Reactor Design Non-Isothermal Reactions

Week 7 Chapter Eight, Steady-State Nonisothermal Reactor Design, Part1

Outline

1. Introduction (Non-isothermal Reactions)

2. The Energy Balance

Reactor Design Non-Isothermal Reactions

Introduction
Consider A B Exothermic, first-order reaction
Adiabatic PFR reactor
Thus temperature will increase with conversion down the length of the reactor

dX rA
1. Mole balance
dV FA0
2. Rate Law rA kCA
k k0 exp( E / RT ) Arrhenius equation

3. Stoichiometry v v0 Liquid phase

FA C Av0
FA0 C A0v0
FA C FA
A C A C A0 C A0 (1 X )
FA0 C A0 FA0
Reactor Design Non-Isothermal Reactions

4. Combining dX rA FA C Av0

dV FA0
dX kCA0 (1 X ) k (1 X )
rA kCA
dV C A0v0 v0
k k0 exp( E / RT )
dX k0 exp( E / RT )(1 X )

dV v0 FA
C A C A0 C A0 (1 X )
We need another equation relating X and T, or FA0
T and V
HRx Heat of Reaction
5. Energy Balance
CPA Heat Capacity
H Rx
T T0 X Adiabatic energy balance Levenspiel plot
CPA
FA0 / -rA
We can now solve the problem.
We can determine -rA as a function of X.
Choose X Calculate T
Calculate k Calculate -rA Calculate (FA0 / -rA)
X
Reactor Design Non-Isothermal Reactions

The Energy Balance (Neglecting potential, kinetic and other form of energy, Ei = Ui)
Ui = Internal energy
n n dE sys Hi = Enthalpy
F
i 1
i0 H i 0 Fi H i Q Ws
i 1 dt Units: [W] = [J/s], [cal/s]

(Energy flow IN) - (Energy flow OUT) + (rate of heat into) - (shaft work) = (rate of accumulation of energy)

n n
At steady-state, no shaft
work
F
i 1
i0 H i 0 Fi H i Q 0
i 1

b c d
Consider the reaction: A B C D
n
a a a
(Energy flow IN) Fi 0 H i 0 FA0 H A0 FB0 H B0 FC 0 H C 0 FD0 H D0 FI 0 H I 0
i 1
n
(Energy flow OUT) FH
i 1
i i FA H A FB H B FC H C FD H D FI H I
Fi 0
where: Fi FA0 (i i X ) i
FA0
 Reactor Design Non-Isothermal Reactions
n
(Energy flow IN) F
i 1
i0 H i 0 FA0 H A0 FB 0 H B 0 FC 0 H C 0 FD 0 H D 0 FI 0 H I 0
n
(Energy flow OUT) FH
i 1
i i FA H A FB H B FC H C FD H D FI H I
Fi 0
where: Fi FA0 (i i X ) i
FA0
n
b c

i 1
Fi H i FA0 (1 X ) H A FA0 ( B X ) H B FA0 (C X ) H C
a a
d
n n
FA0 ( D X ) H D FA0 I H I
Fi 0 H i 0 Fi H i
i 1 i 1
a
FA0 B H B 0
b
( FA0 H A0 FA0 H A FA0 XH A ) ( FB 0 H B 0 FA0 B H B FA0 X HB)
a
FA0C H C 0 FA0 I H I 0
c
( FC 0 H C 0 FA0 C H C FA0 X H C ) ... ( FI 0 H I 0 FA0 I H I )
a
FA0 ( H A0 H A ) ( H B 0 H B ) B ( H C 0 H C )C ... ( H I 0 H I ) I
d c b
H D H C H B H A FA0 X
a a a
Reactor Design Non-Isothermal Reactions

n n

F
i 1
i0 H i 0 Fi H i Q 0
i 1
n n

F
i 1
i0 H i 0 Fi H i
i 1

FA0 ( H A0 H A ) ( H B 0 H B ) B ( H C 0 H C )C ... ( H I 0 H I ) I
d c b
H D H C H B H A FA0 X
a a a

H Rx (T )

Heat of reaction d c b
H Rx (T ) H D (T ) H C (T ) H B (T ) H A (T )
at temperature T a a a
Units: [J / mol of A reacted]

Steady-State n
Energy Balance, FA0 i ( H i 0 H i ) H Rx (T ) FA0 X Q 0
no shaft work i 1
Change in enthalpy
Reactor Design Non-Isothermal Reactions

Steady-State n n

Energy Balance, F
i 1
i0 H i 0 Fi H i Q 0
i 1
Starting point!
no shaft work

Steady-State n

Energy Balance, FA0 i ( H i 0 H i ) H Rx (T ) FA0 X Q 0

no shaft work i 1

Steady-State No Hi 0 Hi CPi (Ti 0 T)

phase change,
constant CP , no n
shaft work FA0 i CPi (T Ti 0 ) H Rx (T ) FA0 X Q 0
Energy Balance i 1

Heat of reaction TR = Reference Temperature

at temperature T
H Rx (T ) H Rx

(TR ) CP (T TR ) =298K

d c b CP = Overall change in the heat

where: CP CPD CPC CPB CPA capacity per mole of A
a a a reacted

Steady-State No
phase change,

n
constant CP , no FA0 i CPi (T Ti 0 ) H Rx

(T ) CP (T TR ) FA0 X Q 0
shaft work i 1
Energy Balance
 Reactor Design Non-Isothermal Reactions

Week 7 Chapter Eight, Steady-State Nonisothermal Reactor Design, Part 2

Outline
1. Adiabatic Operation

2. Adiabatic Tubular Reactor

Reactor Design Non-Isothermal Reactions
Adiabatic Operation
Reactor in industry are frequently carried out adiabatically with heating or cooling
upstream or downstream.
Steady-State No

phase change, n
constant CP , no FA0 i CPi (T Ti 0 ) H Rx

(T ) CP (T TR ) FA0 X Q 0
shaft work i 1
Energy Balance

Steady-State No
phase change,

n
constant CP , no
shaft work, FA0 i CPi (T Ti 0 ) H Rx

(T ) CP (T TR ) FA0 X 0
i 1
adiabatic,
Energy Balance Adiabatic
exothermic
reaction
XEB
Rearranging
iCPi (T Ti 0 ) iCPi (T Ti 0 )
CSTR
X
PFR
X
[H (TR ) CP (T TR )]

Rx
H Rx

(TR ) PBR
Batch

In many cases is negligible T

Reactor Design Non-Isothermal Reactions

Adiabatic Tubular Reactor

X
C i Pi (T Ti 0 )
[H Rx

(TR ) CP (T TR )]
Rearranging and solving for T

X
C i Pi T i CPi Ti 0
H Rx

(TR ) CPT CPTR

X [H Rx

(TR )] XCPT XCPTR i CPi T i CPi Ti 0

T C
i Pi
XCP X [H Rx

(TR )] XCPTR i CPi Ti 0

Energy balance equation X [H Rx

(TR )] XCPTR i CPi Ti 0
T
C i Pi XCP

Mole balance equation dX

FA0 rA ( X , T )
dV
X T k(T) -rA Size the reactor (Chapter 2)
Reactor Design Non-Isothermal Reactions

Adiabatic Tubular Reactor

Energy balance equation X [H Rx

(TR )] XCPTR i CPi Ti 0
T
C i Pi XCP

Mole balance equation dX

FA0 rA ( X , T )
dV

We prefer using a ODE solver (MATLAB or Polymath) to solve coupled energy

and mole balance differential equations
Reactor Design Non-Isothermal Reactions

Adiabatic PFR/PBR algorithm

Elementary reversible gas-phase
Consider A B reaction, no pressure drop, pure
A enters the reactor
dX rA
1. Mole balance (1)
dV FA0
CB (2)
2. Rate Law
rA k C A
KC
E 1 1
k k1 exp Arrhenius equation (3)
R T1 T
H Rx 1 1 Vant Hoff
K C K C 2 (T2 ) exp (4)
equation
R T2 T
3. Stoichiometry Gas phase 0, P P0
T0
C A C A0 (1 X ) (5)
T
T0 (6)
C B C A0 X
T
Reactor Design Non-Isothermal Reactions

4. Combine X T0 (7)
rA kCA0 (1 X )
KC T

5. Energy Balance X [H Rx

(TR )] XCPTR i CPi Ti 0
T
C i Pi XCP

If pure A enters and if CP 0

X [H Rx

(TR )] ACPA T0 A 1
T
ACPA

X [H Rx

(TR )]
T T0 (8)
CPA
Equations 1 to 8 can be solved by:
A. Using a numerical technique and Simpsons rule/Levenspiel plot
B. Using a ODE solver such as Polymath or MATLAB
Reactor Design Non-Isothermal Reactions
dX rA
A. Numerical technique
X3 FA0
Integrating the PFR mole balance V dX dV FA0
0 rA
1. Set X = 0
X [H Rx
(TR )]
2. Calculate T T T0
CPA
E 1 1
3. Calculate k k k1 exp
R T1 T
H Rx 1 1
4. Calculate Kc K C K C 2 (T2 ) exp
R T2 T
5. Calculate T0
T
X T0
6. Calculate -rA rA kCA0 (1 X )
KC T
FA0
7. Calculate
rA
F
8. If X X 3 , X i 1 X i X go to Step 2 9. Prepare table of X vs. A0 ,
r
integrate A
Reactor Design Non-Isothermal Reactions

B. ODE Solver
X T0
1. rA kCA0 (1 X )
KC T
E 1 1
2. k k1 exp
R T1 T
H Rx 1 1
3. K C K C 2 (T2 ) exp
R T2 T
X [H Rx

(TR )]
4. T T0
CPA

5. Enter parameter values k1, CA0, E, R, KC2, H Rx

, CPA,T0, T1, T2.

6. Enter initial values X = 0, V = 0 and final value of reactor volume V = Vf

Reactor Design Non-Isothermal Reactions
Example 8.3 Liquid Phase Isomerization of Normal Butane
Normal butane, C4H10, is to isomerized to isobutane in a flow reactor. Isobutane is more
valuable than Normal butane and sells higher. The reaction is to be carried out adiabatically in
liquid phase under high pressure using trace liquid catalyst. Additional information:

Ho Rx 6900 J/mol butane CPnB 141 J / (kmol K) C A0 9.3 kmol / m3

E 65.7 kJ/mol CPiB 141 J / (kmol K) k 31.1 h -1 at 360 K
KC 3.03 at 60 CPi P 161 J / (kmol K) T feed 330 K
- Calculate the PFR volume necessary to process 163 kmol/h at 70% conversion of a
mixture of 90 mol % n-butane and 10 mol % i-pentane inert.

PFR Solution A B
dX rA V
FA0
X3
1. Mole balance (PFR) 0 r
dX
dV FA0 A
CB E 1 1
2. Rate law rA k C A k k1 exp
KC R T1 T
H Rx 1 1
K C K C 2 (T2 ) exp
R T2 T
Reactor Design Non-Isothermal Reactions

3. Stoichiometry Liquid phase v v0 C A C A0 (1 X ) C B C A0 X

X
rA kCA0 (1 X )
4. Combine C
rA k C A B
KC KC

5. Energy balance Adiabatic, no shaft work, steady state, constant Cp

X [H Rx

(TR )] XCPTR i CPi Ti 0
T
C i Pi XCP

CP CPB CPA 141 141 0

H Rx (T ) H Rx
X [H ]
T T0 Rx
H Rx (TR ) H Rx

iCPi
H Rx H Rx

C p (T TR )
6. Parameter evaluation
0.1
i Pi PA i Pi
C C C 141
0.9
161 159 J/(mol K)

X [(6900)]
T 330 330 43.4 X
159
Reactor Design Non-Isothermal Reactions

65,700 1 1 T 360 1
k 31.1exp 31.1exp 7906 ( h )
8.31 360 T 360T

6,900 1 1 T 333
K C 3.03 exp 3.03 exp 830.3
8 .31 333 T 333 T

7. Equilibrium conversion
At equilibrium,
X Xe
KC
rA kCA0 (1 X ) 0
1 KC
KC
X e f (T )
Find the PFR volume to achieve 70% conversion and plot X , X e ,rA and T

Risky question! For reversible reaction we should ask to achieve 95% of Xe

Xf = 0.95 Xe
Reactor Design Non-Isothermal Reactions

A) Solution by hand calculation - Numerical technique

1. For example, at X = 0.2

2. Calculate T T 330 43.4(0.2) 338.6K

338.6 360
3. Calculate k k 31.1exp 7906 7.76(h 1 )
360(338.6)
4. Calculate Kc 338.6 333
K C 3.03 exp 830.3 2.9
333(338.6)
KC 2.9
5. Calculate Xe Xe 0.74
1 K C 1 2.9

7.76(9.3) (1 0.2)
X 0.2 kmol
6. Calculate -rA
rA kCA0 (1 X ) 52.8 3
KC 2.9 m .h

FA0 FA0 (0.9mol butane/mol total)(163 kmol total/h)

7. Calculate 2.78 m3
r rA kmol
A 52.8 3
m .h
Reactor Design Non-Isothermal Reactions

A) Solution by hand calculation - Numerical technique

FA0

X T k Kc Xe -rA
rA

0 330 4.22 3.1 0.76 39.2 3.74

0.2 338.7 7.76 2.9 0.74 52.8 2.78
0.4 347.3 14.02 2.73 0.73 58.6 2.5
0.6 356.0 24.27 2.57 0.72 37.7 3.88
0.65 358.1 27.74 2.54 0.718 24.5 5.99
0.7 360.3 31.67 2.5 0.715 6.2 23.29

Construct a Levenspiel Plot

Reactor Design Non-Isothermal Reactions

A) Solution by hand calculation - Numerical technique

Use Simpson's one third rule or three-eighths rule to evaluate the reactor
volume for 70% conversion

Simpsons three-eighths rule Simpsons one third rule

X3 X2

X f ( X )dX
3
h f ( X 0 ) 3 f ( X 1 ) 3 f ( X 2 ) f ( X 3 ) X f ( X )dX
h
f ( X 0 ) 4 f ( X 1 ) f ( X 2 )
8 0
3
0

X3 X0 X2 X0
where h X 1 X 0 h X 2 X 0 2h where h X1 X 0 h
3 2

0.7 0.6 0.7

F F F
V A0 dX A0 dX A0 dX
0
rA 0
rA 0.6
rA

X3 X0 0.1
h1 h2
3 2
0.6
0.2 0.05
3
Reactor Design Non-Isothermal Reactions

A) Solution by hand calculation - Numerical technique

0.6 0.7
0.7 FA0 FA0 FA0
V
dX dX dX
0 rA 0
rA 0.6
rA
3 0.6 FA0 FA0 FA0 FA0
x ( 0) 3 ( 0.2 ) 3 ( 0.4) ( 0.6)
8 3 rA rA rA rA
1 0.1 FA0 FA0 FA0
x (0.6) 4 (0.65) (0.7)
3 2 rA rA rA
3 0.6
x 3.74 3(2.78) 3(2.5) 3.88 x 3.88 4(5.99) 23.29m3
1 0.1
8 3 3 3

1.75 0.85 m3
2.60 m3

At the exit, V=2.6 m3, X=0.7, Xe=0.715 and T=360 K

Reactor Design Non-Isothermal Reactions

B) Computer Solution ODE solver

Differential equation as entered by the user

dX rA

dV FA0

Explicit equations as entered by the user

1. C A0 9.3 kmol / m3

2. FA0 0.9x0.163

3. T 330 43.4 X
T 333
4. K C 3.03 exp 830.3
333T
T 360
5. k 31.1exp 7906
KC 360T
6. Xe
1 KC
X
7.
rA kCA0 (1 X )
KC