FA0=10 mol/min, FB0=FC0=0

7. Numerical solution:
Solve with POLYMATH or MATLAB
 The basic algorithm for solving reaction in the membrane reactor

POLMATH solution: kc=0.20 min-1 A  B +C

FA0 10
=10 mol/min

FC
FA
FB 5 FA
FC FA
=4 mol/min
FB

0
0 100 200 300 400 500

Reactor volume, V [L] FA0 − FA 10 − 4

X = = = 0.6
FA0 10
The basic algorithm for solving reaction in the membrane reactor

POLMATH solution: kc=0.0022 min-1 A  B +C

10

FA FA
FB 5
FC FB FC

0
0 100 200 300 400 500

Reactor volume, V [L]

The basic algorithm for solving reaction in the membrane reactor

A  B +C
POLMATH solution: kc=20 min-1
10

FC
FA
FB 5
FC

FB FA
0
0 100 200 300 400 500

Reactor volume, V [L]

 Effects of side stream, RB=kcCB
in a membrane reactor

10 A  B +C
kc=0.20 min-1 FC
FA
FB FA
5

FC FB

0
0 100 200 300 400 500
Reactor volume, V [L]

Large side stream Little side stream

10 10
kc=0.0022 min-1
FC kc=20 min-1
FA FA
FB 5
FA
5
FC FB
FA FB FC
FB FC
0
0 100 200 300 400 500 0
0 100 200 300 400 500
Reactor volume, V [L]
Reactor volume, V [L]
 Effects of changing the inlet flowrate, FA0
in a membrane reactor

FAO=25
FAO=25
FAO=15
FAO=15
FAO=5
FAO=5

FAO=25 FAO=5
FAO=15

FAO=15 FAO=25

FAO=5

As expected, our flow rates increase as FA0 increases. Interestingly though, conversion actually decreases
as FA0 increases. Why? Even though more of reactant A enters the reactor as the flow rate increases, it
spends less time in the reactor, which causes the decrease in conversion.
 Use of membrane reactors to enhance selectivity
 In addition to species leaving the membrane reactor, species can also be
fed to the reactor through the membrane. For example, for the reaction

A + B →C + D

A could be fed only to the entrance, and B could be fed only through the
membrane as shown here.
FB0

FA0 Vt

As we will see in Chapter 6, this arrangement is often used to improve

selectivity when multiple reactions take place.

FB V − FB V + ∆V + RB ∆V + rB ∆V = 0
dFB
= rB + RB (4-44)
dV
RB = FB 0 / Vt
 4.10 Unsteady-State Operation of Stirred Reactors

 Startup of a CSTR : Determine the time to reach steady-state operation

 Semibatch reactor : Predict the concentration and conversion as a function of time

A + B →C + D
M B

CA0 C
A, B
CA A

Startup of a CSTR Semibatch reactor Reactive distillation

-Ammonolysis -Acetylation
-Chlorination -Esterification
-Hydrolysis
 4.10.1 Startup of a CSTR
Time to Reach Steady State for a First-Order Reaction in a CSTR

To determine the time to reach steady-state operation of a CSTR, we begin with the general
mole balance equation applied to a well-mixed CSTR.

dN A
FA0 − FA + rAV = (4-45)
dt

Utilizing the definitions of FA and NA, we have

d (C AV )
C A0 v0 − C A v + rAV =
dt
Conversion does not have any meaning in startup because one cannot separate moles
reacted from moles accumulated. Consequently, we must use concentration rather than
conversion as the variable in our balance equation. For liquid-phase reactions V =V0
and for a constant overflow, v =v0. After dividing by v0 and replacing V/v0 by the space
time τ, we find that
dC A
C A0 − C A + rA τ = τ (4-46)
dt
 4.7.1 Startup of a CSTR
For a first-order reaction: − rA = kC A C A0 − C A + rAτ = τ
dC A
dt
dC A C A − τrA C A0
dC A 1 + τk C A0 + =
+ CA = dt τ τ
dt τ τ
− rA = kC A
C A0   t 
Solution CA = 1 − exp  − (1 + τk )  (4-47)
1 + τk   τ 

Letting ts be the time necessary to reach 99% of the steady state concentration, CAS:
C A0
C AS =
1 + τk

Rearranging (4-47) for CA=0.99CAS yields 0.99 = 1 − exp(−4.6)

τ
t S = 4.6 (4-48)
1 + τk
 4.7.1 Startup of a CSTR

Time to reach steady state in an isothermal CSTR

For most first-order
system, steady

τ
state is achieved in
t S = 4.6 (4-48)
three to four space
1 + τk times

For slow reactions with small k (1>>τk): t S = 4.6τ (4-49)

4.6
For rapid reactions with large k (τk >>1): tS = (4-50)
k
 4.10.2 Motivation of Semibatch Reactors

One of the best reasons to use semibatch reactors is to

enhance selectivity in liquid-phase reactions. For example,
consider two simultaneous reactions.

On reaction produces the desired product D and the other

produces an undesired product U. We want SDU as large
as possible.

rD = k D C C B
kD 2
A+B D A

A+B
kU
U rU = kU C AC 2
B

rD k D C A
S D /U = =
rU kU C B
 Maximizing SD/U for
Rate selectivity two reactants
parameter, S

k1 D (Desired Product)
A+B
k2 U (Undesired Product)

The rate laws are

− rA = k D C A2 C B + kU C AC B2
rD = k D C A2 C B
rU = kU C AC B2

rD k D C A
S D /U = =
rU kU C B

Rate selectivity parameter=Instantaneous selectivity

Different reactors and schemes for minimizing the unwanted product

A B A
B
A
B A
B A B

(a) CSTR (b) tubular reactor (c ) batch (d) semibatch 1 (e) semibatch 2

A A
B B

(f) Tubular reactor with side streams (g) Tubular reactor with side streams

B
A A
B

(h) Tubular reactor with recycle (i) Series of small CSTRs

 4.10.3 Semibatch Reactors : Constant volumetric flow, vo

CB 0 A+ B 
→ C Semibatch
reactor V = V0 + υ 0 t (4-55)
υ0 υ0 volume as a
function of time
B B VdC A
− v0 C A + VrA =
dt
dC A v
A A = rA − 0 C A (4-56)
dt V
Mole balance on A:
Mole balance on B:
[ in ] - [ out ] + [ gen. ] = [ acc. ]
[ in ] - [ out ] + [ gen. ] = [ acc. ]
dN A
0 − 0 + rAV (t ) = (4-51) dN B
dt FB 0 − 0 + rBV (t ) =
dt
d (C AV ) VdC A C A dV
rAV = = + (4-52) dN B
dt dt dt = rBV + FB 0 (4-57)
dt
Overall mass balance of all species: dN B d (VC B ) dV dC B
= = CB +V
[ in ] - [ out ] + [ gen. ] = [ acc. ] dt dt dt dt
d (ρV ) rBV + FB 0 = rBV + v0 C B 0
ρ 0 v0 − 0 + 0 = (4-53)
dt
dV dC B v (C − C B )
= v0 for ρ = ρ 0 (4-54) = rB + 0 B 0 (4-58)
dt dt V
Example 4-9 Isothermal semibatch reactor with 2nd–order reaction

Concentration of CNBr (A) and CH3Br (C) with time

CNBr + CH3NH2  CH3Br + NCNH2 dN C
A + B  C + D = rCV = − rAV
Bromine cyanide Methyl amine Methyl bromide dt
Irreversible liquid phase Isothermal dN C d (CCV ) dCC dV
elementary reaction = =V + CC
in a semibatch reactor dt dt dt dt
t=0, CA0=0.05 gmol/ℓ, CB0=0.025 gmol/ℓ, dCC
v0=0.05ℓ/s, k=2.2ℓ/s·mol, V0=5ℓ =V + v0 CC
dt
Mole balance of A, B, C, and D
dCC v0
− rA = kC AC B C = kC AC B − CC
dt V
dC A v0 dC D v
A = − kC AC B − C A D = kC AC B − 0 C D
dt V dt V
dC B v0
B = − kC AC B + (C B 0 − C B ) Conversion, X
dt V
N A0 − N A C A0V0 − C AV
V = V0 + v0 t X = =
N A0 C A0V0
 Concentration-time trajectories
in Semibatch Reactor

0.05
CNBr + CH3NH2  CH3Br + NCNH2
(A) (B) (C) (D)
0.04
t=0, CA0=0.05 gmol/,
Feeding B: CB0=0.025 gmol/ℓ, v0=0.05ℓ/s,
k=2.2ℓ/s·mol, V0=5ℓ
Concentration

0.03

CA
0.02
CC =CD
0.01

CB
0.00
0 100 200 300 400 500

Time
 Reaction rate-time trajectories
in Semibatch Reactor

0.0025
CNBr + CH3NH2  CH3Br + NCNH2
(A) (B) (C) (D)
0.0020
Reaction rate [mole/s•L)

t=0, CA=0.05 gmol/, CB=0.025 gmol/ℓ,

v0=0.05ℓ/s, k=2.2ℓ/s·mol, V0=5ℓ

0.0015

0.00010

0.00005

0.00
0 50 100 150 200 250
 Reactor equations in terms of number of moles
in semibatch reactor

Mole balance of A and B Concentration of A and B in batch reactor

dN A NA
= rAV (t ) CA =
dt V
dN B NB
= rAV (t ) + RB 0 CB =
dt V
V = V0 + v0 t Rate law − rA = k AC AC B

Combine

dN A N N
Equations in = −k A B N A = f (k , V0 , v0 , FB 0 )
terms of only dt V0 + v0 t
number of
dN B N N
moles !! = − k A B + FB 0
dt V0 + v0 t
 4.10.4 Reactor equations in terms of conversion
in semibatch reactor

A+ B ↔ C+D υ0 υ0
The number of moles of A remaining at any time , t B B
number of moles  number of moles  number of moles 
 of A in the vat  =  of A in the vat  −  of A reacted up 
     
 at time t   initially   to time t  A A

NA = N A0 − N A0 X (4-59)

where X is the mole of A reacted per mole of A

initially in the vat.

The number of moles of B remaining at any time , t

number of moles  number of moles  number of moles  number of moles 
 of B in the vat  =  of B in the vat  +  of B added to  −  of B reacted up 
       
 at time t   initially   the vat   to time t 

t
NB = N Bi + ∫F
0
B 0 dt − N A0 X (4-60)

For a constant molar feed rate 0

N B = N Bi + FB 0 t − N A0 X (4-61)
 4.10.4 Reactor equations in terms of conversion
in semibatch reactor

B
υ0 υ0
B
A+ B ↔ C+D
The concentration of A, B, C, and D
N A N A0 (1 − X )
A A
CA = =
V V0 + v0t
A mole balance on specials A:
N B N Bi + FB 0t − N A0 X
dN A dX CB = =
rAV = = − N A0 (4-62) V V0 + v0t
dt dt (4-65)
NC N X
CC = = A0
The number of moles of C and D can be taken
directly from the stoichiometric table
V V0 + v0t
ND N X
N C = N Ci + N A0 X (4-63) CD = = A0
V V0 + v0t
N D = N Di + N A0 X
Combine (4-66)
The rate law (reversible 2nd-order reaction)
dX
=
[ (
k (1 − X )(N Bi + FB 0 t − N A0 X ) − N A0 X 2 / K C )]
V0 + v0 t
 
dt
C C
− rA = k  C AC B − C D 

(4-64)
 KC  (4-66) can be solved numerically
 Equilibrium conversion
in semibatch reactor
υ0 υ0
CCe C De ( N Ce / V )( N De / V )
B B KC = =
C Ae C Be ( N Ae / V )( N Be / V )
A A
N Ce N De
For reversible reactions carried out in a KC =
semibatch reactor, the maximum attainable N Ae N Be
conversion (i.e., the equilibrium conversion) will
change as the reaction proceeds because more ( N A0 X e )( N A0 X e )
=
reactant is continually to the right. N A0 (1 − X e )( FB 0 t − N A0 X e )
A+ B C+D
N A0 X e2
The rate law (reversible 2nd-order reaction) =
(1 − X e )( FB 0t − N A0 X e ) (4-68)
 C C 
− rA = k  C AC B − C D 

 KC  (4-67) N A0  X 2 
t=  KC X e + e  (4-69)
K C FB 0  1− X e 
 

2
Equilibrium  FB 0 t    FB 0 t  F t
conversion in a K C 1 +  −  K C 1 +  − 4( K C − 1) K C B 0
N A0   N A0  (4-70)
semibatch reactor   N A0
Xe =
2( K C − 1)
 Reactive Distillation

 The distillation of chemically reacting mixtures has become

increasingly common in chemical industries.

 Carrying out these two operations, reaction and distillation,

simultaneously in a single unit results in significantly lower capital cost
and operating costs.

 Reactive distillation is particularly attractive when one of the reaction

products has a lower boiling point, resulting in its volatilization from the
reacting liquid mixture.
 Reactive Distillation
 An example of reactive distillation is the production of methyl
acetate:

 By continually removing the volatile reaction product, methyl

acetate, from the reacting liquid-phase reaction, the reverse reaction is
negligible and the reaction continues to proceed towards completion in
the forward direction.

 Reactive distillation is used with reversible, liquid phase reactions.

Suppose a reversible reaction had the following chemical equation :
 Reactive Distillation
 For many reversible reactions the equilibrium point lies far to the
left and little product is formed :

 However, if one or more of the products are removed more of the

product will be formed because of Le Chatlier's Principle :

 Removing one or more of the products is one of the principles

behind reactive distillation. The reaction mixture is heated and the
product(s) are boiled off. However, caution must be taken that the
reactants won't boil off before the products.
 Unsteady-State Operation of Reactors

For example, Reactive Distillation can be used in removing acetic acid

from water. Acetic acid is the byproduct of several reactions and is very
useful in its own right. Derivatives of acetic acid are used in foods,
pharmaceuticals, explosives, medicinal and solvents. It is also found in
many homes in the form of vinegar. However, it is considered a pollutant
in waste water from a reaction and must be removed.
 Reactive Distillation
Rate Law
To illustrate the effects of reactive distillation lets take the equation :

Taking the reaction to be elementary, the rate law is :

In reactive distillation, one of the products is continually removed causing the

concentration of the removed product to become very small. As a result the reverse
reaction decreases and more product is formed.
 Reactive Distillation
Let’s consider the element reaction in which A and B are charged in equal molar
amounts and species D is continuously boiled off.

A+ B C+D
Balance on species A
dN A
0 − 0 + rAV (t ) = (4-71)
dt

Define conversion as the number of moles of A reacted per mole of A charged

 b 
N A = N A0 (1 − X ); N B = N A0  Θ B − X  = N A0 (1 − X )
 a 

Then, dX (4-74)
N A0 = − rAV (t )
dt
 Reactive Distillation
Balance on species D, which evaporates at a rate FD

dN D
0 − FD + rDV (t ) = (4-75)
dt
Integrating,

number of moles number of moles of D number of moles of D

 = − 
of remaining D  formed by reaction  lost by vaporization 
t
N D = N A0 X − ∫F
0
D dt (4-76)

For elementary reaction,

 C C 
− rA = k  C AC B − C D 

 KC 
 Reactive Distillation
N A0 (1 − X )
CA =
V
NB N A0 (1 − X )
CB = =
V V
NC N A0 X
CC = =
V V
t

CD =
ND
=
N A0 X − ∫F
0
D dt

V V
  t 
∫
X 1
kN A2 0 (1 − X) −
2
 X − FD dt 
 KC  N A0 0 
− rAV = (4-77)
V
 Reactive Distillation
Overall mass balance on all species
d (ρV )
0 − FD ( MWD ) + 0 = (4-78)
dt
where MWD is the molecular weight of D

Constant-density system
dV FD ( MWD )
=− = −αFD (4-79)
dt ρ
 Reactive Distillation
dX
N A0 = − rAV (t ) (4-74)
dt
t
N D = N A0 X − ∫F0
D dt (4-76)

Four
simultaneous   t 
∫
X 1
equations kN A2 0 (1 − X) − 2
 X − FD dt 
 KC  N A0 0 
− rAV = (4-77)
V

dV FD ( MWD )
=− = −αFD (4-79)
dt ρ
Specify the rate of evaporation of D (FD) and solved numerically and simultaneously

 (1) Immediate evaporation

 (2) Inert gas is bubbled through the reactor
 Immediate Evaporation
No accumulation of D
in the liquid phase
V = V0 (1 + ε L X ) (4-83)

dV ( MW ) D C A0
= −αFD (4-79) ε L = − αC A0 =− [ −]
dt ρ
FD = rDV = −rAV (4-80) Combining eq(4-77) with CD=0

dX dX  (1 − X ) 2 
FD = N A0 (4-81) = kC A0  
dt dt  1 + ε L X 
dV Time to achieve a conversion X
(81)  (79) = −αN A0 (4-82)
dX 1  (1 + ε L ) X 1 
t= − ε ln
kC A0  1 − X 1 − X 
L
integration V = V0 − αN A0 X
dX
N A0 = − rAV (t ) 2nd-order reactive distillation
dt
 Inert gas is bubbled through the reactor
The reaction product is carried off by
(1) boil off
(2) inert gas being bubbled through the reactor
Vapor pressure of D
Raoult’s law
PvD ND PvD
y D ( g ) = x D (l ) =
P0 N A + N B + N C + N D P0

Set either the boil off rate by setting the heat flux to the reactor or set the molar
flow rate at which an inert is bubbled through the reactor, FI . The molar flow rate
of D in the gas phase;
FD = y D FT

Assuming only D evaporates, the total molar gas flow rate is the inert gas
molar flow rate plus the molar flow rate of evaporaing species.

FT = FI + FD = FI + y D FT
FI
FT =
1 − yD
 Inert gas is bubbled through the reactor

The molar flow rate of D leaving the liquid is

 yD 
FD =   FI (4-83)
 1 − yD 

This equation is now coupled with all the mole balances, e.g.,

dN A − k(N A N B − N C N D )
=
dt V

dN D k(N A N B − N C N D )
= − FD
dt V
Inert gas is bubbled through the reactor
 Recycle reactor

 autocatalytic reactions
 biochemical operations
 to maintain nearly isothermal operation of the reactor
 to promote a certain selectivity
 Recycle reactor

P Q
FA0 FA1’ Xs FA2 X0
3
FB0 FB1’ FB2 FA3
v0 V01’ etc. FB3
FC3
etc.
R FD3
Vr, FAR , FBR , FCR , etc.
Ft3

Define the recycle parameter R as the moles recycled per mole

of product removed at point Q

FtR FAR FiR

R= = =
Ft 3 F A3 Fi 3
 Recycle reactor

 the conversion per pass Xs

moles of A reacted in a single pass
XS =
mole of A fed to the reactor

XO
XS =
 the overall conversion Xo 1 + R (1 − X O )

moles of A reacted overall

XO =
mole of fresh feed
 Example of the CRE Algorithm

 Consider

 Applying the algorithm to the above reaction occurring

in a Batch, CSTR, and PFR.

 Example of the CRE Algorithm

 Consider

 Applying the algorithm to the above reaction occurring

in a Batch, CSTR, and PFR.

Example of the CRE Algorithm
Example of the CRE Algorithm
 4.11 The Practical Side

A practical guidelines for the operation of chemical reactors have been

presented over the years, and tables and some of these descriptions are
summarized and presented on the CD-ROM and web. The articles are
listed in Table 4-7.

For example, Mukesh gives relationships between the CSTR tank diameter,
T, impeller size diameter, D, tank height, H, and the liquid level, l. To scale
up a pilot plant (1) to a full scale plant (2), the following guidelines are given
D2 T2  2 H 2
= = = =R
D1 T1  1 H1
And the rotational speed, N2, is

N 2 = N1 R − n
Where values of n for different pumping capacities and Froude numbers are
given in Mukesh’s article.
 Closure

After completing this chapter, you should be

able to apply the algorithm building blocks

Evaluation

Combine

Stoichiometry

Rate Law

Mole Balance

To batch reactor, CSTR, PFR, PBR,

membrane reactor, and semibatch reactor.
 Closure
After completing this chapter, you should be able to account for pressure drop
and describe the effect of system variables such as particle size on the
conversion and explain why there is an optimum in the conversion when
catalyst particle size is varies.

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) Smaller heat transfer area
 Homework

P4-7 (a) (b) (c) (d) (e) (f) (g)

P4-25 (a) (b) (c) (d)