CHEMICAL REACTION

ENGINEERING (SKF3223)

Chapter 4:
Isothermal Reaction Design

WAN NORHARYATI WAN SALLEH

[email protected]
RAFIZIANA MD. KASMANI
[email protected]
 1 The general mole
balance equation: Determine the rate law Gas with P=P0 or
6
dN A 4 in terms of the Liquid:
FA0 FA rAdV concentration of the Combine steps 4
dt reacting species: and 5 to obtain

Apply mole balance to specific CC –rA=f(X)

rA k C ACB
reactor design equations: KC
2 Gas phase reaction with
dX 7 pressure drop:
Batch : N A0 rAV
dt
5 Use stoichiometry to express dy
FA0 X concentration as a function of (1 X)
CSTR : V dW 2y
rA conversion
P
dX (i) Liquid-phase or constant y
PFR : FA0 rA volume batch: P0
dV
C A C A0 (1 X ) Semibatch reactors:
dX '
PBR : FA0 rA
dW b V V0 v0t
CB C A0 B X
a
Combine mole balance, rate
law and stoichiometry,
3 Derive: (ii) Gas-phase T=T0: 8 transport law, and pressure
(1 X ) P drop term in an ordinary
rA f (X ) CA C A0 differential equation solver
(1 X ) P0 (ODE solver Polymath)
 ALGORITHM FOR
ISOTHERMAL REACTOR
1. Mole balance
2. Rate law
3. Stoichiometry (specify whether the reaction is gas or
liquid phase)

4. Combine
5. Evaluate (Analytically-Appendix A1, Graphically-Chapter 2,
Numerically-Appendix A4, Polymath software)
 ALGORITHM TO ESTIMATE
REACTION TIMES (BATCH REACTOR)
Mole balance dX rA
V
dt N A0
Rate law
rA kCA rA kC A2
Stoichiometry NA
CA C A0 (1 X )
V=V0 V0

Combine dX dX
k (1 X ) kCA0 (1 X ) 2
dt dt
Integrate X
dX 1 1 X
t N A0 t ln t
0
rAV k 1 X kCA0 (1 X )
 ALGORITHM - CSTR
Mole balance FA0 . X
V
rA
Rate law
rA kCA rA kC A2
Space time V
0

Conversion 1st order: 1st order: 2nd order:

Parallel Series
(1 2 Da) 1 4 Da
1 X
.k Da X 1 2 Da
X
1 .k 1 Da (1 .k ) n
n= number of
C A0 Da kCA0
reactors Da k C An
(1 Da) n
• One of important characteristic in CSTR equation is
Damköhler number , Da
If Da < 0.1, then X < 0.1
• Da number is a dimensionless If Da > 10, then X > 0.9

rA0 .V = Rate of reaction at entrance

Da Entering flow rate of A
FA0
kCA0 .V First order irreversible
Da .k
0 .C A0
reaction

kCA0 .V Second order irreversible

Da .kCA0
0C A0
reaction
 ALGORITHM – TUBULAR
(GAS-PHASE)
(No pressure drop)
Mole X
dX
balance V FA0
0
rA
Rate law
rA kCA rA kC A2
Stoichio-
metry (1 X )
CA C A0
(1 X )
combine X
FA0 (1 X ) X
FA0 (1 X ) 2
V dX V dX
kCA0 0 (1 X ) 2
kCA0 0 (1 X ) 2

FA0 1
(1 ) In X
kC A0 1 X
 PRESSURE DROPS
IN REACTORS
 Liquid-phase reaction: pressure drop can totally ignored
 Gas-phase reaction: Pressure drop will be considered – is very
important - key factor in the success or failure of the reactor operation
 For an ideal gas, the concentration of reacting species i:

i vi X P T0
Ci C A0
1 X P0 T
Fi 0
i , y A0 , v stoichiometriccoefficient
FA0

 When P≠P0, use the differential forms of the PFR/PBR design

equations
 EXAMPLE 2A B C
dX
1. Mole balance - Differential form: FA0 rA'
dW
2. Rate law: rA' kC A2
C A0 (1 X ) P T0
3. From stoichiometry for gas-phase reactions: CA
1 X P0 T
-rA=f(X) 2
C A0 (1 X ) P T0
rA' k
1 X P0 T Isothermal, T = T0

4. Combine
2 2 2 2
dX C A0 (1 X ) P dX kC A0 (1 X ) P
FA0 k
dW 1 X P0 dW v0 1 X P0

5. Relate the pressure drop (P/P0) to the catalyst weight  to determine X as a

function of catalyst weight
 PRESSURE DROPS IN PBR
 Ergun Equation: P = Ibf/ft2 (kPa)
Φ = porosity = void fraction
= volume of void
total bed volume
dP G 1 150(1 ) 1-Φ = volume of solid
3
[ 1.75G] total bed volume
dz gC DP DP gc = 32.174 Ibmft/s2Ibf (conversion
factor)
laminar turbulent Dp = diameter of particle in the bed, ft
(m)
μ = viscosity of gas, Ibm/ft.h (kg/m.s)
z = length of PBR pipe, ft (m)
u = superficial velocity = volumetric
P T0 FT 0 flow/cross section, ft/h (m/s)
 Variable Gas Density: 0 ρ = gas density, ib/ft3 (kg/m3)
P0 T FT G = ρu = superficial mass velocity,
Ibm/ft2h (kg/m2s)

dP G 1 150(1 ) P0 T FT
3
[ 1.75G]
dz 0 g C DP DP P T0 FT 0
 Simplifying yields:

dP P0 T FT
0
dz P T0 FT 0 β0 is a constant
down the reactor
G (1 ) 150(1 ) that depends only
0 1.75G on the properties of
0 gc Dp Dp the PBR and the
entrance conditions

 The catalyst weight up to a distance of z down the reactor is:

W (1 ) Ac z C

Volume of solids Density of solid

 Bulk density: catalyst

b c (1 )
 Ergun equation in terms of catalyst weight:

dP 0 P0 T FT
dW AC (1 ) C P T0 FT 0

 Further simplification yields:

dP T P0 FT 2 0 P
y
dW 2 T0 P / P0 FT 0 AC C (1 ) P0 P0

Use for multiple reactions and membrane reactors

FA0
dy T FT FT FT 0 FA0 X FT 0 1 X
FT 0
dW 2 y T0 FT 0
Use for single reactions in PBR FT FA0
1 X y A0
dy T FT 0 FT 0
(1 X)
dW 2y T0
 ONLY for isothermal with T/T0=0, ε = 0:

P
y (1 W)
P0
 For isothermal with T/T0=0, ε ≠ 0:

dy
(1 X) y 1 W (1 X)
dW 2y

1/ 2
P 2 0 z
y 1
P0 P0
 T/T0 = 0, ε = 0, with ∆P
EXAMPLE A B
dX ' 4
dX kCA2 0 (1 X ) 2 (1 W)
1 FA0 rA
dW dW FA0

' 2 1 kCA2 0
2 r A kC A 2
dX (1 W ) dW
(1 X ) FA0
P
3 CA C A0 (1 X ) C A0 (1 X ) y X kCA2 0 W2
P0 W
1 X FA0 2
P
y (1 W) kCA0W W
P0 1
v0 2
' 2 2 2
X
r kC (1 X ) ( (1 W )) kCA0W W
A A0 1 1
v0 2
rA' kC A2 0 (1 X ) 2 (1 W)
(2v0 ) X
5 Could now solve for X 1 1 [ ][ ]
given W, or for W given X. kCA0 1 X
W
 T/T0 = 0, ε = 0, in the absence of ∆P, (α = 0)

kCA0W
X kCA2 0 v0
rA' kC A2 W X
kC A0W
1 X FA0
1
v0

with ∆P, (α ≠ 0)

2 0 2 0
AC C (1 ) P0 AC b P0

 X decreased with ∆P
 If we increase catalyst size, laminar terms = 0 (Ergun equation)
 By increasing the particle diameter, we decrease the pressure drop
parameter (β0) and thus increase the –rA and the X.
 PRESSURE DROP IN PIPES
 Pressure drop along the length of the pipe:

dP du 2 fG 2
G
dL dL D

D = pipe diameter, cm
u = average velocity of gas, cm/s
f = Fanning friction factor
G = ρu, g/cm2s (mass velocity, constant
along the length of the pipe)
EXAMPLE: Calculating X in a Reactor With ∆P (gas=phase)
1 FB 0 1
A B C B
2 FA0 2

dX 4 rA' kRTC 1A/ 3C B2 / 3

1 FA0 rA'
dW
C A0 (1 X ) y 1/ 3 C A0 (1 X ) y 2 / 3
rA' kRT [ ] [ ]
2 rA' kPA1/ 3 PB2 / 3 1 X 2(1 X )
PA0 C A0 (1 X ) y 1/ 3 C A0 (1 X ) y 2 / 3
PA C A RT rA' k [ ] [ ]
C A0 1 X 2(1 X )
rA' k (C A RT )1/ 3 (CB RT ) 2 / 3 Factoring (1/2)2/3
rA' kRTC 1A/ 3CB2 / 3 1 X
rA' k' y
1 X
3 C A0 (1 X ) P C A0 (1 X ) y
CA
1 X P0 1 X
k' kPA0 (1 / 2) 2 / 3 0.63kPA0
C A0 ( B X / 2) y C A0 (1 X ) y
CB
1 X 2(1 X )
MOLE BALANCES FOR
LIQUID-PHASE b c d
A B C D
a a a
REACTIONS

dCA dCB b
Batch rA rA
dt dt a

CSTR v0 (C A0 C A ) v0 (CB 0 CB )
V V
rA (b / a)rA

PFR dCA dCB b

v0 rA v0 rA
dV dV a

PBR dCA dCB b '

v0 rA' v0 rA
dW dW a
 MOLE BALANCES FOR b c d
A B C D
GAS-PHASE REACTIONS a a a

BATCH CSTR PFR

dN A FA0 FA dFA
rAV V rA
dt rA dV

dN B FB 0 FB dFB
rBV V rB
dt rB dV
dNC FC 0 FC dFC
rCV V rC
dt rC dV
dN D FD 0 FD dFD
rDV V rD
dt rD dV
 GAS-PHASE REACTIONS
dFj 2 rA k AC A C B
1 rj
dV
rA rB rC rD
3 F j T0 a b c d
Cj CT 0 y
FT T
FA T0 4 dFA
CA CT 0 y rA
FT T dV
FB T0 dFA FA T0 FB T0
CB CT 0 y k ACT 0 y y
FT T dV FT T FT T

FT FA FB FC FD FI Isothermal, T=T0:

dy FT dFA FA FB
dW 2 y FT 0 k ACT 0 y y
dV FT FT
 UNSTEADY-STATE OPERATION:
CSTR & SEMIBATCH

 To determine the time necessary to reach steady-state

operation
 To predict the concentration, C and X as a function of time
 Analytical solutions: zero and 1st order reactions
 ODE solvers: other reaction orders
 LIQUID-PHASE REACTIONS (CSTR)
v = v0, V = V0, τ = V0/v0

1
dN A tS = the time necessary to
FA0 FA rAV 4
dt reach 99% of the steady-
state concentration, CAS:
dCA (CA = 0.99CAS)
C A0 CA rA
dt C A0
C AS
2 rA kCA 1 k

dCA 1 k C A0 Slow reactions

CA tS 4 .6
dt with small k
(1>>τk):
3 Initial condition: CA = CA0 at t = 0:
Rapid
reactions with
4.6
C A0 t tS
CA {1 exp[ (1 k ) ]} large k (τk >> k
1 k 1):
 SEMIBATCH REACTOR – in terms of
concentration, C
dN A
General mole balance: rAV (t )
dt
d (C AV ) VdC A dV
In terms of concentration: rAV CA
dt dt dt

Semibatch reactor volume as a function of time: V V0 v0t

Mole balance on A: Mole balance on B:

dC A 0 dCB (C B 0 C B )
rA CA rB 0
dt V dt V
 SEMIBATCH REACTOR – in terms of
conversion, X
A B C D
dN A dX 3 For constant molar feed rate and
1 rAV N A0
dt dt no B initially in system:

NB FB 0t N A0 X
2 CC CD
rA k C ACB
KC
NB N Bi FB 0t N A0 X
CB
V V0 v0t
NA N A0 (1 X )
3 CA
V V0 v0t ND N A0 X
CD
V V0 v0t
NC N A0 X
CC
V V0 v0t
4 dX k[(1 X )( N Bi FB 0t N A0 X ) ( N A0 X 2 / K C )]
dt V0 v0t

5 At equilibrium after feedings pecies B for a time, t, the equilibrium

conversion could be:

CCeCDe N Ce N De ( N A0 X e )( N A0 X e )
KC
C AeCBe N AeN Be N A0 (1 X e )(FB 0t N A0 X e )

N A0 X e2
t KC X e
K C FB 0 1 Xe

2
FB 0t FB 0t tFB 0
Kc 1 KC 1 4( K C 1) K C
N A0 N A0 N A0
Xe
2( K C 1)
 REFERENCES
Main Reference:

1. Fogler,H.S., “Elements of Chemical Reaction Engineering”, 4th

Edition,Prentice Hall, New Jersey, 2006.

Other References:

1. Davis, M.E and Davis, R.J, “Fundamentals of Chemical Reaction

Engineering”, Mc-Graw-Hill, New York, 2003
2. Schmidt, L.D, “The Engineering of Chemical Reactions”, Oxford,
New York, 1998
3. Levenspiel,O., “Chemical Reaction Engineering”, 3rd Edition,
Wiley,New York, 1998
4. Smith,J., “Chemical Engineering Kinetics”, 3rd Edition, McGraw-
Hill, New York, 1981