Lecture 24

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.
 Web Lecture 24
Class Lecture 20 - Tuesday 3/26/2013
CSTR With Heat Effects
—  Multiple Steady States
—  Ignition and Extinction Temperatures

2
 CSTR with Heat Effects

Courtesy of Pfaudler, Inc.

3
 Unsteady State Energy Balance
! !
n n dÊ sys
Q − WS + ∑ Fi 0 H i 0 − ∑ Fi H i =
i =1 i =1 dt
Neglect

Using Ê sys = ∑ Ni E i = ∑ Ni (H i − PVi ) = ∑ N i H i − PV

dE sys d∑ Ni Hi dH i dN i
= = ∑ Ni =∑ H i
dt dt dt dt
dH i dT
= C Pi
dt dt
dN i
= −υi rA V + Fi 0 − Fi
4
dt
 Unsteady State Energy Balance
We obtain after some manipulation:

dT Q ! −W
! − ∑ F C (T − T ) + [− ΔH (T )](− r V )
S i 0 Pi i0 Rx A
=
dt ∑ NiCPi

Collecting terms with Q! = UA(Tand a − T)

! = 0 flow
high coolant
WS
rates, and Fi 0 = FA 0Θi

5
 Unsteady State Energy Balance
⎡ C ⎤
P
⎢ $
!#! 0" ⎥
(ΔH Rx )(rA V ) − ⎢⎢FA 0 ∑ Θi C Pi (T − T0 ) + (UA(T − Ta ))⎥⎥
⎢ ⎥
dT ⎢⎣ ⎥⎦
=
dt ∑ N i C Pi
⎡ R⎛⎜⎝ T ⎞⎟⎠ ⎤
⎢ $!!!!!#!!!!!" ⎥
G ⎝ T ⎠
⎛⎜ ⎞⎟
⎢ $! #! " ⎡ ⎡ ⎤ ⎤ ⎥
FA 0 ⎢ rA V ⎢ ⎢ UA ⎥ ⎥ ⎥
= ⎢ΔH R − ⎢C P0 ⎢T − T0 + (T − Ta )⎥ ⎥ ⎥
∑ N i C Pi ⎢ FA 0 ⎢ ⎢ FA 0 C PS ⎥ ⎥ ⎥
⎢ ⎢⎣ ⎢⎣ '&% ⎥⎦ ⎥⎦ ⎥
κ
⎢ ⎥
6 ⎢⎣ ⎥⎦
 Unsteady State Energy Balance
dT FA 0
= [G (T ) − R(T )]
dt ∑ N i C Pi

G (T ) = (rA V )[ΔH Rx ]

R (T ) = C P0 [(1 + κ )T − (T0 + κTa )]

⎛ T0 + κTa ⎞
R (T) = C P0 (1 + κ )⎜ T − ⎟ = C P0 (1 + κ )(T − TC )
⎝ 1 + κ ⎠
UA T0 + κTa
κ= TC =
FA 0 C P 0 1+ κ
7
 Unsteady State Energy Balance
dT
= G(T) − R(T )
dt

If G(T) > R(T) Temperature Increases

If R(T) > G(T) Temperature Decreases

8
 Steady State Energy Balance for CSTRs
At Steady State
dT dN A
= =0
dt dt
− rA V = FA 0 X

G (T ) − R(T ) = 0
(− ΔH Rx )FA 0 X − FA 0 ∑ Θi C P (T − T0 ) − UA(T − Ta ) = 0
i

Solving for X.
9
 Steady State Energy Balance for CSTRs
Solving for X:

UA
∑ Θi C Pi (T − T0 ) + (T − Ta )
FA 0
X= !
= X EB
− ΔH Rx

Solving for T:

FA 0 X(− ΔH Rx ) + UATa + FA 0 ∑ Θi CPi T0

T=
UA + FA 0 ∑ Θi CPi
10
 Steady State Energy Balance for CSTRs
⎡ UA ⎤
X(− ΔH Rx ) = C P0 ⎢T − T0 + (T − Ta )⎥
⎢⎣ FA 0 C P0 ⎥⎦
UA
Let κ =
FA 0C P0
⎛ T0 + κTa ⎞
X(− ΔH Rx ) = C P0 (T + κT − T0 − κTa ) = C P0 (1 + κ )⎜ T − ⎟
⎝ 1 + κ ⎠
= C P0 (1 + κ )(T − TC )

T0 + κTa
TC =
11 1+ κ
 Steady State Energy Balance for CSTRs
G (T ) R (T )
$!#!" $!! !#!!! "
− X ΔH ο Rx = CP 0 (1 + κ )(T − TC )

C P 0 (1 + κ )(T − TC )
X=
− ΔH Rxο

T = TC +
(−ΔH )(X )
ο
Rx

CP 0 (1+ κ )
12
 Steady State Energy Balance for CSTRs

R(T) Increasing T0

T
Variation of heat removal line with inlet temperature.
13
 Steady State Energy Balance for CSTRs
κ=∞

κ=0
R(T)

Increasing κ

Ta T0 T

14 Variation of heat removal line with κ (κ=UA/CP0FA0)

 FA 0 X
V=
− rA (X, T )

A→B

1) Mole Balances: FA 0 X
V=
− rA

2) Rate Laws: − rA = kCA

15
 3) Stoichiometry: CA = CA 0 (1 − X )

4) Combine: FA 0 X C A 0 υ0 X
V= =
kC A 0 (1 − X ) kC A 0 (1 − X )

X
τk =
1− X
τk τAe−E RT
X= =
1 + τk 1 + Ae−E RT
τAe− E RT
G (T ) = X(− ΔH Rx ) = − E RT
(− ΔH Rx )
16 1 + Ae
 Multiple Steady States (MSS)

Variation of heat generation curve with space-time.

17
 Multiple Steady States (MSS)

Finding Multiple Steady States with T0 varied

18
 Multiple Steady States (MSS)

Finding Multiple Steady States with T0 varied

19
 Multiple Steady States (MSS)

Temperature ignition-extinction curve

20
 Multiple Steady States (MSS)

Stability of multiple state temperatures

21
 MSS - Generating G(T) and R(T)
dT
=1
dt
G (T ) = X ⋅ (− ΔH Rx )
R = C P0 ⋅ (1 + κ )⋅ (T − TC )

Need to solve for X after combining mole

balance, rate law, and stoichiometry.

22
 MSS - Generating G(T) and R(T)
For a first order irreversible reaction
tau ⋅ k
X=
(1 + tau ⋅ k )
⎡ E ⎛ 1 1 ⎞⎤
k = k1 exp⎢ ⎜⎜ − ⎟⎟⎥
⎣ R ⎝ T1 T ⎠⎦
Parameters
Tau , (− ΔH Rx ), k1 , E, R , T1 , TC , kappa, C P0
Then plot G and R as a function of T.
23
 End of Web Lecture 23
Class Lecture 19

24