F2
o .
ni (t )
. .
V (t )
. FN
.
o
FN Molar balance of species i
NR
ni
c i dV
0
Fi Fi rV , k dV N
k 1
ki
V t V t ki
k
i 1
ki
Ai 0 k 1, N R
i 1
Manometer
Q P=f(t) ni ( t )
Heat flux
NR
dn i
dt
r
ki V , k
.V R
k 1
Reactor volume constant (VR=const.)
n
d i
V R dc i
NR
1 dn i
r
ki V , k c1 , c 2 , ...c N
V R dt dt dt k 1
n i c i .V R
1 dn i 1 d c i .V R dc i d ln V R NR
V R dt
VR dt
dt
ci
dt
r
ki V , k
k 1
NR
dc i d ln V R
dt
ki rV ,k c i dt
k 1
T o calculate P ( t ) o r V R ( t )
state equation f(T ,P,V , com position) = 0 is needed
Example
Constant volume isothermal batch reactor, ideal gas mixture
N
RT
P
VR
n j
N
kj
k
j 1
j 1
dP RT N
dn j RT N NR NR
dt
VR
dt
VR
V R
r
kj V , k
R T k rV , k
j 1 j 1 k 1 k 1
P
RT N ci y i *
RT
VR
P
nj
j 1
dV R RT N
dn j RT N NR
RTVR NR
d ci NR
RT NR
dt
P
dt
P
V R kj rV , k P
k rV , k r
ki V , k
ci r
k V ,k
j 1 j 1 k 1 k 1 dt k 1 P k 1
NR
d ln(V R ) RT NR NR
dt
P
r
k V ,k r
ki V , k
y i k rV , k
k 1
k 1 k 1
Example
Constant volume batch reactor, liquid mixture constant pressure
Second order irreversible reaction
d ci
i rV i kc1 c 2 2.5
dt o
c1 2 m ole/l
d c1 2 o
c 2 1 m ole/l
kc1 c 2
dt 1.5
o
c3 0
dc2 ci
c1
kc1 c 2 mol/l 1 c2
dt
c3
d c3 0.5
kc1 c 2
dt
0
o o o o o
c1 c c 2 c , c 2 c1 c c , c 3 c c1
1 2 1 2 1
0 2 4 6
t/min
d c1
c1
d c1
t
c o
c2
o
1
c k d t c1
o o
kc1 c1 c1 c 2
c
o
c
o o
dt c1 c 2 c2 o o
c1 kt
1
o 2
c1 1 1 0
o
e
c1
1
o o
1
c1 c 2 c1 o kt
c1
Continuous-flow reactors
Continuous Stirred Tank Reactor – CSTR
N
ki
Ai 0 k 1, N R
i 1
ni ( t )
V R const V olum e of reactor
NR
d ni
ki rV , k V R
0
Fi Fi
k 1 dt
d nj N N NR NR
dn i
F F VR F F V R k rV , k 0
i 1 o o
r
ki V , k
dt i 1 dt i 1 k 1 k 1
NR
F F V R k rV , k
o
k 1
Fi y i F V R k rV , k V R ki rV , k
o
o o o
dt k 1 i k 1 Fi y i F
dn i P V R dy i NR
F ( y y i ) V R ( ki y i k ) rV , k
o o
i
dt RT dt k 1
o
dy i RTF R T NR
ki
o
= ( y yi )
i
( y i
k
) rV ,k
i 1, N
dt PVR P k 1
Inlet volumetric flow rate is
o
RTF
Vo
P
Mean residence time of reaction mixture (based on inlet flow rate) is given by
VR PVR
o o
Vo RTF
and molar balance of species i becomes finally
dy i 1 RT N R
ki
o
= ( y yi ) (i
y i
k
) rV ,k
i 1, N
dt o P k 1
If only one reaction takes place:
d yi 1 RT
( i y i ) rV
o
= ( yi yi ) i 1, N
dt o P 1.00
NR
Fi Fi V R ki rV , k ,
o
i 1, N
k 1
Fi Fi V R i rV ,
o
i 1, N
o
Fj Fj
using fractional conversion of key species j Xj o
Fj
F j X j VR
o
j
rV ( X j )
o
X j Simple substitution
VR F j
j rV ( X j )
b) T he outlet conversion for given volum e of reactor
o
Fj
Xj rV ( X j ) f ( X j ) 0 Graphical or numerical (iterative)
j
VR solution
Graphical assessment of the CSTR volume
1
j rV ( X j ) Levenspiel
diagram
X j
j rV ( X j )
usually v j 1
X j
Graphical assessment of the outlet conversion
j rV ( X j )
o
Fj
X j
VR
X j
Cascade of CSTR Fj
( n 1) (n)
Fj
(n)
VR
……… X
(n)
j ………
n-th member of
Steady state the cascade
( n 1)
V R i rV ,
(n) (n) (n )
Fi Fi i 1, N n 1, N C ST R
o (n)
(n)
Fj Fj
X j
o
Fj
(n) o (n)
Fj F j (1 X j
)
(n) o i o (n)
Fi Fi Fj X j
j
o
Fj
V
(n) X (n)
j
X
( n 1)
j j
rV ( X
(n)
j
), n 1, N C ST R
R
Graphical assessment of the outlet conversion in the cascade of CSTR
j rV ( X j )
o
Fj
F
o
V
(2) X j
X
(1)
j
j
(1)
X j
R
VR
(1) (2)
X j
X j
X j
Homework 6 VR
(n)
n
Prove that X j 1 (1 k o ) , o
(n)
for first order constant-volume reaction.
Vo
(n)
In the limit lim X ( n ) 1 e k , nV R
oR
j oR
n Vo
Plug Flow reactor – PFR
Tubular reactors
High production capacity
v Catalytic reactors (e.g. ammonia
synthesis)
.
Fi (V R ) Fi (V R VR ) .
.
z z + z VR S R z
VR VR + VR
ci (t , z ) 1 Fi ( t , z ) NR
t
=
SR z
r
ki V , k
(t , z ) i 1, N
k 1
Steady state
NR
dFi
dV R
r
ki V , k
i 1, N
k 1
d Fi
i rV i 1, N
dVR
o
Fj Fj
using fractional conversion of key species j Xj o
Fj
dX j
o
F j j
rV ( X j )
dV R
useful relations:
X j (2)
dX j Fi Fi yi Fi
o
F j
VR yi N
, ci N
X j (1)
j
rV ( X j ) Fj Vm F j
Vm V
j 1 j 1
3 1
V m m o lar vo lu m e (m m o le )
BATCH, CSTR, PFR (PBCR), one reaction, fractional conversion of key component
BATCH 1
1
o X tR
n j
dX j
rV
j j
jV R rV ( X j )
dt t R
0 0
1
o X tR
c j
j
dX j
rV ( X j )
dt t R
CSTR
PFR
j 0 0
X j
CSTR o 1 o 1 X
1
j
F j
X j
F j
X j
VR
1 1
j
rV ( X ) j j
rV ( X j ) PBCR
Packed Bed Catalytic Reactor
PFR 1 1 o X
1
o X
1
F
o X j
dX F
o X j
dX F j
j
dX j
F j
j
dX j
VR
j
j
j
j W
rM
rM ( X j )
j 0
rV ( X j ) j 0
rV ( X j ) j 0 j 0
Mean residence time
VR
V
BATCH, PFR
1
o X
c j
j
dX j
rV ( X j )
o
j 0 VR
o
Vo
CSTR
o 1
cj X j volumetric flow rate (m3/s) of reaction
1
o Vo mixture at inlet conditions
j
rV ( X ) j
Gas Hourly Space Velocity
3
G as volum etric flow rate(m /hr)
G H SV 3
V olum e of reactor (m )
NR = 1 i
Ai 0 = i j – subscript of key component
i 1 i 1
BATCH FLOW
i i
ni ni i ni Fi Fi i rV .dV R Fi
o o o o o o
n j .X j
F j .X j
j
j
N N
n i n . n
o o
n
o o o o
n j .X F F F j .X j
i 1
i
i 1 j
j
j
o i o i o i o o i o
ni n j .X j xi
o o
x j .X Fi F j .X j
xi x j .X j
ni j k
j
Fi j
j
xi xi
n o o o F o o o
n n .X j j
1 x .Xj j
F F .X j j
1 x j .X j
j
j
j
j
i o i o
xi
o o
x j .X xi x j .X j
ni ni xi 1 j
j
Fi Fi xi 1 j
ci ci
V n .V m Vm Vm V F .V m Vm Vm o
1
o
x .X 1 x j .X j
j
j j
j
Vm - m o lar vo lu m e o f reactio n m ix tu re
3
(m /m o l)
Gas phase - Ideal state behavior
RT
Vm
o i o P o i o
xi x j .X j
xi x j .X j
xi Pi P j Fi Fi Pi P j
ci ci
RT RT RT o V RT RT RT o
1 x j .X j
F. 1 x j .X j
P j
P j
ni ni Fi Fi
ci ci
V T Po o V T Po o
Vo (1 x X j)
To P j
j Vo 1 xj X j
To P j
o i o o i o
o i o o i o
ni n j . X j c c . X
Fi F j . X j ci c j . X j
i j j
T P 1 T P j
o j
o T P 1 T P
o o o j
o j
T Po V o T Po o o
1 xj X j 1 xj X j T Po V o T Po
j 1 xj X j 1 xj X j
j
j j
Homework 7
Calculate volume of PFR to produce 150 kt ethylen/year. Reaction of the 1st order
takes place at 1100 K and 0,6 Mpa. Final conversion of ethan is 80 %. Reaction rate is given by
rV = k. cA
Assumptions:
Ideal gas, molar weight of ethylen is 28,054 kg/kmol.
K. J. Laidler and B. W. Wojciechowski: Kinetics and Mechanisms of the Thermal Decomposition of Ethane.
I. The Uninhibited Reaction, Proceedings of the Royal Society of London. Series A, Mathematical and
Physical Sciences, Vol. 260, No. 1300 pp. 91-102
Homework 4 (due after Chapter 4)
Calculate volumes of CSTR a PFR working at 150 oC and 300 kPa to produce 1 t COCl2/day
with CO conversion equal to 95 %. A mixture of CO and Cl2 (molar ratio 1:1) is fed at 300
kPa and 150 oC.
Data
k(423 K) = 0.07 (m3mol-1)3/2.s-1
MCOCl2 = 98.92 kg/kmol.
Answer:
1 10 / 98.92 / 24 3600
6
o F3
F1 1
0.1231 63 m o l/s
X 1
0.9 5
o 1 o 1
F1 X1 F1 X1 0.1231 63 0. 95
V C ST R 5/2
5/2
1 rV ( X )
1
1
1 P
5/2
1 X 1
300 10 3
1 0.95
5/2
k
1
1
0.07
RT 2 X 1 8.3145 423 2 0.95
3
0.0503 m
1
o X 5 / 2 0.95 5/2
o 0.95
F dX o
2 X1
j
j j F1 dX 1 F1 R T
V PFR
rV ( X j )
1
5/2 5/2
k P
1 X
dX 1
j 0 0 P 1 X1 0 1
k
RT 2 X 1
5/2
0.123163 8.31 45 423 3 3
3 79.42692225 2.08 10 m
0.07 300 1 0
Summary