Steady State

Plug Flow Reactor

Hernandez│Pine
Plug Flow Reactor
• usually operated continuously at steady-state, apart from start-up and
shutdown periods
• may be used for either gas-phase or liquid-phase reactions

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Uses of a PFR
The PFR model is frequently used for a reactor
in which the reacting system (gas or liquid) flows
at relatively high velocity (high Re, to approach
PF) through an otherwise empty vessel or one
that may be packed with solid particles. The
reactor may be used in large-scale operation for
commercial production, or in laboratory- or pilot-
scale operation to obtain design data.
Types of PFR

a. b. c.

Many single-phase The reactor Figure (c) also

reactions, such as incorporates a fixed- represents a fixed-
the dehydrogenation bed of solid particles bed catalytic reactor,
of ethane for of catalyst; that is, but one in which the
production of the particles do not catalyst particles are
ethylene, take place move. The packed either inside
in reactors arrangement in (b) is or outside of tubes.
represented by an for adiabatic
empty tube or vessel operation.
 Design Equation for a PFR

Material Balance
input = output + disappearance by reaction + accumulation

accumulation = 0 (for steady state)

input of A, moles/time = FA

output of A, moles/time = FA + dFA

disappearance of A by reaction, moles/time = (-rA)dV

𝐹𝐴 = 𝐹𝐴 + 𝑑𝐹𝐴 + (−𝑟𝐴)𝑑𝑉 Equation A Equation B

𝑉 𝜏 𝑋 𝑑𝑋 𝑉𝐶𝐴0 𝑋 𝑑𝑋
Since 𝑑𝐹𝐴 = 𝑑 𝐹𝐴0 1 − 𝑋𝐴 = −𝐹𝐴0 𝑑𝑋𝐴 = = ‫׬‬0 𝐴𝑓 −𝑟 𝐴 𝜏= = 𝐶𝐴0 ‫׬‬0 𝐴𝑓 −𝑟 𝐴
𝐹𝐴0 𝐶𝐴0 𝐴 𝐹𝐴0 𝐴
𝐹𝐴0 𝑑𝑋𝐴 = −𝑟𝐴 𝑑𝑉
𝑉 𝑑𝑉 𝑋 𝑑𝑋
‫׬‬0 = ‫׬‬0 𝐴𝑓 −𝑟 𝐴
𝐹𝐴0 𝐴
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 Design Equation for a PFR

General expressions for A and B would be: Equations A and B would be:
𝑉 𝑋 𝑑𝑋𝐴 𝑉 𝜏 𝑋 𝑑𝑋𝐴 −1 𝐶𝐴𝑓 𝑑𝐶𝐴
= ‫𝑓𝐴 𝑋׬‬ = = ‫׬‬0 𝐴𝑓 = ‫׬‬
𝐹𝐴0 𝐴𝑖 −𝑟𝐴 𝐹𝐴0 𝐶𝐴0 −𝑟𝐴 𝐶𝐴0 𝐶𝐴0 −𝑟𝐴

𝑋 𝑑𝑋𝐴 𝑋 𝑑𝑋𝐴 𝐶 𝑑𝐶𝐴

𝜏 = 𝐶𝐴0 ‫𝑓𝐴 𝑋׬‬ 𝜏 = 𝐶𝐴0 ‫׬‬0 𝐴𝑓 = − ‫𝑓𝐴 𝐶׬‬
𝐴𝑖 −𝑟𝐴 −𝑟𝐴 𝐴0 −𝑟𝐴

For constant density system:

𝐶𝐴
𝑋𝐴 = 1 −
𝐶𝐴0

𝑑𝐶𝐴
𝑑𝑋𝐴 = −
𝐶𝐴0

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Constant Density

• For systems of changing density it is more convenient to use conversions;

however, there is no particular preference for constant density systems.

• Whatever its form, the performance equations interrelate the rate of reaction,
the extent of reaction, the reactor volume, and the feed rate, and if any one of
these quantities is unknown it can be found from the other three.

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 Kinetic Expressions in Eq. A

𝑉𝐶𝐴0 𝑀+𝑟𝑋𝐴𝑒 𝑋𝐴
𝑘𝜏 = = 𝐶𝐴0 𝑋𝐴 𝑘1 𝜏 = [− 1 + 𝜀𝐴 𝑋𝐴𝑒 ln 1 − − 𝜀𝐴 𝑋𝐴 ]
𝐹𝐴0 𝑀+𝑟 𝑋𝐴𝑒

First-order reversible reaction

Zero order homogeneous
reaction 𝐶𝑅0
𝐴 ↔ 𝑟𝑅, ൗ𝐶 = 𝑀
𝐴0

Second-order irreversible reaction

First-order irreversible reaction 𝐴 + 𝐵 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑤𝑖𝑡ℎ 𝑒𝑞𝑢𝑖𝑚𝑜𝑙𝑎𝑟 𝑓𝑒𝑒𝑑
𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
Or 2𝐴 → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

𝑘𝜏 = − 1 + 𝜀𝐴 ln 1 − 𝑋𝐴 − 𝜀𝐴 𝑋𝐴 𝑋𝐴
𝐶𝐴0 𝑘𝜏 = 2𝜀𝐴 1 + 𝜀𝐴 ln 1 − 𝑋𝐴 + 𝜀 2𝐴 𝑋𝐴 + (𝜀𝐴 + 1)2
1 − 𝑋𝐴
Where the density is constant, put 𝜀 = 0 to obtain the simplified
performance equation.

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 Constant
and Varying • For systems of constant density (constant-volume batch and
constant-density plug flow) the performance equations are

Densities identical,𝜏 for plug flow is equivalent to t for the batch

reactor, and the equations can be used interchangeably.
• For systems of changing density there is no direct
correspondence between the batch and the plug flow
equations and the correct equation must be used for each
particular situation. In this case the performance equations
cannot be used interchangeably.

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 Holding Time and Space Time for Flow Reactors

Space Time
Time needed to treat one reactor volume of feed

𝑋𝐴
𝑑𝑋𝐴
𝑡 = 𝐶𝐴0 න
0 (−𝑟𝐴 ) 1 + 𝜀𝐴 𝑋𝐴
𝑉𝐶𝐴0 𝑉
𝜏= =
𝐹𝐴0 𝑣0

Holding Time
The residence time of flowing material in the reactor

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Constant Density
Systems
𝑉
𝜏=𝑡=
𝑣
Note that the value of t depends on what happens in the reactor,
while the value of τ is independent of what happens in the reactor.

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Performance Equations for nth Order Kinetics and 𝜀𝐴 = 0
Performance Equations for nth Order Kinetics and 𝜀𝐴 ≠ 0
A homogeneous gas reaction 𝐴 → 3𝑅 has a reported rate at 215 °C
−2 1Τ 𝑚𝑜𝑙𝑒
−𝑟𝐴 = 10 𝐶𝐴 2
(𝑙𝑖𝑡𝑒𝑟)(𝑠𝑒𝑐𝑜𝑛𝑑)

Find the space-time needed for 80% conversion of a 50% A-50% inert feed
to a plug flow reactor operating at 215 °C and 5 atm (𝐶𝐴0 =
0.0625 𝑚𝑜𝑙𝑒Τ𝑙𝑖𝑡𝑒𝑟).

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A homogeneous gas decomposition of phosphine 4𝑃𝐻3 → 𝑃4(𝑔) + 6𝐻2
proceeds at 649 °C with the first order rate
−𝑟𝑃𝐻3 = 10ൗℎ𝑟 𝐶𝑃𝐻3
What size of plug flow reactor operating at 649 °C and 460 kPa can produce
80% conversion of feed consisting of 40 mol of pure phosphine per hour?

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Thank You!