3- Design Equations for Flow Reactors

For a batch reactor, we saw that conversion increases with time spent in the reactor. For continuous-flow
systems, this time usually increases with increasing reactor volume, thats is to say, the bigger/longer the
reactor, the more time it will take the reactants to flow completely through the reactor and thus, the more time
to react. Consequently, the conversion X is a function of reactor volume V. If FA0 is the molar flow rate of species
A fed to a system operated at steady state, the molar rate at which species A is reacting within the entire system
will be FA0.X

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑

𝐹𝐴0 . 𝑋 = . = = 𝐹𝐴0 − 𝐹𝐴
𝑡𝑖𝑚𝑒 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑 𝑡𝑖𝑚𝑒

𝑁𝐴0 − 𝑁𝐴 𝑁𝐴0 𝑁𝐴
𝑁𝐴0 𝑁𝐴0 − 𝑁𝐴
𝑡 𝑡 𝑡
𝑡 𝑁𝐴0
We obtain the following relation:

𝐹𝐴0 − 𝑋. 𝐹𝐴0 = 𝐹𝐴
Molar flow rate at which A leaves
Molar flow rate at which A is fed to the system
the system
Molar rate at which A is consumed within
the system

Rearranging gives:

𝐹𝐴 = 𝐹𝐴0 (1 − 𝑋) (8)

The entering molar flow rate of species A, FA0 (mol/s), is just the product of the entering concentration, CA0
(mol/m3), and the entering volumetric flow rate, (m3/s):

𝐹𝐴0 = 𝐶𝐴0 𝑉′ (9)

For liquid systems, the volume flow rate, , is constant and equal to V’, and CA0 is commonly given in terms of
molarity, for example, CA0 = 2 mol/m3.
For gas systems, CA0 can be calculated from the entering mole fraction, yA0, the temperature T0, and pressure P0,
using the ideal gas law or some other gas law. For an ideal gas:

𝑃𝐴0 𝑉 = 𝑁𝐴0 𝑅𝑇
𝑁𝐴0
𝑃𝐴0 = 𝑅𝑇 = 𝐶𝐴0 𝑅𝑇
𝑉
𝑁𝐴0
𝑃0 𝑦𝐴0 = 𝑅𝑇 = 𝐶𝐴0 𝑅𝑇
𝑉
𝑃0 𝑦𝐴0
𝐶𝐴0 = (10)
𝑅𝑇
3-1 CSTR (Also Known as a Backmix Reactor or a Vat)

Recall that the CSTR is modeled as being well mixed such that there are no spatial variations in the reactor.
For the general reaction:
(2)

the CSTR mole balance Equation can be arranged to:

𝐹𝐴0 − 𝐹𝐴
𝑉= (11)
−𝑟𝐴

We substitute for FA in terms of FA0 and X:

𝐹𝐴 = 𝐹𝐴0 (1 − 𝑋) (12)

and then substitute Equation (12) into (11):

𝐹𝐴0 − 𝐹𝐴0 (1 − 𝑋)
𝑉=
−𝑟𝐴
Simplifying, we see that the CSTR volume necessary to achieve a specified conversion X is:

𝐹𝐴0 𝑋
𝑉= (13)
(−𝑟𝐴 )
CSTR Equation design

Because the reactor is perfectly mixed, the exit composition from the reactor is identical to the composition
inside the reactor, and, therefore, the rate of reaction, –rA, is evaluated at the exit conditions.
3-2 Tubular Flow Reactor (PFR)
We model the tubular reactor as having the fluid flowing in plug flow, that’s is to say no radial gradients in
concentration, temperature, or reaction rate. As the reactants enter and flow axially down the reactor, they
are consumed and the conversion increases along the length of the reactor. To develop the PFR
design equation, we first multiply both sides of the tubular reactor design equation by –1. We then express
the mole balance equation for species A in the reaction as:

𝑑𝐹𝐴
− = −𝑟𝐴 (14)
𝑑𝑉

For a flow system, FA has previously been given in terms of the entering molar flow rate FA0 and the
conversion X:
𝐹𝐴 = 𝐹𝐴0 − 𝐹𝐴0 𝑋
Differentiating:
𝑑𝐹𝐴 = 𝑑𝐹𝐴0 − 𝑑(𝐹𝐴0 𝑋)
 𝑑𝐹𝐴 = −𝐹𝐴0 𝑑𝑋

and substituting into Equation (14), gives the differential form of the design equation for a plug-flow reactor
(PFR):
𝐹𝐴0 𝑑𝑋
= −𝑟𝐴 (15)
𝑑𝑉
PFR Equation design

We separate now the variables and integrate with the limits V=0 when X=0 to obtain the plug-flow reactor
volume necessary to achieve a specified conversion X:

𝑑𝑋
𝑑𝑉 = −𝐹𝐴0
𝑟𝐴
𝑋
𝑑𝑋
𝑉 = 𝐹𝐴0 න (16)
(−𝑟𝐴 )
0
3-3 Packed-Bed Reactor (PBR)

Packed-bed reactors are tubular reactors filled with catalyst particles. In PBRs it is the weight of catalyst W that
is important, rather than the reactor volume.
The derivation of the differential and integral forms of the design equations for packed-bed reactors are
analogous to those for a PFR[cf. Equations (15) and (16)].

That is to say, substituting Equation (12) for FA in the mole balance Equation (differential form) related to PBRs
reactor:
𝑑𝑋
𝐹𝐴0 = −𝑟𝐴′ (17)
𝑑𝑊
PBR Equation design

The differential form of the design equation [i.e., Equation (17)] must be used when analyzing reactors that
have a pressure drop along the length of the reactor.
In the absence of pressure drop, that is to say, ΔP = 0, we can integrate Equation (17) with limits X = 0 at W = 0,
and when W = W then X = X to obtain:
𝑑𝑋
𝑑𝑊 = 𝐹𝐴0
(−𝑟𝐴′ )

𝑋
𝑑𝑋
𝑊 = 𝐹𝐴0 න (18)
(−𝑟𝐴 )
0

Equation (18) can be used to determine the catalyst weight W (mass) necessary to achieve a conversion X when
the total pressure remains constant.
4- Sizing Continuous-Flow Reactors

In this section, we are going to show how we can size CSTRs and PFRs (that’s is to say how to determine their
reactor volumes) from knowledge of the rate of reaction, –rA, as a function of conversion, X [thahs is to say, –rA
= f(X)]. The rate of disappearance of A, –rA, is almost always a function of the concentrations of the various
species present.

When only one reaction is occurring, each of the concentrations can be expressed as a function of the
conversion X ; consequently, –rA can be expressed as a function of X.

Starting from the relations:

𝐹𝐴 = 𝐹𝐴0 − 𝐹𝐴0 𝑋
𝐹𝐴0 = 𝐶𝐴0 𝑉′ 𝐶𝐴 = 𝐶𝐴0 − 𝐶𝐴0 𝑋 𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋)
𝐹𝐴 = 𝐶𝐴 𝑉′
In case first-order reaction:

−𝑟𝐴 = 𝑘𝐶𝐴 = 𝑘𝐶𝐴0 (1 − 𝑋)

Where:

K: the specific (constant) reaction rate and is a function only of temperature

CA0 :the entering concentration of A

We note in Equations (13) and (16) that the reactor volume is a function of the reciprocal of –rA. For this first-
order dependence, a plot of the reciprocal rate of reaction (1/–rA) as a function of conversion X, gives a curve
similar to the one shown in the following Figure

1 1 1
=
−𝑟𝐴 𝑘𝐶𝐴0 1 − 𝑋
 Typical curve of the reciprocal rate as a
function of conversion .

We can use the Figure above to size CSTRs and PFRs for different entering flow rates. By sizing we mean either
determine the reactor volume for a specified conversion or determine the conversion for a specified reactor
volume.
Before sizing flow reactors, let’s consider some insights. If a reaction is carried out isothermally, the rate is
usually greatest at the start of the reaction when the concentration of reactant is greatest (that’s when there is
negligible conversion [X ≅ 0])
Hence, the reciprocal rate (1/–rA) will be small. Near the end of the reaction, when the reactant has been
mostly used up and thus the concentration of A is small (That’s, the conversion is large), the reaction rate will
be small. Consequently, the reciprocal rate (1/–rA) is large.

For all irreversible reactions of greater than zero order, as we approach complete conversion where all the
limiting reactant is used up, that’s to say X = 1, the reciprocal rate approaches infinity as does the reactor
volume.
A B+C

Consequently, we see that an infinite reactor volume is necessary to reach complete conversion, X = 1
For reversible reactions (A B), the maximum conversion is the equilibrium conversion Xe. At equilibrium, the
reaction rate is zero (rA = 0).
A B+C
Therefore:

and we see that an infinite reactor volume would also be necessary to obtain the exact equilibrium conversion,
X = Xe.

4-1 Examples of Reactor Design and Staging Given rA = f(X)

To illustrate the design of continuous-flow reactors (i.e., CSTRs and PFRs), we consider the isothermal gas-
phase isomerization.
A B

We are going to the laboratory to determine the rate of chemical reaction as a function of the conversion of
reactant A. The laboratory measurements given in the following Table show the chemical reaction rate as a
function of conversion. The temperature was 500 K (440°F), the total pressure was 830 kPa (8.2 atm), and the
initial charge to the reactor was pure A. The entering molar flow of A rate is F A0 = 0.4 mol/s.
Recalling the CSTR and PFR design equations, (13) and (16), we see that the reactor volume varies directly with
𝐹 𝑋
the molar flow rate FA0 and with the reciprocal of –rA (1/-rA), for example 𝑉 = 𝐴0 . Consequently, to size
(−𝑟𝐴 )
reactors, we first convert the raw data in Table below, which gives –rA as a function of X first to (1/-rA) as a
function of X. Next, we multiply by the entering molar flow rate, FA0, to obtain (FA0/-rA) as a function of X as
shown in the following Table of the processed data for FA0 = 0.4 mol/s.