Reactor design

Chapter Four

Chapter Four
Non- Isothermal Reactors Design
Many reactions are scientifically to:
1- Exothermic reaction
2- Endothermic reaction .

Effect of temperature on rate of reaction

1- Irreversible reactions
Arrhinus equation
k = A exp(-E/RT)
k E 1 1
ln 1  [  ]
k 2 R T2 T1

2- Reversible reactions:
From vant hoff equation
K1 H R 1 1
ln  [  ]
K2 R T2 T1

Energy Balance on Batch reactor

0 0
[accumulation of heat] = [heat flow in] - [heat flow out] + [heat generation by reaction]
+ [External heat exchange] + Ws

dE
Accumulation of heat = dt
E = mt cv (T-To)
dE dT
 mt .cv
dt dt
mt:Total mass of mixture kg.
cv : Heat capacity of mixture at constant volume (kJ/kg.K).
T : outlet temperature (K)
T0 :inlet temperature (K).

External heat exchange = Q External = U A (Ts - T)

U : Overall heat transfer coefficient (watt/m 2.K)
Ts : Temperature of heating or cooling coil or fluid (of jacket)
 if the reactor is operated adiabatically (Q External =0).

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Reactor design
Chapter Four

heat generation by reaction = QGeneration

= -  HR .(-rA.V)
 HR :Heat of reaction (kJ/kmol A)
V : reactor volume (m3)
-rA : rate of reaction (kmol/m3.sec)

Ws : work shaft =0
By substitution of each value of heat in energy balance equation;

dT
m t . cv.   H R (-rA .V)  UA(Ts - T)
dt
(Energy balance equation of BR)

Material Balance equation of BR

x
dx
t  N A0  By differentiation
0
 rA .V
dx
dt  N A0
 rA .V
subs. In energy balance equation
dx
(  rA .V )  N A0 .
dt
dT dx
mt.cv.  N A0 ( H R )  UA(Ts  T )
dt dt

H R  H R0  cp(T  Tref )
0 0
* H R0   i H i product   i H i reac tan t
cp   i cpi product   i cpi reac tan t

If cp  0  H R  H R0

H R0 : Heat of reaction at reference temperature (Tref) =25 0C

Operation Conditions
1- Isothermal o peration
dT
(T=T0) dt
0

a) adiabatically (Qexternal=0)
There is no heat effect on reaction rate or reactor volume
There is no need to heat balance on reactor.

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Reactor design
Chapter Four

b) with heat exchange:

Qexternal= - QGeneration
H R (-rA .V)  UA(Ts  T )
H R (-rA .V)
Ts  T0 
UA

2-Non-isothermal operation: (T≠T0)

a) adiabatically; (Qexternal=0)

dT dx
mt .cv   N A0 H R
dt dt
T x
mt .cv  dT   N A0 H R  dx
T0 0 Adiabatic Temperature as a function of x
mt .cv.(T  To )   N A0 H R x

T  To 
N A0 .H R
x
To calculate the time of reaction the above equation is
mt.cv subs. in material balance equation of BR
x
dx
t  N A0 
0
 rA .V

Example
For 1st. order reaction constant volume
 rA  kC A0 (1  x)  rA  ( Ae  E / RT )C A0 (1  x)
E
 rA  A exp[ ]C A0 (1  x )
N A 0 .H R
R (T0  x)
mt .cv
By subs. in design equation of BR to calculate the time of reaction:
x
N dx
t  A0
V  E
0 C A0 (1  x)[ A exp
N .H R
R (T0  A0 x)
mt .cv
x
C dx
t  A0
C A0  E
0 (1  x )[ A exp
N A0 .H R
R (T0  x)
mt .cv

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Reactor design
Chapter Four

This equation can be solved by Simpson rule to calculate the time of reaction at a given
conversion.

b) with heat exchange:

E.B
dT  N A0 .H R dx UA
  (Ts  T ) ………. Eq1
dt mt .cv dt mt .cv

M.B
dx  rA .V

dt N A0
dx Ae  E / RT C A0 (1  x ).V
(n=1,  =0)

dt N A0
dx
dt
 Ae  E / RT (1  x) …………..Eq2
Eq1 and Eq2 is solved by Euler method.

Example 1
What should be the removing heat to maintain the 10 lit of batch reactor isothermal for the
reaction A B, (k= 0.05 min-1) at 300 K, HR30 0K= -20 kCal/mol A, CA0= 2 mol/lit
and 90% conversion ?.

Solution
From E.B
Qexternal= - QGeneration
Qexternal= H R (rA .V )
From M.B
-rA=kCA0(1-x) [n=1,  =0] sbs. In E.B equation

Qexternal= H (kC (1  x).V )

R A0 …….. eq.1
kCal mol
Qexternal=  20 mol * 0.05 min * 2 llit (1  0.9).10lit
1

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Reactor design
Chapter Four

Qexternal= -2 kCal/min

We can draw the relationship between Qexternal with time of reaction from:
x
dx
t  C A0 
0
kC A0 (1  x ) Time (min)
5
1
t ln(1  x )  46 min
k
0
x  1  e kt 0 10 20 30 40 50
By subs. The last equation in eq.1 -5

external(kCal/min)
Qexternal  H R ( kC A 0 e  kt ).V
conversion &Q -10

-15

-20

-25
We can draw the relationship between Temperature (Ts)&of
heat removal coolant
conversion with coil
time with time of
reaction …. H.w

Energy Balance on Plug flow reactor

M.B on PFR
x
dx
V  FA 0  By differentiation
0
 rA
dx  rA
   rA .dV  FA0 .dx
dV FA 0
E.B on PFR
 Ft cpmix dT  UdA(Ts  T )  H R (  rA .dV )  0
Ft cpmix dT  UdA(Ts  T )  H R ( FA0 .dx)  0
divided by dV

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Reactor design
Chapter Four

dT UdA H R FA0 dx
 (Ts  T )  .
dV Ft cpmix dV Ft cpmix dV
dA DdZ 4
 
dV (D / 4)dZ
2
D

dT 4U F H R dx
 (Ts  T )  A0 . E.B equation of PFR
dV DFt cp mix Ft cp mix dV

Ft : Total mole flow rate of out let mixture

D : Reactor diameter
cpmix : Average heat capacity of inlet and outlet mixture
cpmixin  cpmix out
cpmix 
2
cpmix in  yi cpi

Operation Conditions
dT
1- Isothermal operation : (T=T0) dV
0

a) adiabatically (Qexternal=0)
There is no heat effect on reaction rate or reactor volume
There is no need to heat balance on reactor.

b) with heat exchange:

Qexternal= - QGeneration
4U F .H R dx
(Ts  T )  A0 .
DFt cp mix Ft cp mix dV
4U dx
solved with M.B equation through (dx/dV)
(Ts  T )  FA0 H R .
D dV

2- Non-isothermal operation: (T0≠ T)

a) adiabatically: (Qexternal =0)
dT F H R dx
  A0 .
dV Ft .cp mix dV
F H R
T  T0  A0 x Adiabatic Temperature (outlet temperature)
Ft cpmix

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Reactor design
Chapter Four

b) with heat exchange:

dT 4U F H R dx
 (Ts  T )  A0 .
dV DFt cp mix Ft cp mix dV

Example 2
106 kmol/hr of gas mixture at 900 k and 5 atm passed through tube of 10 cm long. The data
for reaction A + B D, are:
Feed composition is : 40% mol A, 40% mol B, 20 % mol inert
cpA =cpB = 6 cal/mol.K, cpD = 10 cal/mol.K, cpI = 5 cal/mol.k
k777K=4.87*108 lit/mol.hr, k834K = 18.1 *108 lit/mol.hr
 HR= 8900 cal/mol A.
Find the reaction volume for 4% conversion under adiabatic temperature, then compare it
with the isothermal volume.

Solution
E.B
For the adiabatic temperature:
FA0 H R
T  T0  x
Ft cpmix

component Reactor Feed Reactor Effluent θi

A =0.4*109 1

B 0.4*109 1

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Reactor design
Chapter Four

D 0 0

Inert 0.2*109 0.5

 Ft  FA  FB  FI  FD

Ft  FA0 [(1  x)  (1  x)  0.5  x

Ft  FA0 ( 2.5  x)
at x=0 Ft=Ft0=2.5FA0
at x=0.04 Ft=2.46 FA0
cpmixin  cpmix out
cpmix 
2
cpmix in  yi cpi
cpmixin  ( y A in * cp A )  ( y B in * cp B )  ( y I in * cp I )
cpmixin  (0.4 * 6)  (0.4 * 6)  (0.2 * 5)
cpmixin  5.8Cal / mol.K
cpmix out  yi cpi
cpmixout  ( y A out * cp A )  ( y B out * cpB )  ( y I out * cpI )  ( y Dout * cpD )
FA F F F
cpmixout  ( * 6)  ( B * 6)  ( I * 5)  ( D * 10)
Ft Ft Ft Ft
FA0 (1  x) F (1  x) 0.5 FA0 FA0 x
cpmixout  ( * 6)  ( A0 * 6)  ( * 5)  ( * 10)
FA0 (2.5  x) FA0 (2.5  x) FA0 (2.5  x ) FA0 (2.5  x )
cpmixout  5.86Cal / mol.K
cpmix  5.83Cal / mol.K
By subs. Ft and cpmix in adiabatic temp. equation

FA0 * 8900
T  900  x
2.46 FA0 * 5.83

T  900  610.634 x …………. Eq1

M.B
 rA  kC A C B
1 x   b / ax
 rA  kC A0 ( )C A 0 ( B )
1  x 1  x
2 1 x 2 2 1 x 2
 rA  kC A0 ( )   rA  kC A0 ( )
1  x 1  0.4 x
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Reactor design
Chapter Four

k1 E 1 1
ln  [  ]
k 2 R T2 T1
T1 = 777 K k1= 4.87*108
T2 = 834 K k2= 18.1*108
E/R=7974.88 A= 1.396 *1013 lit/mol.hr
7974.88
k  1.396 * 1013 exp( )
T
By subs in reaction rate equation:
7974.88 2 1 x 2
 rA  1.396 *1013 exp(  )C A0 ( ) …….. Eq2
T 1  0.4 x
By subs Eq1 . in Eq2.

7974.88 2 1 x 2
 rA  1.396 *1013 exp(
900  610.634 x
)C A0 (
1  0.4 x
) ……. Eq.3

x
dx
V  FA0 
0
 rA
0.04
dx
V  FA0 
0 1.396 *1013 exp(
7974.88 2 1 x 2
)C A 0 ( )
900  610.634 x 1  0.4 x
0.04
FA0 dx
2 
V  13
1.396 *10 * C A0 0 exp( 7974.88 1 x 2
)( )
900  610.634 x 1  0.4 x
To calculate the adiabatic volume of PFR , the last equation solved by Simpson’s rule

y A0 PT 0 0.4 * 5atm
C A0    0.027mol / lit
RT atm.m 3
0.082 * 900 K
mol.K
FA 0  y A0 * Ft 0  FA0  0.4 *10 9 mol / hr
0.04
dx

2
V  3.93 *10
7974.88 1 x 2
0 exp( )( )
900  610.634 x 1  0.4 x
x y
0 7051.374 Y0
0.005 7311.332 Y1
0.01 7581.707 Y2
0.015 7863.765 Y3
0.02 8164.46 Y4
0.025 8471.004 Y5
0.03 8794.251 Y6
0.035 9132.233 Y7
0.04 9485.6 Yn

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Reactor design
Chapter Four
h
A [ y 0  y n  4 y odd  2 y even ]
3
A  327.892
V  3.93 * 10  2 A
V  12.888lit

To calculate the isothermal volume :

0.04
FA0 dx
V 
1.396 *1013 * C A0
2 
0 exp(
7974 . 88 1 x 2
)( )
900 1  0.4 x
0.04
0.4 *109 dx
V 
7974 . 88  1  x 2
1.396 *1013 * exp( ) * (0.027) 2 0 ( )
900 1  0.4 x
0.04
dx
V  277.154 
0 (
1  x 2
)
1  0.4 x
0.04 0.04
1  0.4 x 2 (1  0.4) 2 2(0.4)(1  0.4)
0 1  x
( )  0 (1  x) 2  1 x
 (0.4) 2

0.04
1  0.4 x 2 1 1

0
(
1 x
) dx  0.36 * [
1  0.04
 1]  0.48 * ln[
1  0.04
]  0.16

0.04
1  0.4 x 2

0
(
1 x
) dx  0.195

V  54.045lit

Energy Balance on Continuous Stirred Tank reactor:

Ft cpmix (T  T0 )  UA(T  Ts )  FA0 ( x  x0 )H R  0

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Reactor design
Chapter Four

M.B
V x

FA 0  rA

Operation Conditions
1- Isothermal operation : (T=T0)
a) adiabatically (Qexternal=0)
There is no heat effect on reaction rate or reactor volume
There is no need to heat balance on reactor.

b) with heat exchange:

UA(T  Ts )   FA0 ( x  x0 ) H R

Ts  T0 
H R FA 0
x
[FA0.x=-rA.V]
UA

2-Non-isothermal operation: (T≠T0)

a) adiabatically; (Qexternal=0)

FA0 H R
T  T0  x
Ft cpmix
Adiabatic Temperature which solved with M.B to obtain adiabatic volume of reactor

c) with heat exchange:

H R FA0 UA
T  T0  x (T  Ts )
cpmixFt cpmixFt
Outlet temperature susbs. In M.B to calculate the reactor volume.

Example 3
The first order reaction A B is carried out in the gas phase with inlet temperature 500 K and
4 atm, the feed is pure A
Data:
Cpmix = 58 kJ/kmol.K
Heat of reaction = -15380 kJ/kmol A
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Reactor design
Chapter Four

k = 1.3 *109 e-15000/T

Q0 = 0.2 m3/sec

1- For adiabatic CSTR with 3 m3, find the outlet temperature and conversion.
2- For adiabatic PFR, find the reactor volume for 50% conversion.

Solution
E.B
FA0 H R
T  T0  x
Ft cpmix

Ft  FA  FB
Ft  FA0 (1  x)  FA0 x
Ft  FA0
15380FA 0
T  500  x
58 FA0
T  500  265.17 x
M.B
y A0 .PT 0 1* 4
C A0    0.098kmol / m 3
RT0 0.082 * 500
FA0  Q0 C A0  0.2 * 0.098  0.0195kmol / sec
 rA  kC A0 (1  x )
 rA  1.3 * 10 9 exp(15000 / T )C A0 (1  x )
1- for CSTR
V x

FA 0  rA

3 x

0.0195 1.3 * 10 * 0.098(1  x) exp( 15000 / T )
9

x
19.6 * 10 9 
 15000
(1  x) exp[ ]
(500  265.17 x)
By trail & error
X=0.5
T=632.585 K.

2-For PFR:

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Reactor design
Chapter Four
x
dx
V  FA0 
0
 rA
x
V * 0.098 *1.3 *109 dx

0.0195 0 (1  x ) exp
 15000
500  265.17 x
By Simpson’s rule:
x y
0 1.069*1013 Y0
0.1 2.621*1012 Y1
0.2 7.522*1011 Y2
0.3 2.485*1011 Y3
0.4 9.343*1010 Y4
0.5 3.973*1010 Yn
h
A [ y0  yn  4 yodd  2 yeven
3
A=7.469*1011

Sheet NO. 4
Q1/ It is desired to produce 0.045 mol/liter of C from the following exothermic reaction liquid
phase reaction 2A C + D in a mixed flow reactor with 45% conversion calculate:
1- the volume of reactor and temperature of coolant coil if it is operated isothermally.
2- the volume of reactor and outlet temperature if it is operated adiabatically.
Data:-
Feed temperature 77 0C

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 Reactor design
Chapter Four

UA= 1200 J/min.K

Specific reaction rate constant k at 0 0C= 0.02m3/kmol.min.
Activation energy (E)=4000 kJ/kmol
Heat of reaction = - 8000 kJ/kmol
Heat capacity of mixture= 20 kJ/kmol.K
Volumetric feed flow rate =30 liter/min.

Q2 /The first order gas phase reaction A B is to be carried out in an adiabatic CSTR. If 0.6
0
kmol/hr of pure A is fed to reactor at 60 C and 2 atm. Calculate the outlet temperature , and
reactor volume at 70% conversion.
k1 = 1.08*105 exp(-5050.5/T)
K= 2.5*108 exp[(10000/T)-25.25]
cpA = 84 j/mol .K
cpB = 252 j/mol .K
∆HR = -8.4*104 j/mol A

Q3/ At what time and conversion the energy can be removed from 0.02 m3 batch reactor operated
with first order liquid phase reaction A B in order to keep the temperature constant. The
following data :
T0= 300 K
k (300 K)= 0.05 min-1
∆HR = -20 kCal/mol A
CA0 = 2 mol/lit
Q = - 2 kCal/min

Q4/ It is desired to fed 0.002 m3/s of pure acetone (gas phase) into a tubular reactor (2.5 cm
diameter) at 1035 K. The external heating energy is supplied to maintain the operation isothermal
with 20% conversion.
C3H6O C2H2O + CH4
1- Calculate the volume of the isothermal reactor.
2- Determine the temperature profile of reactor surface down the tube.
CA0 = 18.8 mol/ m3
k(1035 K) = 3.85 s-1
∆HR = 78.758 j/mol acetone, U = 0.11 j/ m2.s.K

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 Reactor design
Chapter Four

Q5/ The elementary gas phase reaction (A B) is to be carried out in CSTR (V=3 m3)
followed by a PFR.A feed stream of pure A enters the CSTR at a volumetric flow rate of 3.79
m3/hr and 25 0C. It is desired to achieve 97% total conversion.
1- Calculate the temperature and conversion for the outlet stream from CSTR if it is operated
adiabatically.
2- Determine the length of PFR if it is operated isothermally (ID= 25 cm).
k= 9.078*1015 Exp (-14570/T) hr-1
∆HR = - 41633 kJ/kmol A
cpmix = 2.93 kJ/kg.k
Mwt=90 kg/kmol

Q6/ A liquid stream (70% mol A & 30% mol inert) enters a CSTR at 27 0C, at a rate of 50
liter/min in which the following reaction take place A B+C. Find the reactor volume for
90% conversion and the outlet temperature for the following cases:
1-Adiabatic operation.
2- with 34.2 kcal/min of heat added to reactor.
Data:
CpA= 4 cal/mol.K , CpB= 2.4 cal/mol.K , CpC= 5 cal/mol.K , Cpinert= 4.5 cal/mol.K
k = 2.6*1017 exp(-12581.8/T) hr-1
∆HR= -300 cal/mol A
CA0 = 2 mol/liter

Q7/ The exothermic gas phase reaction 2A C+D is carried out in a CSTR to achieve 45%
of A. Pure A is fed at pressure of 2.87 atm and a temperature of 77 0C. Calculate the volume and
operating temperature of reactor.
DATA
Coolant temp.= 57 0C
U.A=1200 J/min.K
Specific reaction rate constant (k) at 0 0C=0.02 m3/kmol.min
Activation Energy (E)= 4000 kJ/kmol
Heat of reaction = -80000 kJ/kmol A
Cp = 20 Kj/kmol.K
Volumetric flow rate = 30 liter/min

Q8/ Determine the operating temperature for 90% conversion required to produce 400 kg of Y
in 6000 min for the irreversible reaction Z Y, under :
1- Isothermal operation.
2- Adiabatic operation with feed temperature of 92 0C.
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 Reactor design
Chapter Four

Data
k =2.7* 1014 exp (-15000/T) (min-1) , where T in K
∆Hr = - 85 Cal/mol Z
Heat capacity of mixture (cv) = 0.48 Cal/g.K, Mwt Z= Mwt Y = 24 g/mol

Q9/ The first order gas phase reaction A B is to be carried out in an adiabatic CSTR. If 0.6
kmol/hr of A with 40% inert is fed to reactor at 60 0C and 2 atm. CB0=0. Calculate the outlet
temperature , and reactor volume at 70% conversion.
k1 = 1.08*105 exp(-5050.5/T) (hr-1)
K= 2.5*108 exp[(10000/T)-25.25]
cpA = 84 j/mol .K
cpB = 252 j/mol .K
∆HR = -8.4*104 j/mol A

16