CHEE 321: Chemical Reaction Engineering: (Fogler 2.5, 4.3, 8.5) (Fogler 3.2.3, Examples in CH 4 and 8)

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CHEE 321: Chemical Reaction Engineering

4. Reactor Design Complications (Single Reactions)


4a. Multiple Reactors (Fogler 2.5, 4.3, 8.5)
Reversible Reactions (Fogler 3.2.3, examples in Ch 4 and 8)

CSTR in series
CA0
X=0
v0

V1 ; k1

CA1

CA2

X=X1

X=X2

V2 ; k2

Liquid-phase (v = v0), first-order reaction

Mole Balance on CSTR-1

Mole Balance on CSTR-2

FA0 FA
v [C C A1 ]
V1 =
= 0 A0
k1C A1
(rA ) at X = X 1

V2 =

1k1 =

[C A0 C A1 ] C A0
=
1
C A1
C A1

C A1 =

C A0
1 + 1k1

Fogler 2.5, 4.3.2

v [C C A 2 ]
FA1 FA 2
= 0 A1
k 2C A 2
(rA ) at X = X 2

2 k2 =

[C A1 C A 2 ] C A1
=
1
C A2
C A2
C A2 =

C A2 =

C A1
1 + 2k2

C A0
[1 + 1k1 ][1 + 2 k 2 ]

n-Equal Sized CSTR in series


CA0
X=0
v0

CAn

CA n-1

V
=
v0
C A1 =

C A0
1+ k

C A2 =

X=Xn

All CSTRs are operated at same temperature


[ k is same in all reactors]
C A1
1+ k

C An
Fogler 4.3.2

X=Xn-1

C A3 =

C A2
1+ k

C An =

C An 1
1+ k

C A0
C A0
=
=
n
n
(1 + k )
(1 + Da)

CSTRs: Damkohler Number (Da)


Da is a dimensionless number that can provide a quick estimate of the
degree of conversion in continuous flow reactors.
( rA0 ) V
Da =
FA0

First-order reaction
rA0 V V (kC A0 )
Da =
=
= k
FA0
v0C A0

Note: rate is calculated


at inlet conditions

Second-order reaction
rA0 V V (kC A2 0 )
Da =
=
= k C A0
FA0
v0C A0

Da 0.1 usually results in conversion less than 10%


Da 10 usually results in conversion greater than 90%

n-Equal Sized CSTR in series

n Equal-sized CSTRs - Which is a better configuration?


Parallel or Series
v0/n

CA1

X=X1

v0/n
CA2

CA0
X=0
v0

If you had n-equal sized reactors


available and had the option of
setting them in series or parallel,
which configuration would you
choose to achieve maximum
conversion for a first-order reaction
occurring in liquid phase?

X=X2

v0/n
CA3

v0/n
Fogler 4.3.3

X=X3

X = Xmix
-See Fogler 4.3, Ex. 4-2
-Remember your Levenspiel plots

CAn

X=Xn

Why run reactors in parallel?

Reaction Rates for Reversible Reactions


Reaction:

aA + bB cC + dD

Reaction rates for reversible reactions. Whats so special about them?

The reaction occurs in both the forward and reverse directions

The rate law must have expressions for both forward and reverse
reactions

The rate must be thermodynamically consistent. That is, rate laws (if
expressed in terms of concentration) must reduce to thermodynamic
relationship relating reacting species concentrations at chemical
equilibrium.

KC =

CCc ,eq CDd ,eq


C Aa ,eq CBb ,eq

Strictly speaking - All reactions are reversible !!

Thermodynamics: Equilibrium Constant


aA + bB cC + dD

KC =

c
d
CC,eq
CD,eq
a
b
CA,eq
CB,eq

Units are (mol/L)d+c-a-b

See Fogler Appendix C for a discussion of chemical equilibrium. Various


forms of reaction equilibrium constant are used in literature:
K or Reaction Equilibrium Constant (in terms of activities)
Kp or Pressure Equilibrium Constant
KC or Concentration Equilibrium Constant
For ideal gas system, concentration can be expressed in terms of partial pressure Ci =

KC =

c
d
pC,eq
pD,eq
a
b
pA,eq
pB,eq

pi
RT

( RT )( c d + b + a )

= K P ( RT )( a )

Fogler 3.2.3

Reversible Reactions and Reaction Rate


kB

2 C 6 H 6 C12 H10 + H 2
k B

Benzene Diphenyl

Let B = C6H6, D=C12H10

Define reaction rates wrt Benzene


Rate of disappearance of B

Rate of formation of B
rB ,rev = k B CD CH 2

rB , for = k B CB2

Net rate of B formation:

rB = k B CB2 + k B CD CH 2

At equilibrium: rB = 0 = k B CB2 ,eq + k B CD ,eqCH

2 , eq

k B CD ,eq CH 2 ,eq
=
= KC
2
k B
CB ,eq

Therefore,

2 CD CH 2
rB = k B CB

K
C

Note: rD= 0.5 rB


Fogler 3.2.3

Example: CSTR, constant volumetric flow


The elementary liquid-phase reaction
k1

R +S
A + B

k2

is to take place in a 120 L steady-state mixed reactor. Two feed


streams, one containing 2.8 mol-A/L and the other containing 1.6
mol-B/L, are to be introduced in equal volumes into the reactor, and
75% conversion of the limiting component is desired. What should
be the flow rate of each stream? Assume a constant density
throughout, with k1= 7 Lmol-1min-1 and k2= 3 Lmol-1min-1 .

Adiabatic Operation & Equilibrium Conversion


For a reactor operating adiabatically, the maximum conversion that
may be achieved is the equilibrium conversion.
How can we calculate this ?

Reaction
:

A+ B C +

Equilibrium

Step-1: Calculate Xe as a function of T


c/a
d /a
CCe
C De
KC = [ 1 b / a ]
C Ae C Be

But Kc=f(T)
c

c
d
{C A0 ( C + X e )}a {C A0 ( D + X e )} a
a
a
]
KC = [
b
b
{C A0 (1 X e )} {C A0 ( B X e )}a
a

Fogler 8.5

Adiabatic Operation & Equilibrium Conversion


Step-2: Calculate XEB as a function of Temperature from Steady State Energy
Balance Equation

X EB

=
i

pi

Equilibrium

(T T0 )

H Rxn (T )

The above equation is obtained by


substituting Q =0 and Ws=0 in the
general EB equation below
n

Q Ws FA0 [ i C pi dT ] [ FA0 X H Rxn (T ) ] = 0


i =1 T0

Assumptions made?

Fogler 8.5

Adiabatic Operation & Equilibrium Conversion


Equilibrium

Increasing the inlet


temperature results
in shifting of the
EB equation to the
RIGHT

Xe

Adiabatic Temperature

T01

T02

For an example of how to construct


this plot, see Fogler E8-6

Fogler 8.5

Exothermic Reactions: Achieving Higher


Conversion by Inter-stage Cooling

For an example of how to construct


this plot, see Fogler E8-7

Endothermic Reaction and Adiabatic Conversion

Equilibrium

Increasing the inlet


temperature results
in shifting of the
EB equation to the
RIGHT

Xe

Adiabatic Temperature

T01

T02

Endothermic Reactions: Achieving Higher


Conversion by Inter-stage Heating

Xe
X3

X2

X EB =

X1

~
i C pi (T T0 )
H Rxn (T )

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