Ch 8: Steady – State Non-isothermal Reactor Design

Energy Balances, Rationale and Overview

Calculate the volume necessary to achieve a conversion, X, in a PFR for a first-
order, exothermic reaction carried out adiabatically.
For an adiabatic, exothermic reaction the temperature profile might look something
like this:

The combined mole balance, rate law, and stoichiometry yield:

To solve this equation we need to relate X and T. We will use the Energy
Balance to relate X and T. For example, for an adiabatic reaction, , the
energy balance can be written in the form

set X, then calculate T, -VA, and , increment X, then plot vs. X

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1. Adiabatic (Q = 0); CSTR, PFR, Batch and PBR:

2. CSTR with heat exchanger, UA(Ta-T) and large coolant flow rate.

3 . PFR/PBR with heat exchange

3A. In terms of conversion, X

3B. In terms of molar flow rates, Fi

2
 4. For Multiple Reactions

5. Coolant Balance

These are eq’ns we will use to solve rxn engineering problems with heat changes.

3. Energy Balance

Typical units for each term are J/s; i.e. Watts

3
Energy Balance
1st Law of Thermodynamics:

dE = dQ – dW (for a closed system)

Energy of the Heat flow to Work done by the

system the system system on the
surroundings

dE • •
= Q− W + Fin E in - Fout E out {for an open system}
dt 123
rate of energy
added to the
system by mass
flow

Evaluation of the Work Term:

•
W = Wf + Ws

flow shaft
n ~ n ~
= −∑ Fi ⋅ P ⋅ V i + ∑ Fi ⋅ P ⋅ V i + Ws
i =1 in i =1 out

~
Combining with Hi = Ui + P Vi

dE sys • • n n
= Q+ W s − ∑ Fi ⋅ H i in + ∑ Fi ⋅ H i out
dt i =1 i =1

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 (1)

1. Replace Ei by Ei=Hi-PVi
2. Express Hi in terms of enthalpies of formation and heat capacities
3. Express Fi in terms of either conversion or rates of reaction
4. Define ∆HRX
5. Define ∆CP
6. Manipulate so that the overall energy balance is either in terms of the
Equations above 1.A, 1.B, 2, 3A, 3B, or 4 depending on the application

Step 1:
Substitute

, and

into equation (1) to obtain the General Energy Balance Equation.

General Energy Balance:

For steady state operation:

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We need to put the above equation into a form that we can easily use to relate X
and T in order to size reactors. To achieve this goal, we write the molar flow rates
in terms of conversion and the enthalpies as a function of temperature. We now
will "dissect" both Fi and Hi.

Flow Rates, Fi

For the generalized reaction:

(2)

In general,
Fi0
Fi = FA0 (Θi +ν i X) where Θi = (3)
FA0
b c d
ν A = -1 ν B = - νC = νD =
a a a

Then
n n

∑H i0 ⋅ Fi0 - ∑ H i ⋅ Fi = FA0 [(H A0 - H A ) + (H B0 - H B ) Θ B ] + ...........

i =1 i =1

n n ⎡ ⎤
= FA0 ∑ [(H i0 - H i ) Θ i ] - ∑ ⎢(ν i ⋅ H i ) FA0 ⋅ X ⎥ (4)
i =1 i =1 ⎢
14 2 43 ⎥
⎣ ∆H RX ⎦
d c b (5)
∆H RX = HD + HC - HB - HA
a a a

(6)
∑F i0 H i0 − ∑ Fi H i = FA0 ∑ Θi (H i0 - H i ) - ∆H RX (T) FA0 X

⎧ dE ⎫
for st - st ⎨ = 0⎬; combining (1) and (6) :
⎩ dt ⎭
• • n
(7)
Q - W + FA0 ∑ Θi (H i0 - H i ) - ∆H RX (T) FA0 X = 0
i =1

If a phase change takes place, it will be included in ∆H RX .

6
Assuming no phase change:

H i = H i (TR ) + ∆H Qi
o
(8)

Enthalpy of Change in enthalpy when T

formation at TR is changed from TR to T.
(ref. temp.)

If there is a phase change:

TM T
H i = H i (TR ) + ∫ C ps,i ⋅ dT + ∆H mi (Tm ) + ∫ C pl,i dT
o
(9)
TR TR

T2

∆H Qi = ∫ C pi ⋅ dT (if no phase change) (10)

T1

T
H i = H i (TR ) + ∫ C pi ⋅ dT
o (11)
TR

Cp = α i + βi ⋅ T + γ i ⋅ T 2
T
H i − H i0 = ∫C
Ti0
pi ⋅ dT = C pi ⋅ [T - Ti0 ] (12)

Substitute into (7) :

• • n
Q - W + FA0 ∑Θ i =1
i ⋅ C pi ⋅ [T - Ti0 ] - ∆ H RX (T) FA0 X = 0 (13)

Combine eq’n (11) & (5)

∆H RX = ∆H RX + ∆C p (T - TR ) (14)
o

where
d c b
∆ H RX = H D (TR ) + H C (TR ) - H B (TR ) - H A (TR )
o o o o o
(15)
a a a

d c b (16)
∆C p = C pD + C pC - C pB - C pA
a a a

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Combine (13) and (14)
• •
[ ]
n
Q - W + FA0 ∑ Θi ⋅ C pi ⋅ [T - Ti0 ] - ∆H RX + ∆C p (T - TR ) ⋅ FA0 X = 0
o
(17)
i =1

Adiabatic Operation:
•
⎫
Ws = 0⎪
X=
∑Θ C (T - Tio )
[ ]
i pi
• ⎬
- ∆HRX + ∆Cp (T - TR )
o
Q = 0 ⎪⎭

for an exothermic, adiabatic rxn

X for an exo. rxn why does X
increase?
This is from E balance, not
mole balance.

∆H RX > ∆C p (T - TR )
o

T so X vs T is linear!!!

Adiabatic Tubular Reactor

Rearrange (18):

T=
[ o
]
X ⋅ - H RX + ∑ Θ i ⋅ C pi To + X ⋅ ∆C p ⋅ TR
(19)
∑Θ ⋅C i pi + X ⋅ ∆C p

Combine with differential mole balance:

dX
FA0 = - rA (X, T) (20)
dV

To obtain T, X and conc’n profiles along the reactor!

Use (19) to construct a table of T vs X.
Obtain k(T) as a function of X Æ -rA as a function of X.
Look at Table 8-2A.

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Steady – State Tubular Reactor with Heat Exchange:
• •
∆ Q = U ⋅ ∆A (Ta - T) = Ua ⋅ (Ta - T) ⋅ ∆V assume Ws = 0

FA0
∑F ⋅H
i i T ∑F ⋅H
i i FAe
To
Te
V V+∆V

•
∆ Q+ ∑ Fi ⋅ H i V
− ∑ Fi ⋅ H i V + ∆V
=0 (1)
•
The heat flow to the reactor ∆ Q
Overall heat transfer coefficient (U)
Heat exchange area (∆A)
Difference between ambient temperature (Ta) and reactor temperature (T)
•
∆ Q = U ⋅ ∆A (Ta - T) = Ua ⋅ ∆V ⋅ (Ta - T) (2)
A 4
= Diameter of reactor
V D

If ∆V Æ 0

d ∑ (Fi ⋅ H i )
Ua (Ta - T) = (3)
dV
dFi
mole balance : = ri = ν i (-rA ) (4)
dV
diff. Eq' n (3) H i = C pi ⋅ dT

Ua (Ta - T) =
∑ dFi ⋅ H i - ∑ Fi
dH i (5) dH i dT
dV dV = C pi ⋅ (6)
dV dV

Combine (5) & (4) & (6)

dT
Ua (Ta - T) = ∑ν i ⋅ H i ⋅ (-rA ) - ∑ Fi ⋅ C pi (7)
1 4 2 43 dV
∆H RX

9
Æ Rearrange:

6Heat
4 generated
7 48 6 Heat4 7removed
48
dT rA ⋅ ∆H RX − Ua (T - Ta)
= (8)
dV ∑ Fi ⋅ Cpi
Fi = FA0 ⋅ (Θ + ν i X)
Ua (Ta - T) + rA ⋅ ∆H RX
dT
= {for a PFR}
dV FA0 ⋅ (∑ Θ i + ν i X + ∆C p ⋅ X )
Substitute into (8)

⋅ (Ta - T) + (rA ') ⋅ ∆H RX

Ua
dT ρ
for a PBR {dW = ρb dV} = b
dW ∑F ⋅C
i pi

dX - rA
These eq’ns will be coupled with mole balance eq’ns
=
dV FA0

Balance on the Coolant Heat Transfer Fluid:

Heat transfer fluid

Tao

R1
R2
FA0, To
V V + ∆V Reactants

The fluid will keep the rxn temperature constant for endo/exo – thermic rxns
You might have
A. Co – current Flow
B. Counter – current Flow

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A. Co – Current Flow
The Energy Balance Ta: coolant temperature

mc, Hc mc, Hc
• • •
E in - E out + Q conduction = 0 FA, T FA, T
V V + ∆V
• •
mc Hc - mc Hc + Ua (T - Ta) ∆V = 0 V
V V + ∆V V + ∆V

Divide by ∆V and take limit as ∆V Æ 0

• exothermic
dH c Tao
mc ⋅ + Ua (T - Ta) = 0
dV

dH c dT dTa Ua (T - Ta)
= Cp a ⇒ = • Tao endothermic
dV dV dV mc ⋅ Cp

B. Counter – Current Flow

Ta2 Ta
FAo, To dTa Ua (Ta - T)
T = •
dV m c ⋅ C pc
V V + ∆V
V=0 V = Vf

At the entrance X = 0; V = 0; Ta = Ta2

At the exit V = Vf; Ta = Tao
The sol’n to the counter-current flow problem to find {T X} is a trial & error
procedure.
Assume a coolant temp at the entrance (Ta2)
Solve ODEs to calculate X, T and Ta as a function of V:
Find Ta(V = Vo)

If Ta (V = Vo ) - Ta2 < ε → Ta (V = Vo ) = Ta2

Else assume another Ta2

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Equilibrium Conversion
As T X {For endothermic rxns}
As T X {For exothermic rxns}

Exothermic Rxns:

Kc
Xe = {1st order rxn}
1 + Kc

From Le Chaltlier’s Law Kp

Kc =
(Kc as T if ∆H<0) exothermic (RT )γ

To find the max X in an exothermic rxn carried adiabatically:

Energy balance
To1 >To
Xe =
∑Θ i ⋅ C pi ⋅ (T - To )
Xe − ∆H RXN (T )
Xe1
⎧if To is changed to To1 ⎫
⎨ ⎬
⎩as T Xe ⎭
To To1
Adabatic temperature

⎧ dlnK ~
⎫
⎪ ∆ H (T) ∆H o
RXN (TR ) + ∆ C p (T - TR )
⎪
= =
p RXN
⎪ dT R ⋅ T2 R ⋅ T2 ⎪
⎪⎪ ~ ⎪⎪
⎨ if ∆ C p = 0 ⎬
⎪ ⎪
⎪K (T ) = K (T ) exp⎧ ∆H RXN (TR ) ⎛⎜ 1 − 1 ⎞⎟⎫
o
⎪
⎪ p 2 p 1 ⎨ ⎜ ⎟ ⎬ ⎪
⎪⎩ ⎩ R ⎝ T1 T2 ⎠⎭ ⎪⎭

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 To increase the conversion in an exothermic rxn, use multiple reactors with
interstate cooling:

Xe

Xeb

For Endothermic Rxn (you need heating)

Xe

Optimum Feed Temperature

∆H rx
Adiabatic Reactor of fixed size T = To - ⋅X
C pA
Reversible & Exothermic Rxn if ∆H rx < 0 as X ;T
X
2

3 1

350 500 600

T, K

As T Xe but the (-rA) decreases!

(so the conversion is achieved at the end of the reactor)
So there must be an optimum temperature to achieve max X.
Curve A: Rxn rate slow, rxn dictated by rate of rxn and reactor volume
As T ,r ,X
Curve B: Rxn rate very rapid. Virtual equilibrium reached in X dictated by equilibrium
conversion

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Adiabatic Rxn Algorithm

Suppose

1. Choose X

Calculate T

Calculate k

Calculate T/To

Calculate CA

Calculate CB

Calculate KC

Calculate -rA

2. Increment X and then repeat calculations.

3. When finished, plot vs. X or use some numerical technique to find V.

Levenspiel Plot for an

exothermic, adiabatic reaction.

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Consider:

PFR Shaded area is the volume.

For an exit conversion of 40% For an exit conversion of 70%

CSTR Shaded area is the reactor volume.

For an exit conversion of 40% For an exit conversion of 70%

We see for 40% conversion very little volume is required.

CSTR+PFR

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For an intermediate conversion of 40% and exit conversion of 70%

Looks like the best arrangement is a CSTR with a 40% conversion followed by
a PFR up to 70% conversion.

Evaluating the Heat Exchanger Term

Energy transferred between the reactor and the coolant:

Assuming the temperature inside the CSTR, T, is spatially uniform:

16
 At high coolant flow rates the exponential term will be small, so we can expand
the exponential term as a Taylor Series, where the terms of second order or
greater are neglected, then:

Since the coolant flow rate is high, Ta1 Ta2 Ta:

Multiple Steady States (MSS)

where Heat generated term

Heat removed term

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R(T):
Varying Entering Temperature
R(T)
Slope = Cpo (1+κ)

Increase To

T
Vary non-adiabatic parameter κ:
if you increase FA0 (molar flow rate) or decrease heat – exch area then κ will
decrease
⎧⎪ Ua ⎫⎪
R(T) ⎨κ = ⎬
κ=∞ ⎪⎩ FA0 C p0 ⎪⎭
κ= 0
T + κ ⋅ Ta
Tc = 0
κ decrease 1+ κ

Ta To
T

G(T)

G(T) High E increasing T

G(T)

Low E

T T

For a first order rxn:

τ ⋅k
X=
1+τ ⋅ k

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Ignition – Extinction Curve:
The point of intersection of G(T) and R(T) give Tst-st.
By plotting Tst-st vs To, we obtain ignition – extinction curve.

Upper st-st

As To Tst-st

Lower st-st

Ignition temp

Extinction temp

Runaway Rxns in a CSTR:

R(T),
G(T)

T0 + κ ⋅ Ta
Tc =
1+ κ Tc T*
Tangency point

R ⋅ T *2
∆Trc = T * - Tc =
E
Reactor T

if this diff. is exceeded, transition to the upper st – st will occur.

At this high temp, it is undesirable or even dangerous.

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PFR

dT Ua (Ta - T) + (-rA )(-∆H Rxn (T))

= m
(for a single rxn)
∑ Fi Cpi
dV
i =1

When q multiple rxns occur with m species:

[ ]
q
Ua (Ta - T) + ∑ (-rij ) - ∆H Rxn,ij (T)
dT i : rxn
= i =1
m

∑F C
dV j : species
j pj
j=1

Ex: Rxn 1 :
A ⎯⎯→
k1
B
B ⎯⎯→
k2
C

dT Ua (Ta - T) + (-r1A )[- ∆H Rxn,1A (T) ] + (-r2B )[- ∆H Rxn,2B (T) ]

=
dV FA C pA + FB C pB + FC C pC

CSTR
• • n
Q - W s + FA0 ∑Θ i ⋅ C pi ⋅ [T - T0 ] - [∆ H RXN (T) ]⋅ [rA V ] = 0 (for a single rxn)
i =1

When q multiple rxns take place

• • 0 n q
Q - W s + FA0 ∑Θ
i =1
i ⋅ C pi ⋅ [T - T0 ] - V ⋅ ∑ rij ∆ H RXN, ij (T) = 0
i =1
n q
UA(T a - T) + FA0 ∑ Θ i ⋅ C pi ⋅ [T - T0 ] - V ⋅ ∑ rij ∆H RXN, ij (T) = 0
i =1 i =1

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