LESSON TWO: STEADY-STATE NON-ISOTHERMAL REACTIONS
To understand the heat effects in reactor design lets
consider a situation wherein we are interested in
determing the volume (V) of a PFR.
The reaction is first-order, exothermic and adiabatic
The conversion is given as X
Design Steps:
dX rA
[Link] Balance:
dV FA0
E 1 1
rA ki exp C A
[Link] Law: R T1 T
C A C A0 1 X
[Link]:
E 1 1
ki exp
dX R T1 T
C A0 1 X
[Link]: dV FA0
2
5. Evaluate:
We cannot solve this equation because we don’t
have X either as a function of V or T.
We need another equation. That equation is:
The Energy Balance
Energy Balance
Reactor
Energy Balance
Q
Reactor
Rate of flow
of heat to the
system from
the
surroundings
Q
(J/s)
Energy Balance
Q W
Reactor
Rate of flow
Rate of work
of heat to the
system from - done by the
system on the
the
surroundings
surroundings
Q - W
(J/s) (J/s)
Energy Balance
Q W
Fin
Reactor
Ein
Rate of flow Rate of energy
Rate of work
of heat to the added to the
system from - done by the
system on the
+ system by
the mass flow into
surroundings
surroundings the system
Q - W + Fin Ein
(J/s) (J/s) (J/s)
Energy Balance
Q W
Fin Fout
Reactor
Ein Eout
Rate of flow Rate of energy Rate of energy
Rate of work
of heat to the added to the leaving system
system from - done by the
system on the
+ system by - by mass flow
the mass flow into out of the
surroundings
surroundings the system system
Q - W + Fin Ein - Fout Eout
(J/s) (J/s) (J/s) (J/s)
Energy Balance
Q W
Fin Fout
Reactor
Ein Eout
Rate of Rate of flow Rate of energy Rate of energy
Rate of work
accumulation of heat to the added to the leaving system
of energy = system from - done by the
system on the
+ system by - by mass flow
within the the mass flow into out of the
surroundings
system surroundings the system system
dEˆ sys
dt = Q - W + Fin Ein - Fout Eout
(J/s) (J/s) (J/s) (J/s) (J/s)
Energy Balance
Q
Fi in Fi out
e.g., FA 0 e.g., FA
H i in H i out
e.g., H A 0 W S e.g., H
A
Energy Balance on an open system: schematic.
dE system
W
Q F E
S i 0 i 0 in FE
i i out 1
dt
10
To put the above equations into usable form, we
shall:
1. Replace Ui by Ui=Hi-PVi
2. Express Hi in terms of heat capacities
3. Express Fi in terms of either conversion or rates
of reaction
4. Define ΔHRx
5. Define ΔCP
6. Manipulate so that the overall energy balance
is in terms of ”User Friendly Equations”
11
Definitions and Assumptions:
=0 =0
E i U i PE i KEi Other energies small compared to internal
W flow work shaft work
~ ~ ~ m3
flow work Fi 0 P0 Vi 0 Fi PVi V
mol
Recall:
12
Substituting for
Steady State: W
Q F H F H 0
S i0 i0 i i
13
We know:
F H F H
i0 i0 A0 i i0
Therefore:
14
Further definitions:
For No Phase Changes
C
T
H i T H TR
0
i TR Pi dT
Enthalpy of formation at temperature TR
Constant Heat Capacities
H i T H i0 TR CPi T TR
H i0 H i CPi T T0
H H C T T
i i i
0
i i Pi R
Heat of reaction at temperature T
15
i i i i iCPi T TR
H H 0
d ˆ c ˆ b ˆ
iCPi CP a CPD a CPC a CPB Cˆ PA
ˆ ˆ
Substituting back into the Energy Balance
Adiabatic (Q=0) and no Work (WS 0)
16
Further definitions:
d c b
H Rx HD HC HB HA
a a a
d c b
C P C PD C PC C PB C PA
a a a
17
Adiabatic Energy Balance
Adiabatic (Q=0) and no Work (WS 0)
T T0
~
X H R TR Cˆ P T TR
T0
X H R T
~
i C Pi XCˆ P i C Pi XCˆ P
T
Exothermic
T0
X 18
User Friendly Equations Relate T and X or F i
1. Adiabatic CSTR, PFR, Batch or PBR
T T
H X
o
Rx EB
0
C i Pi
19
EXAMPLE ONE: DESIGN OF ADIABATIC CSTR AND COMPARISON WITH PFR
Adiabatic Operation CSTR
FA0
FI
A B
Elementary liquid phase reaction carried out in a CSTR
The feed consists of both - Inerts I and Species A with
the ratio of inerts I to the species A being 2 to 1.
20
Adiabatic Operation CSTR
Assuming the reaction is irreversible for CSTR,
A B, (KC = ) what reactor volume is necessary to
achieve 80% conversion?
If the exiting temperature to the reactor is 360K, what
is the corresponding reactor volume?
Make a Levenspiel Plot and then determine the PFR
reactor volume for 60% conversion and 95%
conversion. Compare with the CSTR volumes at
these conversions.
Now assume the reaction is reversible, make a plot of
the equilibrium conversion as a function of
temperature between 290K and 400K.
21
CSTR: Adiabatic Example
(exothermic)
FA0
FI
A B
𝑇=?
FA 0 X
1) Mole Balances: V
rA exit
22
CSTR: Adiabatic Example
Reversible Irrversible
2) Rate Laws: CB
rA k C A -rA= kCA
KC
E 1 1
R T1 T
k k1e
H Rx 1 1
K C K C1 exp
R T2 T
3) Stoichiometry: C A C A 0 1 X
C B C A 0 X
23
CSTR: Adiabatic Example
4) Energy Balance
Adiabatic, ∆Cp=0
T T0
H Rx X
T
H Rx X
0
i C Pi C PA I C PI
20,000 20,000
T 300 X 300 X
164 2 18 164 36
T 300 100 X
24
CSTR: Adiabatic Example
Irreversible for Parts (a) through (c)
rA kC A 0 1 X (i.e., K C )
(a) Given X = 0.8, find T and V
Calc Calc Calc Calc
Given X T k rA V
Calc KC
(if reversible)
25
CSTR: Adiabatic Example
Given X, Calculate T and V
FA 0 X FA 0 X
V
rA exit kC A 0 1 X
T 300 1000.8 380K
10,000 1 1
k 0.1 exp 3.81
1.989 298 380
V
FA 0 X
50.8
2.82 dm 3
rA 3.8121 0.8
26
CSTR: Adiabatic Example
(c) Levenspiel Plot
FA 0 FA 0
rA kC A 0 1 X
T 300 100X
Calc Calc Calc FA 0
Calc
Choose X T k rA
rA
27
CSTR: Adiabatic Example
(c) Levenspiel Plot
28
CSTR: Adiabatic Example
30
CSTR X = 0.6 T = 360 K
25
20
-Fa0/Ra
15
10
CSTR 60%
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CSTR X = 0.95 T = 395 K
29
CSTR: Adiabatic Example
30
PFR X = 0.6
25
20
-Fa0/Ra
15
10
PFR 60%
5
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
PFR X = 0.95
30
CSTR: Adiabatic Example - Summary
CSTR X = 0.6 T = 360 V = 2.05 dm3
PFR X = 0.6 Texit = 360 V = 5.28 dm3
CSTR X = 0.95 T = 395 V = 7.59 dm3
PFR X = 0.95 Texit = 395 V = 6.62 dm3
31
EXAMPLE TWO: ADIABATIC PFR
The feed consists of both inerts I and Species A with the ratio of inerts to the species A
being 2 to 1.
Plot X, Xe, T and Rate (Rate A = –rA) as a function of V for adiabatic operation.
SOLUTION
STEP ONE : MOLE BALANCE (1)
STEP TWO : RATE LAWS
(2)
(3)
Arrhenius Equation
(4) Van’t Hoff Equation
STEP THREE : STOICHIOMETRY (5)
(6)
STEP FOUR : EQUILIBRIUM
(7)
STEP FIVE : ADIABATIC ENERGY (8)
(Q= 0 ; WS = 0)
STEP SIX: GENERATE DATA
X T KC XE k1 rA FAO/-rA
0 300 1000 0,999001 0,1 0,2 25
0,1 310,2041 332,0216 0,996997 0,173547 0,31228 16,01128
0,2 320,4082 118,2583 0,991615 0,290793 0,464285 10,76924
0,3 330,6122 44,8923 0,97821 0,47197 0,654449 7,640009
0,4 340,8163 18,05932 0,947532 0,744131 0,859993 5,813999
0,5 351,0204 7,659903 0,884525 1,142585 0,99342 5,033117
0,6 361,2245 3,410273 0,773257 1,712401 0,767365 6,515808
0,65 366,3265 2,31427 0,698274 2,078705 0,287418 17,39626
0,667715 368,1342 2,022453 0,669143 2,223621 0,00949 526,8526
0,667715 368,1342 2,022453 0,669143 2,223621 0,00949 526,8526
0,667715 368,1342 2,022453 0,669143 2,223621 0,00949 526,8526
STEP SEVEN: DRAW LEVENSPIEL PLOT AND CALCULATE VOLUMES
30
25
20
FAO/-rA
15
10
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
X
STEP EIGHT: DETERMINE VOLUME VARIOUS CONVERSIONS ( Use trapezoidal or Simpsons rule to determine volume)
V X
0 0
2,05 0,1
3,39 0,2
4,31 0,3
4,98 0,4
5,53 0,5
6,1 0,6
6,7 0,65
7 0,6677
10 0,667715
10 0,667715
STEP NINE: PLOT X, Xe, T and Rate (Rate A = –rA) as a function of V for adiabatic operation
xe
Volume (m3)
Temperature in K
T vs V
Rate vs Volume
-rA
EXAMPLE THREE: ADIABATIC CSTR WITH HEAT EXCHANGE AND SHAFT WORK
1. The following reaction goes to 75% completion in a 300 liter CSTR. A and B are fed to the reactor at
identical rates of 1.5 mol/s at a temperature of 270C. Specific heats (in J/mol-K) of A, B and C are 200,
180 and 190, respectively.
A B 2C
The reactor is jacketed by water at a temperature of 200C. The overall heat transfer coefficient has been
estimated at 225 J/(m2.s.K), while the heat transfer area is 1 m2. Mixing is ensured through an agitator,
which contributes a work of 15 KW to the reactor. The heat of reaction is -35,000 J/mole of A. Calculate
the steady state temperature in the reactor by assuming that the heat of reaction is independent of
temperature.
SOLUTION
Q W
F H F H 0
S i0 i0 i i
STEADY STATE ENERGY BALANCE
INTRODUCING HEAT OF
REACTION AND CONVERSION
𝑄=𝑈𝐴(˙ 𝑇 −𝑇𝑎) Heat Transfer ( heat removed)
-= ()
( ) ˙ ˙
𝑈𝐴 𝑇−𝑇𝑎 − 𝑊 𝑆 +𝐹 𝐴𝑂 ∑ 𝜃𝑖 𝐶 𝑃𝑖 𝑇−𝐹 𝐴𝑂 ∑ 𝜃𝑖 𝐶 𝑃𝑖 𝑇 0+𝐹 𝐴𝑂 𝑋∆𝐻 𝑅𝑥=0−
˙
𝑈𝐴𝑇
+𝐹
𝐴𝑂
A
∑
𝜃
B
𝑖
=
𝐶
1
𝑃𝑖 𝑇=¿𝐹 𝐴𝑂 ∑
Use equation 8-50 from the text
= Equimolar
𝜃 𝑖 𝐶 𝑃𝑖 𝑇 0 −𝐹 𝐴𝑂 𝑋∆𝐻 𝑅𝑥 +𝑊𝑠+𝑈𝐴𝑇𝑎−¿
Q W
X H Rx = i C pi (T Ti 0 )
FA0
FA0 X ( H Rx ) F0 (C pA C pB )T0 UATa W
T 12 points
F0 (C pA C pB ) UA
1.5 0.75 (35000) 1.5 (200 180) 300 225 1 293 15000
T
1.5 (200 180) 225 1
=366.4 K
EXAMPLE FOUR: ADIABATIC BATCH REACTOR
Reagent A undergoes an essentially irreversible isomerization reaction that obeys first-order kinetics:
A→B
Both A and B are liquids at room temperature and both have extremely high boiling points. Determine the reactor
volumes necessary to produce 2 million kg of B in 7000 h of operation:
(a) If the reactor operates isothermally at 163∘C.
(b) If the reactor operates adiabatically.
Use the following data and assumptions.
Reaction rate expression r = kCA
Rate constant at 163∘C 0.8 h−1
Activation energy 28,960 cal/g-mol
Heat of reaction −83 cal∕g-mol
Molecular weight 250
The heat capacities of species A and B may be assumed to be identical and to be 0.5 cal/(g ⋅ ∘C). Their densities may be
assumed to be to 0.9 g/cm3 .
The times necessary to fill and drain the reactor are 10 and 12 min, respectively. It may be assumed that negligible
reaction occurs during the 14 min it takes to heat the feed from the temperature at which it enters the reactor to
163∘C. After 97% of the A has been isomerized, the hot product mixture is discharged to a cooling tank.
SOLUTION
STEP 4: GENERATE DATA OF 1/[k2 (1-x)] vs x
X Y
X k2 1/[k2*(1-x)]
0,005 0,852928 1,178323
0,1 2,755187 0,40328
0,2 8,693815 0,14378
0,3 25,36084 0,05633
0,4 68,92731 0,02418
0,5 175,7284 0,011381
0,6 422,764 0,005913
0,7 964,7878 0,003455
0,8 2098,216 0,002383
0,9 4366,49 0,00229
0,97 7118,669 0,004683
STEP 5: DRAW THE CURVE AND DETERMINE AREA UNDER THE CURVE
Area under the
-1/rA
curve = 0.124 hrs
Conversion, X
Total batch time = 0.124 + (14+10+12)/60 = 0,724 hrs
Number of batches = 7000 hr/ 0,73 hr per batch = 9669 batches
Mass per batch = 2 000 000/9669 = 206.85 kg
Volume of reactor = 206.85/900 = 0.23 m3