Isothermal Reactor Design

Objectives
Ø Define common terminologies
eg. Conversion, concentration, etc.
Ø Introduction for design of isothermal and ideal reactors
Batch reactor, continuous-stirred tank reactor (CSTR), plug flow
reactor (PFR), and packed bed reactor (PBR)
Outline
Ø Reaction equilibrium and equilibrium conversion
Ø Conversion, concentration, and stoichiometry
Ø Mole balance and reactor design equations
Ø Algorithm for reactor design
Ø Examples
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 Interdisciplinary Lecture

For Reaction Engineering, we need to combine

1. Reaction Kinetic
2. Mass Transfer
3. Heat Transfer
4. Fluid Mechanics (velocity profile, residence time, pressure)
5. Thermodynamics (Final rxn rate)
6. Numerical

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 Reaction Equilibrium
Definition
Ø At certain rxn. conditions, the final destination (or state) a
reaction can reach.
Before Equilibrium, the reaction results (in kinetic region) changes with the contact
(residence) time.
Closed system
Residence time = Reaction time

Flow system
V = reactor volume
v0 = volumetric flow rate at inlet
Residence time, τ = V/v0
Space velocity = v0/V
For Plug Flow Reactor (PFR):
dFA d(FA/v0)
rA = rA =
dV dτ 3
(looks like to be steady) (becomes dynamic)
 Equilibrium Conversion
For Reaction,
aA + bB ← → cC + dD at equilibrium,

Change of total free energy, dG = 0

əG əG əG əG
dG = ( əN dNC + əN dND) + ( əN dNA + əN dNB) = GCdNC + GDdND + GAdNA + GBdNB
C D A B

where GA, GB, GC, GD: partial molar free energy

Define extent of Reaction, β:
NA0-NA NB0-NB NC-NC0 ND-ND0
β= a = b = c = d
→ NA = NA0 – aβ, NB = NB0 – bβ, NC = NC0 + cβ, ND = ND0 + dβ
dNA = – adβ, dNB = – bdβ, dNC = cdβ, dND = ddβ
However,
Gj – Gj0 = RTlnaj
(where Gj0 = free energy at standard state, aj = activity of compound j)

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Therefore,
dG = [(GC0 + RTlnaC)c + (GD0 + RTlnaD)d – (GA0 + RTlnaA)a – (GB0 + RTlnaB)b]dβ = 0

And if we define ΔGR0 = cGC0 + dGD0 – aGA0 – bGB0

ΔGR0 + RT(clnaC + dlnaD – alnaA – blnaB) = 0

→ -ΔGR0 = ln aCc aDd = lnK

RT aAa aBb
where K is equilibrium constant

Standard state:
Gas phase: ideal gas at P = 1 bar (1.023 atm)
Liquid phase: either the pure material or it in a solution at concentration of unity

For ideal liquid solution, aj = Cj

For ideal gas, aj = Pj (same value when measuring pressure in the unit of atm)

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 How to Obtain K(T)
Since ΔGR0 = ΔHR0 - TΔSR0,
-ΔGR0 -ΔHR0 ΔSR0
lnK = = +
RT RT R
dlnK ΔHR0
→ = (van’t Hoff Eq.)
dT RT2
ΔHR0
→ lnK = (1/R) ∫ T2 dT + I

However, ΔHR0 = ∫ ΔCp0 dT + J (where ΔCp = Δα + ΔβT + ΔγT2)

→ ΔHR0 = ΔαT + (Δβ/2)T2 + (Δγ/3) T3 + J’ …………………….(1)

→ lnK = (Δα/R)lnT + (Δβ/2R)T + (Δγ/6R)T2 – (J’/RT) + I’

→ ΔGR0 = -RTlnK = J’ - (ΔαT)lnT - (Δβ/2)T2 - (Δγ/6)T3 - RTI’ …………………….(2)

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where Δα, Δβ, Δγ, ΔHR0 and ΔGR0 at 25oC can be obtained from thermodynamic data,
from (1) & (2) to solve I’ and J’ at 25oC,
→ ΔHR0 and ΔGR0 can be calculated at any given Temp.
→ K = exp(-ΔGR0/RT) can be calculated at any given Temp.

→ cC + dD
For gas phase rxn. (ideal): aA + bB ←
K = exp(-ΔGR0/RT)
= (PCcPDd/PAaPBb)
= (RT)(c+d-a-b)(CCcCDd/CAaCBb)
→ KC ≡ (CCcCDd/CAaCBb) = K (RT)(a+b-c-d)

Equilibrium conversion
Ø Equilibrium constant = fn(conc.)
Ø Concentration = fn(conversion)

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 Conversion and Concentration

For Reaction,
aA + bB → cC + dD
Conversion of A:
for closed system based on mole of A, NA0, at the beginning of reaction (t = 0),
NA0 - NA
at t = t, xA = , NA = NA0(1-xA)
NA0
For flow system based on mole flow rate of A, FA0, at reactor inlet,
FA0 - FA
xA = , FA = FA0(1-xA)
FA0

Concentration :
in closed system, CA = NA/V (mole of A in a unit volume)
in flow system, CA = FA/v (v = total volumetric flow rate)

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 Stoichiometric Table
Batch System

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Flow System

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 Concentration vs. Conversion
For a single rxn., how to correlate concentration with conversion?
(i) For a closed system, eg. batch reactor, V = const.
N A N A0 (1 - x A )
CA = = = C A0 (1 - x A )
V V
b b
N B 0 - N A 0 x A N A 0 (Q B - x A ) N B0
N a a b
CB = B = = = C A 0 (Q B - x A ) QB =
V V V a N A0
i i
N I 0 - N A 0 x A N A 0 (Q I - x A ) NI0
NI a a i
CI = = = = C A 0 (Q I - x A ) QI =
V V V a N A0
c d
CCe C De
With given initial condition, xAe can be solved from the equli. eq., i.e. K C = a b
C AeC Be

(ii) For a flow system, if it is isotherm, isobar and a equimolar rxn.(for gas phase
rxn.), total flow volumetric flow rate remains constant throughout the system,
i.e. v = v0 at the inlet. i
F F (1 - x A ) FA0 (Q I - xA )
a i
C A = A = A0 = C A0 (1 - x A ) CI = = C A 0 (Q I - xA )
v v v a
xAe can be estimated with given inlet condition 11
(iii) For an Ideal gas system, v = v P0 FT T .
0
P FT 0 T0
From stiochoimetric table,
FT c + d - b - a , where y = F /F
= 1 + y A0 x A ( ) A0 A0 T0
FT 0 a
For equilibrium conversion x = xAe,
c d
FC 0 + FA0 x Ae FD 0 + FA0 x Ae
c d ( a )c ( a )d
CCe C De v v
KC = a b =
C AeC Be b
FB 0 - FA0 x Ae
F - FA0 x Ae a a
( A0 ) ( )b
v v
Numerical method is required for most cases.

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Expressing Concentration as
a Function of Conversion

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Concentration in a Gas Flow System

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 Thermodynamics vs. Kinetic

ΔGRǂ
Reactants
ΔGR0
Products

If ΔGR0 < 0, K = exp(- ΔGR0 /RT) may be a large number, rxn. is favored for producing the
products from Thermodynamic point of view.
However, there is a activation energy from Kinetic point of view,
ǂ ǂ ǂ ǂ ǂ
DG DH R DS R DS DH R
i.e. rate constant, k = exp(- R ) = exp(- + ) = exp( R ) exp(- )
RT RT R R RT
E
= A exp(- )
RT
where A: Arrhenius energy, E: activation energy

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 Reaction Rate
Definition
Ø Change of mole of reactants or products due to reaction
per unit time per unit size of the reaction system
Unit Size
1. Unit reaction volume: for homogeneous reaction
2. If reaction occurs only on the surface of the catalyst (solid)
(1) unit catalyst surface
(2) unit catalyst weight (if surface area per weight is constant)
(3) unit catalyst volume (if surface area per volume is constant)
3. Unit interface area: two phase reaction occurs only at interface

Rxn. Rate = fn(Temp., Conc.)

eg. –rA = kCAaCBb
Where conc. = mole of reactants or products (available for the rxn.) per
unit reactor volume
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Mole Balance

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 Common Reactors
Batch Reactors

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Continuous-Flow Reactors
Ø Continuous-Stirred Tank Reactor (CSTR)

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Continuous-Flow Reactors
Ø Tubular Reactor
Plug-flow Reactor (PFR)
Packed-bed Reactor (PBR)

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 Design Equations – 1
Design Equations for four commom reactors derived from mole
balance:

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 Design Equations – 2
In terms of the conversion, the reactor design equations become

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Solution Algorithm for Isothermal Reactor Design

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Solution Algorithm – 1. Conversion

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~ Differential form of Ergun Eg. for packed bed
(p.180 on Fogler 4th ed.)

* Analytical soln. of Ergun eq.

- for ε = 0 or εx << 1,
and isothermal (T = T0)
dy α
=−
dW 2y
P
I.C. : at W = 0, y = = 1
P0
P
→y= = (1− αW )0.5
P0 25
Solution Algorithm – 2. Not conversion

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 Isothermal Ideal Reactor – 1. Ideal Batch
aA + bB ← → cC + dD
1 dN A
-
From mole balance, Ar = -
V dt
i NI0
From stiochoimetric table, N I = N A0 (Q I - x A ) , where Q I =
a N A0
P0 N T T
For ideal gas, V = V0
P N T 0 T0
c + d -a -b
NT 0 + N A0 x A
NT a
If T = T0, P = P0, V = V0 = V0
NT 0 NT 0

then Ci = (Ni / V) can be expressed in terms of NA or xA

* therefore, in ideal batch reactor, we can have only one variable, NA (or xA).
c + d -a -b N A0
Define d A = y
, A0 =
a NT 0
N N A0 (1 - x A ) (1 - x A )
CA = A = = C A0 = C A0 fn( x A )
V V0 (1 + d A y A0 x A ) (1 + d A y A0 x A )
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If - rA = kC A C B ,
1 n 2 n

1 dN A
then - rA = -
V dt
dx A
→ kC Cn1
A
n2
B = C A0 f1 ( x A )
dt
dx A
k[C A0 f 2 ( x A )] [C B 0 f 3 ( x A )] = C A0 f1 ( x A )
n1 n2

dt
n1 n2
n1 -1 n2 [ f ( x )] [ f ( x )] dx A
kC A0 C B 0 2 A 3 A
=
f1 ( x A ) dt
dx A
→ = kC An10-1C Bn20 f ( x A )
dt
I.C.: at t = 0, xA = xA0, Ci = Ci0

Scale up: the same conversion will be reached at the same time as long as the initial
conditions and reaction condition are the same even for reactors with different size

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 Isothermal Ideal Reactor – 2. Ideal CSTR at S.S.

{FA,FB,FC,FD, v} From mole balance,

FA0 - FA
= -rA = kC An1 C Bn2
V
FA0 x A C A0 v0 x A
= = kC An1 C Bn2
V V
{FA0,FB0,FC0,FD0, vo}
C A0 x A
or {CA0,CB0,CC0,CD0} = k[C A0 f1 ( x A )]n1 [C B 0 f 2 ( x A )]n2
t
xA
= kC An10-1C Bn20 f ( x A )
t

Scale up: the same conversion will be reached at the same residence time as
long as the inlet conditions and reaction condition are the same even for
reactors with different size

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 Isothermal Ideal Reactor – 3. PFR
dFA
From mole balance, - rA = - , B.C.: at V = 0, FA = FA0
dV
Since FA = FA0(1-xA), FA = CAv, FA0 = CA0V0
dx A
thus - rA = FA0 = kC An1 C Bn2 = kC An10C Bn20 f1 ( x A )
dV
dx A
→ = kC An10-1C Bn20 f1 ( x A )
dt
Scale up: the same conversion will be reached at the residence time as long as the
inlet conditions and reaction condition are the same even for reactors with different
size
In order to satisfy τ1 = τ2, we should choose V2 to satisfy (V1/v01) = (V2/v02)

* Considering the backmixing, CSTR and PFR represents two extreme situation
Partial backmixing: PFR with recycle or CSTR in series
PFR can be considered as infinite CSTRs in series
dC
In reality, FA = C Av + DA AC (- A )
convection dz
Diffusion (=0, in PFR, since v predominates FA)
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Example – 1

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32
d) In series:
(i) CSTR + PFR
V × (-rA1 ) 200 × 0.07 ×12 × (1 - x1CSTR ) 2 x2 PFR dx 800
x1CSTR =
FA0
=
10
òx1CSTR (1 - x) 2 = 0.007 ò0 dV
x12CSTR - 2.71x1CSTR + 1 = 0 x2 PFR = 0.865
x1CSTR = 0.441
(ii) PFR + CSTR at 300K
x1PFR = 0.85
V × (-rA 2 ) 200 × 0.07 ×12 × (1 - x2CSTR ) 2
( x2CSTR - x1PFR ) = =
FA0 10
x22CSTR - 2.71x2CSTR + 1.67 = 0
x2CSTR = 0.948

In parallel:
xCSTR = 0.554, xPFR = 0.918
10 × (1 - xFinal ) = 5 × (1 - xCSTR ) + 5 × (1 - xPFR )
xCSTR + xPFR
xFinal = = 0.736
2
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 Example – 2

CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O

A + B C + D

-rA = kCA = kCA0 (1-xA)(P/P0)

k = 1.2 (dm3/g-cat/min)
FT0 = 10 (mol/min)
FA0 = FB0 = 5 (mol/min)
P0 = 10 (atm)
T = 118 oC
α = 0.01 (g-1) 34
 dx kC
= A0 (1 - 0.01W ) 0.5 dw
(1 - x) FA0
x kC A0 100 W
[ln(1 - x)] xif = [ (1 - 0.01W )1.5 ] Wif
FA0 1.5
0.5 ×10
1.2 ×
(1 - 0.9) 0.082 × 391 100 [(1 - 0.01W )1.5 - 1]
ln = 0.9
(1 - 0) 5 1.5
W0.9 = 81.87 g
W0.05 = 1.38 g , W0.85 = 61.41g

1.38 g
81.87 g

20.46 g 35
Example – 3

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Combine (E4-9.1) and (E4-9.3)

(E4-9.1)

(E4-9.3)

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Reaction Equilibrium
Substituting Kc = 1.2, CT0 = 0.1, FBe = 2(FA0-FAe)

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