Summary

• General material balance of reacting system

• Batch reactor
• Continuous-flow reactors: CSTR (Continuous Stirred Tank Reactor)
PFR (Plug Flow Reactor)
• Steady state of CSTR and PFR
• Design tasks : outlet (final conversion), given volume of reactor x volume
of reactor, given outlet conversion
 4. The material balances for isothermal ideal reactor models
T=const. Outlet convective molar
flows (mol/s)
Arbitrary volume element F1
Inlet convective molar F2
flows (mol/s) N
o
F1  ki
Ai  0 k  1, N R .
i 1

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

Overall molar balance

N N NR NR
n
  Fi o  Fi      ki  rV , k dV  F  F     k  rV , k dV 
o
  V V t
i 1 i 1 k 1 k 1
 Laboratory
Pharmaceutical industry
Batch reactors Special chemicals
Polymers
.
Vconst. Mixer .
.
T=const.
Perfect mixing N

 ki
Ai  0 k  1, N R
i 1

Manometer
Q P=f(t) ni ( t )
Heat flux

V R ( t )  V olum e of reaction m ixture

Molar balance of species i

NR
 ni
  ki  rV , k d V 
0
Fi  Fi 
k 1
VR t

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

Reactor pressure constant (P = konst.)

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

Constant pressure isothermal batch reactor, ideal gas mixture

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

A1(l) + A2(l)  A3(l) rV  kc1 c 2 ,

o
t  0, c1  c1 , c 2  c 2 , c 3  0
o

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

Molar balance of species i

NR
d ni
  ki rV , k V R 
0
Fi  Fi 
k 1 dt

Overall molar balance

NR
dn
 
o
F F  r VR 
k V ,k
k 1 dt

We need suplementary information

• state behavior of reaction mixture
• start-up (shut-down) molar flow rates of individual species
 N
Constant pressure isothermal CSTR, ideal gas mixture RT  n j  pVR
i 1
It arises from overall molar balance (volume of reactor, VR is constant)
N

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

and molar balance of species i becomes

dn i  o NR
 NR

 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

Example 0.80 N2O

Start-up of an isothermal CSTR
0.60
N 2O g   N 2  g   1 / 2O 2  g 
yi (-)
4 3 o (fractional) conversion of N2O*)
V R  0.1 l = 10 m , T = 320 C , P  101 kP a 0.40
X1 =(F1o – F1)/F1o
5 1 1 -3
rV = kPN 2 O , k  2.028 x10 m ole.P a . m in .m
o o o
y1  1, y 2  y 3  y 4  0
o
(1= N 2 O , 2= O 2 , 3= N 2 , 4= H e)
0.20 N2 O2
He
t  0, y1  0  y 2  y 3  0, y 4  1
0.00
o 1 0 1 2 3 4 5
t (s)
Numerical solution of balance
equations *) The equation is valid only at steady state
 Steady state

NR

Fi  Fi  V R   ki rV , k ,
o
i  1, N
k 1

If only one reaction takes place:

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 )

a) T he volum e of reactor for given outle t conversion

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

Molar balance of species i

 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

If only one reaction takes place:

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 )

Liquid Hourly Space Velocity

3
Liquid volum etric flow rate (m /hr)
L H SV  3
V olum e of reactor (m )
 Tasks

1. Calculate the volume of reactor (mass of catalyst) (CSTR,

PFR, PBCR) or time of reaction (BATCH) to obtain given
conversion.

2. Calculate the outlet conversion for given volume of reactor.

3. Calculate the reaction rate in laboratory reactor to obtain

kinetic law and estimate the kinetic parameters.
 N N

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

C2H6(g)  C2H4(g) + H2(g)

takes place at 1100 K and 0,6 Mpa. Final conversion of ethan is 80 %. Reaction rate is given by

rV = k. cA

k (1000 K) = 0,072 s-1 E = 343,6 kJ/mol

Pure ethan is fed into the reactor.

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:

VCSTR = 0.053 m3 VPFR = 0.0021 m3

o i o
o
Fi   Fi Fi  Fi  Fj X j
CO(g) + Cl2(g) → COCl2(g)  j

steady state; j - key com ponent

IN OUT
o
F1 F1  F1  1  X 1 
o
CO (1)
F2  F1  1  X 1 
o o
Cl2 (2) F1
o
COCl2 (3) 0 F3  F1 X 1
F  F1  2  X 1 
o o o
 F  2 F1
 RT 3
ideal gas  V m  [m /m ol]
P
F1 F1 P F1 P F1 1  X 1 
o
P 1  X 1  3
c C O  c1       c C l 2  c 2 [m ol/m ]
F1  2  X 1  2  X1
o
V Vm F RT F RT RT
5/2 5/2
3/2  P   1 X1  3
rV  kc C O c C l 2  k     [m ol/m /s]
 RT   2  X 1 

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

• General material balance of reacting system

• Batch reactor
• Continuous-flow reactors: CSTR (Continuous Stirred Tank Reactor)
PFR (Plug Flow Reactor)
• Steady state of CSTR and PFR
• Design tasks : outlet (final conversion), given volume of reactor x volume
of reactor, given outlet conversion