IQ2011B 

Chemical reactor design

Module 3: Non-isothermal
reactors
IQ2011B – Chemical reactor design

Mass balance general equation

The molar balance for species j is:

𝑑𝑁
𝐹 𝐹 𝑟 𝑑𝑉
𝑑𝑡

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IQ2011B Chemical reactor design

General energy balance equation

𝑑𝐸
𝑚 𝐸 𝑚 𝐸 𝑄 𝑊
𝑑𝑡
1
𝐸 𝑈 𝐸 𝐸 𝑚𝑢 𝑈 𝑚𝑔ℎ
2
𝑊 𝑊 𝑊
𝐻 𝑈 𝑊 𝑈 𝑝𝑉
Ignoring potential and kinetic energy, and shaft work:
𝑑𝑈
𝑚 𝐻 𝑚 𝐻 𝑄
𝑑𝑡

Energy Balance (Closed Systems)

The first Law of Thermodynamics for Closed Systems states:
Heat Flow
Work of the
Total to the
System on the
Energy System
Surroundings

dE = dQ  dW
gc is the factor to convert
from mass to force
1𝑣 𝑔𝑧 kg m lb ft
𝑑 𝑈 𝑔 1 32.2
2𝑔 𝑔 Ns lb s

At constant volume dU = dQ and also

H = U + pV and for liquids and solids pV is negligible so Q ≈ ∆H

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IQ2011B Chemical reactor design

Energy Balance (Open Systems)

For open systems, the first law is expressed:
Specific energy Specific energy
associated with associated with
System of the mE mS
System

dEsist   1 v 2 gz   1 v 2 gz 
QW  E  Ĥ 
S m   m S  Ĥ   
dt Entradas  2 g c g c Salidas  2 g c gc 
Heat Shaft
flow work

Steady state and disregarding kinetic and potential energy:

𝑄 𝑚 ∑ 𝐻 𝑚 ∑ 𝐻

Energy Balance (Open Systems)

Due to steady state mE = mS and using molar flows
𝑄 𝐹𝐻 𝐹𝐻

And according to the stoichiometric table

𝑖
𝐹 𝐹 𝐹 𝑥
𝑎
 i   i 
 
Q   Fi 0  FA 0x A Ĥi    Fi 0  FA 0x A Ĥi
Salidas  a  Entradas  a 

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IQ2011B Chemical reactor design

Energy Balance
Heat of reaction @ T
Rearranging:

c d b 
 
Q F i0 Ĥi  F i0 Ĥi  FA 0x A  ĤC  ĤD  ĤB  Ĥ A 
Salidas Entradas a a a 

And with:
c d b
ĤRXN ( T)  ĤC  ĤD  ĤB  ĤA
a a a

Energy Balance

Simplifying:
 
Q  F (Ĥ  Ĥ
i
i0 i i0 )  FA 0x A ĤRXN ( T)

If there is no phase change: a + bT + cT2 + dT3

T
Ĥi ( T)  Ĥ0fi ( TR )  
TR
Cpi dT

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IQ2011B Chemical reactor design

Energy Balance
Replacing:
Ĥi ( T)  Ĥi 0 ( T)  Ĥ0fi ( TR )  CpidT  Ĥ0fi ( TR )  CpidT
T Ti 0

  TR   
TR 

T Ti 0
 
TR
CpidT  
TR
Cpi dT

T
 
Ti 0
CpidT

Energy Balance
Replacing

F 
T
 
Q Cpi dT  FA 0x A ĤRXN ( T)
i0
Ti 0
i

And the heat of reaction is expressed:

   
TR T
ĤRXN  Cpi dT  Ĥ0RXN  CpidT
T TR
Re activos Pr oductos

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IQ2011B Chemical reactor design

Energy Balance
Taking into account the coefficients:
i
 
T
ĤRXN  Ĥ0RXN  Cpi dT
a TR

Convective Heat of
heat flow reaction

 i 
   
T T
 
Q Fi 0 Cpi dT  FA 0x A Ĥ0RXN  Cpi dT
i
Ti 0  a TR 

Heat flow to the

surrounding area

Energy Balance
Using Constant Cp's:
  F C p ( T  T )  F x Ĥ0   i C p ( T  T )
Q i0 i i0 A0 A  RXN i R 
 a 
Simplifying:

  F C p ( T  T )  F x Ĥ0   C p( T  T )
Q i0 i i0 A0 A RXN R  
𝑖
∆𝐶𝑝 𝐶𝑝
𝑎

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IQ2011B Chemical reactor design

Energy Balance in BRs

For a batch reactor, instead of F molar flows, we have moles N:

Sensitive and
latent heat of
the mixture

i i0 A0 A RXN 
 t  N C p ( T  T )  N x Ĥ0   C p ( T  T )
Q i i R 
Heat flow with Heat of reaction
the
surroundings

This would be a BdeE accumulated from the beginning to the end

of the reaction, where Q = UA(Tm – T)

Energy Balance in BRs

For an instant of time t:
 dt  N Cp dT  N dx Ĥ
Q i i A0 A RXN

But from the BdeM, NA0dxA = (– rAV)dt:

  N Cp dT  ( r V )Ĥ
Q i i A RXN
dt

dT UA( Tm  T)  ( rA V )ĤRXN


dt N iCpi

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IQ2011B Chemical reactor design

Energy Balance in CSTRs

Taking the equation:

i i0 A0 A RXN 
  F C p ( T  T )  F x Ĥ0   C p ( T  T )
Q i0 i R 
where Q = UA(Tm – T) and A is the heat transfer area.

Energy Balance in PFRs

Taking the equation:
UDL( Tm  T)  Fi 0 C pi ( T  Ti 0 )  FA 0x A ĤRXN
where Q = UA(Tm – T). Again, this is a cumulative BdeE from the
input to the output of the PFR. On a dV:
UdA ( Tm  T)  FiCpi dT  FA 0dx A ĤRXN

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IQ2011B Chemical reactor design

Energy Balance in PFRs

But FA0dxA = – rAdV. Rearranging:
UDdz( Tm  T)  FiCpi dT  ( rA A Tdz )ĤRXN

where AT = D2/4. Dividing between dz and simplifying:

dT UD( Tm  T)  ( rA A T )ĤRXN


dz FiCpi

Batch
It can be analyzed with the following simplifications:
a) You have a constant temperature or a temperature program.
b) You have a specified heat flow (zero, constant, or a function of
time.
c) The system operates neither isothermal nor adiabatic.

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IQ2011B Chemical reactor design

a) Specified temperature
To calculate the heat flow, Qtotal is cleared and derived with
respect to time:

𝑑𝑄 𝑑 ∑ 𝑁 𝐶𝑝 𝑇 𝑇 ∆𝐻 𝑁 𝑋
𝑄 𝑡
𝑑𝑡 𝑑𝑡

 H0RXN  CpT  TR 

This gives us the heat flow program required to maintain the

specified temperature conditions.

b) Specified heat flow

The BdeE is a nonlinear equation relating T and XA that must be solved simultaneously with
the EDO of the BdeM. In the case of an adiabatic batch reactor:
𝛥𝐻rxn 𝑁 𝑋 ∑𝑁 Cp 𝑇 𝑇

Clearing T as a function of XA:

Δ𝐻 𝑁 𝑋
𝑇 𝑇
Σ𝑁 𝐶𝑝

When XA tends to 1, it is known as the adiabatic elevation of temperature.

Δ𝐻 𝑁 Complete
𝑇 𝑇 Conversion
Σ𝑁 𝐶𝑝

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IQ2011B Chemical reactor design

c) Non-isothermal, non-adiabatic
In this case the BdeM equation cannot be solved independently
of the BdeE and only applies a simultaneous solution of the
EDOs.

𝑑𝑋 𝑉
𝑟
𝑑𝑡 𝑁

𝑑𝑇 ∆𝐻 𝑟 𝑉 𝑈𝐴 𝑇 𝑇
𝑑𝑡 ∑ 𝑁 𝐶𝑝

CSTR

i i0 A0 A 
  F C p ( T  T )  F x Ĥ0   C p ( T  T )
Q i0 RXN i R 
where T is the operating temperature of the reactor, Cp
represents the effect of the T on the HRXN, Q = UA(Tm – T)
and A is the heat transfer area.

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IQ2011B Chemical reactor design

PFR
Mass Balance:
xA
dx A dx A D2
V  FA 0
0  rA

dz 4FA 0
( rA )

Energy Balance: Momentum Balance:

dT UD( Tm  T)  ( rA A T )ĤRXN 𝑑𝑝 𝜌𝑣

 2𝑓
dz FiCpi 𝑑𝑧 𝐷𝑔

Transfer of Energy to the Surroundings

Additionally, if there is heat transfer with the surroundings
(cooling/heating fluid), the BdeE can be considered in the heat
transfer medium:

dTm UD( T  Tm )

dz m
 ECpE

Where mE is the mass flow of the medium and CpE its specific
heat.

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