Reactors with Heat Exchange

CL324

Prof. Swati Bhattacharya 1

Heat Exchange
Consider a tubular reactor in which heat is added through the walls.
Δ𝑄ሶ = 𝑈Δ𝐴(𝑇𝑎 − 𝑇)

Look at the heat balance equation

dE sys
 Fi 0 Ei 0 −  Fi Ei + Q − W =
dt

Prof. Swati Bhattacharya 2

Heat Exchange
dE sys
 i0 i0  i i
F E − F E +  − W
Q =
dt

In steady state:
𝑑𝐸𝑠𝑦𝑠
=0
𝑑𝑡
Prof. Swati Bhattacharya 3
Steady State Tubular Reactor with Heat
Exchange 𝑇 Δ𝑉 Δ𝑄ሶ = UΔ𝐴 𝑇 − 𝑇 = 𝑈𝑎 𝑇 − 𝑇 ΔV
𝑎 𝑎 𝑎

𝑇0 𝐹𝐴0 𝐹𝐴Θ
𝑇
෍ 𝐹𝑖 𝐻𝑖 𝑇Θ
𝑖

𝑉 𝑉 + Δ𝑉
Consider a reactor in which heat is added or removed through cylindrical walls.
Assume no radial gradients.
Carry out energy balance on a volume Δ𝑉 with 𝑊ሶ 𝑆 = 0.

So: Δ𝑄ሶ + ∑𝐹𝑖 𝐻𝑖 ȁ𝑉 − ∑𝐻𝑖 𝐹𝑖 ȁ𝑉+Δ𝑉 = 0 Eqn.1, Steady State

Prof. Swati Bhattacharya 4

Here, ΔQሶ is the heat flow to the reactor, 𝑈, the heat transfer
coefficient, Δ𝐴 is the heat exchange area, 𝑇𝑎 is the ambient
temperature.
Δ𝑄ሶ = 𝑈Δ𝐴 𝑇𝑎 − 𝑇 = 𝑈𝑎Δ𝑉 𝑇𝑎 − 𝑇 ,
Where 𝑎 = heat exchange area per unit volume of reactor.
For the tubular reactor,
𝐴 𝜋𝐷𝐿 4
𝑎 = = 𝜋𝐷2𝐿 = where 𝐷 = 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟
𝑉 𝐷
4

Substituting in Eqn 1: Δ𝑄ሶ + ∑𝐹𝑖 𝐻𝑖 ȁ𝑉 − ∑𝐻𝑖 𝐹𝑖 ȁ𝑉+Δ𝑉 = 0

𝑑
𝑈a 𝑇𝑎 − 𝑇 − (∑ 𝐹𝑖 𝐻𝑖 ) = 0
𝑑𝑉
Prof. Swati Bhattacharya 5
 𝑑
𝑈a 𝑇𝑎 − 𝑇 − (∑ 𝐹𝑖 𝐻𝑖 ) = 0
𝑑𝑉
Expanding :

𝑑𝐹𝑖 𝑑𝐻𝑖
𝑈a 𝑇𝑎 − 𝑇 − ෍ 𝐻𝑖 − ෍ 𝐹𝑖 = 0
𝑑𝑉 𝑑𝑉

Prof. Swati Bhattacharya 6

 𝑑𝐹𝑖
Mole balance on Species i: = 𝑟𝑖 = 𝜈𝑖 (−𝑟𝐴 ),
𝑑𝑉
𝜈𝑖 =stoichiometric coefficient
𝑑𝐻𝑖 𝑑𝑇
Also = 𝐶𝑃𝑖
𝑑𝑉 𝑑𝑉

𝑑𝑇
Hence, 𝑈𝑎 𝑇𝑎 − 𝑇 − ∑𝜈𝑖 𝐻𝑖 −𝑟𝐴 − ∑𝐹𝑖 𝐶𝑝𝑖 =0
𝑑𝑉

Note
∑𝜈𝑖 𝐻𝑖 = Δ𝐻𝑅𝑋

Re-arranging:

𝑑𝑇 𝑟𝐴 Δ𝐻𝑅𝑋 − 𝑈𝑎(𝑇 − 𝑇𝑎 ) 𝐻𝑒𝑎𝑡 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 − 𝐻𝑒𝑎𝑡 𝑅𝑒𝑚𝑜𝑣𝑒𝑑

= =
𝑑𝑉 ∑𝐹𝑖 𝐶𝑃𝑖 ∑𝐹𝑖 𝐶𝑃𝑖

Prof. Swati Bhattacharya 7

 𝑑𝑇 𝑟𝐴 Δ𝐻𝑅𝑋 − 𝑈𝑎(𝑇 − 𝑇𝑎 ) 𝐻𝑒𝑎𝑡 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 − 𝐻𝑒𝑎𝑡 𝑅𝑒𝑚𝑜𝑣𝑒𝑑
= =
𝑑𝑉 ∑𝐹𝑖 𝐶𝑃𝑖 ∑𝐹𝑖 𝐶𝑃𝑖

Eqn.2
𝐹𝑖 = 𝐹𝐴0 (Θ𝑖 + 𝑋𝜈𝑖 )

Is coupled with mole balances of each species.

Eqn 2 can also be re-written using stoichiometry:

𝑑𝑇 𝑈𝑎 𝑇𝑎 (𝑉) − 𝑇 + 𝑟𝐴 ΔHRX
=
𝑑𝑉 𝐹𝐴0 (∑Θ𝑖 𝐶𝑃𝑖 + Δ𝐶𝑃 𝑋)
Prof. Swati Bhattacharya 8
For a packed bed reactor 𝑑𝑊 = 𝜌𝑏 𝑑𝑉

𝑈𝑎
𝑇𝑎 −𝑇 +𝑟𝑎′ Δ𝐻𝑅𝑋
𝑑𝑇 𝜌𝑏
= (Eqn 3)
𝑑𝑊 ∑𝐹𝑖 𝐶𝑃𝑖

The change of temperature with volume down a reactor may be

written
𝑑𝑇
= 𝑔(𝑋, 𝑇) (Eqn 4) and this may be coupled with the mole balance
𝑑𝑉

𝑑𝑋 𝑟𝐴
= − = 𝑓(𝑋, 𝑇) (Eqn 5)
𝑑𝑉 𝐹𝐴0

Prof. Swati Bhattacharya 9

How to use the equations
Cases :
Case A: Constant 𝑇𝑎 , Eg. 𝑇𝑎 = 300𝐾
Case B: Co-current flow
The reactant and coolant flow in same direction.
Variation of coolant temperature down the reactor is
𝑑𝑇𝑎 𝑈𝑎(𝑇−𝑇𝑎 )
= Eqn (6)
𝑑𝑉 𝑚ሶ 𝑐 𝐶𝑃𝑐
At the entrance 𝑉 = 0, X = 0, Ta0
At the exit 𝑉 = 𝑉𝑓 , Ta = Ta
𝑇, 𝑇𝑎 can both be functions of 𝑉.
Energy balance on coolant in volume
between 𝑉 and 𝑉 + Δ𝑉
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑖𝑛 − 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑢𝑡
+ 𝑅𝑎𝑡𝑒 𝑜𝑓 ℎ𝑒𝑎𝑡 𝑎𝑑𝑑𝑒𝑑 = 0

ሶ
𝑚ሶ 𝐶 𝐻𝐶 ቚ − 𝑚𝐶 𝐻𝐶 ቚ + 𝑈𝑎 𝑇 − 𝑇𝑎 = 0
𝑉 𝑉+Δ𝑉

𝑚ሶ𝐶 = mass flow rate of coolant

𝑇𝑎 (𝑉) = coolant temperature
Energy balance on coolant in volume
between 𝑉 and 𝑉 + Δ𝑉

Divide by Δ𝑉 and taking the limit Δ𝑉 → 0:

𝑑𝐻𝐶
−𝑚𝐶 + 𝑈𝑎 𝑇 − 𝑇𝑎 = 0
𝑑𝑉

𝑑𝐻𝐶 𝑑𝑇𝑎
Change in enthalpy of coolant: = 𝐶𝑃𝐶
𝑑𝑉 𝑑𝑉

𝑑𝑇𝑎 𝑈𝑎 𝑇−𝑇𝑎
So: = . At entrance 𝑉 = 0. 𝑋 = 0, 𝑇𝑎 = 𝑇𝑎0
𝑑𝑉 𝑚ሶ 𝑐 𝐶𝑃 𝐶
Energy balance on coolant in volume
between 𝑉 and 𝑉 + Δ𝑉
ሶ
𝑚ሶ 𝐶 𝐻𝐶 ቚ − 𝑚𝐶 𝐻𝐶 ቚ + 𝑈𝑎 𝑇 − 𝑇𝑎 = 0
𝑉 𝑉+Δ𝑉
Divide by Δ𝑉 and taking the limit Δ𝑉 → 0:
𝑑𝐻𝐶
−𝑚𝐶 + 𝑈𝑎 𝑇 − 𝑇𝑎 = 0
𝑑𝑉

𝑑𝐻𝐶 𝑑𝑇𝑎
Change in enthalpy of coolant: = 𝐶𝑃𝐶
𝑑𝑉 𝑑𝑉
Energy balance on coolant in volume
between 𝑉 and 𝑉 + Δ𝑉
𝑑𝐻𝐶 𝑑𝑇𝑎
Change in enthalpy of coolant: = 𝐶𝑃𝐶
𝑑𝑉 𝑑𝑉
Variation of 𝑇𝑎 down the reactor:

𝑑𝑇𝑎 𝑈𝑎 𝑇−𝑇𝑎
So: =
𝑑𝑉 𝑚ሶ 𝑐 𝐶𝑃 𝐶
At entrance 𝑉 = 0. 𝑋 = 0, 𝑇𝑎 = 𝑇𝑎0
 Heat transfer fluid temperature profiles

𝑇𝑎 𝑇𝑎
Endothermic
𝑇𝑎𝑜
Exothermic

𝑉
 Energy Balance with Counter Current Flow
Case C:

Variation of coolant temperature down the reactor is

𝑑𝑇𝑎 𝑈𝑎(𝑇𝑎 −𝑇)
= (Eqn 7)
𝑑𝑉 𝑚ሶ 𝑐 𝐶𝑃𝑐

At entrance: 𝑉 = 0, 𝑋 = 0, 𝑇𝑎 = 𝑇𝑎2
At exit: 𝑉 = 𝑉𝑓 , 𝑇𝑎 = 𝑇𝑎0
Heat Exchanger Energy Balance: Variable Ta
Counter-current
In - Out + Heat Added = 0
m C H C V + V
− m C H C V
+ UaV (T − Ta ) = 0

dH C
m C + Ua(T − Ta ) = 0
dV

dTa Ua(Ta − T ) At exit: 𝑉 = 𝑉𝑓 , 𝑇𝑎 = 𝑇𝑎0

=
dV m C C PC At entrance: 𝑉 = 0, 𝑇𝑎 = 𝑇𝑎2
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 Energy Balance with Counter Current Flow
Case C:

Variation of coolant temperature down the reactor is

𝑑𝑇𝑎 𝑈𝑎(𝑇𝑎 −𝑇)
= (Eqn 7)
𝑑𝑉 𝑚ሶ 𝑐 𝐶𝑃𝑐

At entrance: 𝑉 = 0, 𝑋 = 0, 𝑇𝑎 = 𝑇𝑎2
At exit: 𝑉 = 𝑉𝑓 , 𝑇𝑎 = 𝑇𝑎0
 Counter-Current Flow
Solution requires trial and error, since we first need to find both 𝑋 and 𝑇𝑎 .

Example. If we have an exothermic reaction,

Coolant stream enters at 𝑉 = 𝑉𝑓 at temperature 𝑇𝑎 = 𝑇𝑎0 = 300 𝐾 (say)
▪ Assume a coolant temperature at 𝑉 = 0, 𝑋 = 0, 𝑇𝑎0 = 340 (guess)
▪ Use ODE solver to find 𝑋, 𝑇 𝑎𝑛𝑑 𝑇𝑎 as a function of 𝑉 (or length of the tube)
▪ Suppose the solution gives a different 𝑇𝑎 at exit, 𝑇𝑎𝑓1 = 310 𝐾 (solution)
▪ Repeat with different guess of 𝑇𝑎0 = 330𝐾.
▪ Again with ODE solver, find 𝑇𝑎𝑓2 .
▪ As in shooting method, try to find the actual solution.
Heat Exchanger – Example
Case 1 – Constant Ta
Elementary liquid phase reaction carried out in a PFR

Heat Exchange
c
m Fluid
Ta
FA0 T
FI AB

The feed consists of both inerts I and species A

 ratio of inerts to the species A being 2 to 1.
with the
20
Heat Exchanger – Example
Case 1 – Constant Ta
1) Mole Balance:
𝑑𝑋 −𝑟𝐴 1
(1) =
𝑑𝑉 𝐹𝐴0 2

𝐶𝐵
(2) 𝑟𝐴 = − 𝑘 𝐶𝐴 −
𝐾𝐶
2) Rate Laws:

𝐸 1 1
(3) 𝑘 = 𝑘1 exp −
𝑅 𝑇1 𝑇

Δ𝐻𝑅𝑥 1 1
(4) 𝐾𝐶 = 𝐾𝐶2 exp −
𝑅 𝑇2 𝑇
21
Heat Exchanger – Example
Case 1 – Constant Ta
3) Stoichiometry: 𝐶𝐴 = 𝐶𝐴0 1 − 𝑋 5

𝐶𝐵 = 𝐶𝐴0 (Θ𝐵 + 𝑋)

4) Heat Effects: 𝑑𝑇 Δ𝐻𝑅 −𝑟𝐴 − 𝑈𝑎 𝑇 − 𝑇𝑎

= 7
𝑑𝑉 𝐹𝐴0 ∑ 𝜃𝑖 𝐶𝑃𝑖

Δ𝐶𝑃 = 0

𝑘𝐶
𝑋𝑒𝑞 = 8
1 + 𝑘𝐶

෍ 𝜃𝑖 𝐶𝑃𝑖 = 𝐶𝑃𝐴 + 𝜃𝐼 𝐶𝑃𝐼 9 22

Heat Exchanger – Example
Case 1 – Constant Ta

Parameters: Δ𝐻𝑅 , 𝐸, 𝑅, 𝑇1 , 𝑇2 ,
𝑘1 , 𝑘𝐶2 , 𝑈𝑎, 𝑇𝑎 ,
𝐹𝐴0 ,
𝐶𝐴0 , 𝐶𝑃𝐴 , 𝐶𝑃𝐼 , 𝜃𝐼 ,
𝑟𝑎𝑡𝑒 = −𝑟𝐴

23
PFR Heat Effects
Heat Heat
generated removed

𝑑𝑇 𝑄𝑔 − 𝑄𝑟
=
𝑑𝑉 ∑ 𝐹𝑖 𝐶𝑃𝑖

å i Pi å A0 i i Pi A0 ëå i Pi P û
F C = F (q + u X ) C = F é q C + DC X ù

dT ( DH R ) ( rA ) -Ua (T - Ta )
=
dV FA0 éëåqiCPi + DCP X ùû
24
 Heat Exchanger – Example
Case 1 – Constant Ta
Parameters: H R , E , R, T1 , T2 ,
k1 , kC 2 , Ua, Ta , FA0 ,
C A0 , C PA , C PI ,  I ,
rate = −rA

So, given a problem with the above parameters, you can proceed.

25
PFR Heat Effects
Heat Heat
generated removed

dT Q g − Q r
=
dV  Fi C Pi

å i Pi å A0 i i Pi A0 ëå i Pi P û
F C = F (q + u X ) C = F é q C + DC X ù

dT ( DH R ) ( rA ) -Ua (T - Ta )
=
dV FA0 éëåqiCPi + DCP X ùû
26
Heat Exchanger – Example
Case 2 – Adiabatic
dX −rA
Mole Balance: =
dV FA 0
Energy Balance:
Adiabatic and ΔCP=0
Ua=0 
T = T0 +
( −H Rx ) X
 i CPi
Additional Parameters

T0 ,  i CPi = CPA + I CPI 27