Isothermal Reactor Design
Isothermal Reactor Design
Isothermal Reactor Design
반응공학 1
Objectives
• Describe the algorithm that allows the reader to solve chemical react
ion engineering problems through logic rather than memorization.
FUTURE
Microplant Full-scale
(Lab-bench-scale unit) Production
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
1 10 Seconds
This time is the time t needed to reduce the reactant concentration in a batch reactor
from an initial value CA0 to some specified value CA.
Typical cycle times for a batch polymerization process
t t = tf + t e + t R + t c
Activity Time (h)
1. Heat to reaction temperature, te 1.5-3.0
2. Charge feed to the reactor and agitate, tf 1.0-2.0
3. Carry out reaction, tR Varies (5-60)
4. Empty and clean reactor, tc 0.5-1.0
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
Time Concentration of EG
(min) (kmol/m3)
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 + B C
NC=NAoX=NAo-NA
C A0 CC
ln kt
C A0 rA (0.311 min 1 )C A
We see that a plot ln[(CA0-CC)/CA0] as a
function of t will be a straight line with a
slope –k.
Design of CSTR
Design Equation for a CSTR
FA0 X
Mole balance V
( rA ) exit
C CA V C A0 C A
V v0 A0 the space time
rA v0 rA
Combine
C A0 C A
kC A
Solving for the effluent concentration of A, we obtain
C A0
CA C A0 (1 X )
1 k Relationship between
space time and
conversion for a 1st-
k order liquid-phase rxn
X
1 k
Reaction Damköhler number
rA0V Rate of Reaction at Entrance " a reaction rate"
Da
FA 0 Entering Flow Rate of A " a convection rate"
rA0V kC A2 0V
For 2nd-order irreversible reaction Da kC A0
FA0 v 0 C A0
Da 0.1 will usually give less than 10% conversion.
Da 10.0 will usually give greater than 90% conversion.
k Da
For first order reaction, X = =
1 + k 1 + Da
CSTRs in Series
CA0 CA1, X1
v0
CA2, X2
-rA1, V1 -rA2, V2
For first-order irreversible reaction with no volume change (v=v0) is carried out in t
wo CSTRs placed in series. The effluent concentration of A from reactor 1 is
C A0
C A1
1 1k1
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 A2
1 2 k 2 1 2 k 2 1 1k1
C A0 C A0
C An
1 k n 1 Da n
The conversion and the rate of disappearance of A for these n tank reactors
in series would be
X= 1-CA/CAo
1 kC A0
X 1 1 rAn kC An
1 k n =1-
(1+Da)n 1 k n
Conversion as a Function of Reactors in Series
for different Damkohler numbers for a first-order recation
Da=k=1
Da=k=0.5
Da=k=0.1
X1 X 2 X n X i
V FA0 X i
n n rAi
-r-r
Ai,Ai,VV
i , i Xi
FA0n
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 the -r-rAn, ,VVn, Xn
An n
reactant were fed in one stream to one large reactor of
volume V
A Second-Order Reaction in a CSTR
V
FA 0 X FA 0 X
(4-14) 1 2kC A0 1 4kC A0
rA kC A2 2kC A0
0.88
0.67
6 60
Example 4-2: Producing 200 Million Pound/Year in a CSTR
dX
F A0
dV
rA =
vo
kCAo ( X
1-X )
must be used when there is a DP or heat
exchange between PFR & the surrounds.
1
V/vo= = kC
Ao
( X
1-X )
In the absence of DP or heat exchange, the kCAo Da2
integral form of the PFR design equation X= =
is used.
1+kCAo 1 + Da2
(Da2=Damköhler number for a 2nd-order RXN)
X dX
V FA0 0 rA For n-th order RXN, Dan=kCAon-1
For Gas-Phase Reaction
X dX
V FA0
0 kC A2
Conversion as a Function of Distance Down the Reactor
v (1 0.5 X )v0
v=vo(1+X) the reactant spends more time
v (1 2 X )v0
the reactant spends less time
ö
V(m3)
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=vo(1+X)
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.
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
the 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
Pressure Drop and Rate Law
i vi X P To
(4-18) C i C A0
1 X P0 T
• For example,
- the second order isomerization reaction in a packed-bed reactor
2A B + C
-the differential form of the mole balance
dX gmoles
FA0 rA
dW g catalyst min
- rate law
rA kC A2
- the larger the pressure drop from frictional losses, the smaller the reaction rate
• Combining with the mole balance and assuming isothermal operation (T=To)
2 2
dX C A0 (1 X ) P
FA0 k
dW 1 X P
0
• Dividing by FA0
2 2
dX kC A0 1 X P
dW v0 1 X P0
Pressure Drop and Rate Law
dX
f ( X , P) (4-21)
dW
- that is, we need to relate the pressure drop to the catalyst weight
P f (W )
Flow Through a Packed Bed
• The majority of gas-phase reactions are catalyzed by passing the reactant
through a packed of catalyst particles
dP G 1 150(1 )
3 1.75G (4-22)
dz g c D p Dp
laminar turbulent
• The gas density is the only parameter that varies with pressure on the right-hand
side. So, calculate the pressure drop through the bed laminar turbulent
Flow through a Packed Bed
• Equation of continuity
m 0 m
m o = m
0 v0 v
- 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
v v0 0 (3-41)
P T F
0 T0
• Then,
v0 P T0 FT 0 (4-23)
0 0
v P0 T FT
Pressure Drop in a Packed Bed Reactor
• then, Ergun equation
dP G (1 ) 150(1 ) P0 T FT
1.75G
dz 0 g c D p 3 Dp T F
P 0 T0
• Simplifying dP P0 T FT
0 (4-24)
dz P T0 FT 0
G (1 ) 150(1 )
0 1.75G (4-25)
dP 3
0 g c D p Dp
We need
dW
dW c (1 ) Ac dz
Pressure Drop in a Packed Bed Reactor
• then, Ergun equation
dP 0 P0 T FT
dW Ac (1 ) c P T0 FT 0
dP T P0 FT
• Simplifying (4-27)
dW 2 T0 P / P0 F
T0
dP
dy T F P0T
Let y=P/Po (1 X ) (4-28)
dW 2y
2 T0 PF/ To
P0
2 0
(4-29)
Ac c (1 ) P0
F FT FA 0
FT FT 0 FT 0 X FT 0 1 A0 X 1 X y A0
FT 0 FT 0 FT 0
Pressure drop in a packed bed reactor
dP
dy T P0
(1+X)(1 X ) (4-30)
dW 2y
2 T0 P / P0
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 special case of 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
dP
dy T P0
(1+X)(1 X ) (4-30)
dW 2y
2 T0 P / P0
Analytical Solution
Isothermal (T=To) dy
dP P0
with ε = 0 dW 2y
2 ( P / P0 )
dy dy2
dW = - dW = -
2y
Pressure ratio P
y= 1 W (4-33)
only for ε = 0 P0
2 0
Ac (1 ) c P0
W (1 ) Ac z c (4-26)
Pressure as a P 2 z
function of y= 1 0 =f (z) (4-34)
P0 P0
reactor length, z
Pressure Drop in Pipes
Pressure drop along the length of the pipe
dP d 2 fG 2 P dP 2 dP 2 fG 2
G 0 G 0
dL dL D 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 0 D P
Rearranging, we get
P0 4 fG 2
1 pV p
P 0 P0 Ac D
A B
dX kC A2 0
dW
FA0
(1 X ) 2 1 W 1/ 2 2
kC A0W W
1
v0 2 (4-38)
X
kC W W
1 A 0 1
v0 2
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.
Example 4-5 and Example 4-6
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
Synthesizing a Chemical Plant
1 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
Cat. CH2OH
C2H4O + H2O
CH2OH
Synthesizing a Chemical Plant
Must write a mole balance on each species when molar flow rate
s (Fi) and concentrations (Ci) are used as variables
b c d
A B C D
a a a
rA rB rC rD
a b c d
rA k AC A C B
Liquid Phase
For liquid-phase reaction with no volume change Concentration is the preferred variable
aA bB cC dD
b c d
A B C D
a a a
Mole balance for liquid-phase reactions
dC A dC B b
Batch rA rA
dt dt a
v0 (C A0 C A ) v0 (C B 0 C B )
CSTR V V
rA (b / a)rA
dC A dC B b
PFR v0 rA v0 rA
dV dV a
dC A dC B b
PBR v0 rA v0 rA
dW dW a
Gas Phase
For gas phase reactions
need to be expressed in terms of the molar flow rates
dF j
rj (1-11)
dV
y
Fj P T0
C j CT 0
P
T
(3-42)
FT 0
dy - FT
= (4-28, T=To)
dW 2y FTo
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 F FC dFC
rCV V C0 rC
dt rC dV
dN D F FD dFD
rDV V D0 rD
dt rD dV
Algorithm for Gas Phase Reaction
Rate law:
rA k AC A C B
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
a y 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
Algorithm for Gas Phase Reaction
Combine:
dFA FA FB dFB b FA FB
k ACT 0 k ACT 0
dV FT FT dV a FT FT
dFC c FA FB dFB d FA FB
k ACT 0 k ACT 0
dV a FT FT dV a FT FT
- Specify the entering number: FA0, FB0, FC0, FD0, and final value: Vfinal
The gas phase reaction, 2NOCl 2NO + Cl2, 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 micro reactor 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.
Solution
For one channel,
FAo=22.6 mol/s
FB=19.2 mol/s, X=0.85
dF j
1. Mole balance: rj 2. Rate law:
dV
dFA -rA=kCA2, k=0.29 dm3/mol-sec
= rA
dV
dFB
= rB
dV
dFC
= rC
dV
3. Stoichiometry: Gas phase with T=To and P=Po, then v=vo(FT/FTo)
3-1. Relative rate
rA rB rC
= =
-1 1 1/2
rB = -rA, rC= -0.5rA
3-2. Concentration
By applying Equation (3-42)
CA=CTo(FA/FT), CB=CTo(FB/FT), CC=CTo(FC/FT) with FT=FA+FB+FC
4. Combine 5. Evaluate
-rA=kCA2=kCTo2(FA/FT)2
CTo=Po/RT=(1641)/(8.314)(698K)
dFA =0.286 mol/dm3=0.286 mmol/cm3
= -kCTo2(FA/FT)2
dV
dFB
= kCTo2(FA/FT)2 Use Polymath to solve the ODE
dV
dFC = 0.5kC 2(F /F )2
To A T
dV
FA
FB
FC
Membrane Reactors
Membrane reactors are most commonly used when a reaction involves some for
m 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, whi
ch 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 coate
d with or is made of a material that contains catalyst, which means that the membr
ane 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 sid
e.
Membrane Reactors
A B +
C
CH2CH3 CH=CH
+ H2 (B)
RB V
RB=kcCB V+V
There are
1. Mole balance: two “OUT”
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
2. Rate law:
C C
rA k C A B C ;
rB rA ; rC rA
KC
3. Transport out the sides of the reactor:
RB k C C B
4. Stoichiometry:
FA F F
C A CT 0 ; C B CT 0 B ; CC CT 0 C
FT FT FT
FT FA FB FC
rA rB rC
Basic Algorithm for Solving Reaction in the Membrane Reactor
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
Effects of Side Stream, RB=kcCB
in a membrane reactor
10
kc=0.20 min-1 FC
FA
FA Conversion
FB 5
FB X=(10-4)/10=0.6
FC
0
0 100 200 300 400 500
Reactor volume, V [L]
10 10
kc=0.0022 min-1
FC kc=20 min -1
FA FA
FA
FB 5 5
FC FA FB FB FC
FB
0 FC
0 100 200 300 400 500 0
0 100 200 300 400 500
Reactor volume, V [L]
Reactor volume, V [L]
Unsteady-State Operation of Stirred Reactors
A A, B
Semibatch reactor
(b) ammonolysis, chlorination, hydrolysis
(c) acetylation reaction, esterification reaction
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
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 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 , we find that
dC A
C A0 C A rA (4-46)
dt
Startup of a CSTR
For a first-order reaction: rA kC A
dC A 1 k C A0
CA
dt
C A0 t
Solution CA 1 exp (1 k ) (4-47)
1 k
Letting ts be the time necessary to reach 99% of the steady state concentration, C AS:
C A0
C AS
1 k
0.05
CA
0.02
CC
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
0.0020
(A) (B) (C) (D)
Reaction rate [mole/s•L)
0.00010
0.00005
0.00
0 50 100 150 200 250
Reactor Equations in terms of Conversion
in semibatch reactor
A B CD 0 0
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
A A
at time t initially to time t
NA N A0 N A0 X (4-59)
N B N Bi FB 0 t N A0 X (4-61)
Reactor Equations in terms of Conversion
in semibatch reactor
0 0 A B CD
B B
The concentration of A and B
A A NA N (1 X )
CA A0
V V0 v0 t
A mole balance on specials A:
NB N FB 0 t N A0 X
dN A CB Bi
rAV (4-62) V V0 v0 t
dt NC N A0 X
CC
The number of moles of C and D cab be taken V V0 v0 t
directly from the stoichiometric table
ND N A0 X
N C N Ci N A0 X CA
V V0 v0 t
(4-63)
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
dt V0 v0 t
C C
rA k C AC B C D
(4-65)
KC (4-66) can be solved numerically
Equilibrium conversion
in semibatch reactor
0 0
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 semibatc KC
h reactor, the maximum attainable conversion (i. N Ae N Be
e., the equilibrium conversion) will change as the
reaction proceeds because more reactant is conti ( N A0 X e )( N A0 X e )
nually to the right. N A0 (1 X e )( FB 0 t N A0 X e )
A B CD
N A0 X e2
The rate law (reversible 2nd-order reaction)
(1 X e )( FB 0 t N A0 X e ) (4-68)
C C
rA k C AC B C D
KC N A0 X 2
t KC X e e (4-69)
K C FB 0 1 X e
2
Equilibrium conv FB 0 t FB 0 t F t
ersion in a semiba K C 1 K C 1 4( K C 1) K C B 0
N A0 N A0 N A0 (4-70)
tch reactor
Xe
2( K C 1)
Reactive Distillation
However, if one or more of the products are removed more of the product w
ill be formed because of Le Chatlier's Principle :
P4-11B
P4-12B
P4-13B
P4-14C