Plug Flow Reactor

CAPE3320/5311M Reaction Engineering

Xiaojun Lai

1.27 Chemical Engineering

[email protected]
Plug Flow Reactor
STEADY-STATE REACTOR

 Plug flow (PFR, Plug flow, Piston flow, ideal tubular, unmixed flow)

 There may be lateral mixing (radial)

 No axial mixing: the residence time in the reactor is the same for all elements of fluid.
  Similar to CSTR (mixed flow reactor)

Pulse input

0 
Mass Balance in a small volume section of in a steady state PFR

XA XA+dXA
 FA = FA0(1 - XA)

- dFA = (-rA)dV

FA0 dXA = (-rA)dV

Performance equation of PFR Calculate V 0  FA0 CA0 skilfully
 Example For a 1st order reaction A  R, -rA = kCA

𝐶𝐴𝑓 𝐶𝐴𝑓
  𝑉 𝑑𝐶𝐴 𝑑𝐶𝐴   𝐶𝐴0
= = ∫
 𝐶𝐴 0
=∫
− 𝑟 𝐴 𝐶𝐴 0 𝑘 𝐶 𝐴
ln
( )
𝐶 𝐴𝑓
=𝑘  (Same as Batch reactor)

2nd order reaction 2A  R, -rA = kCA2

𝐶𝐴𝑓 𝐶𝐴𝑓
  𝑉 𝑑𝐶𝐴 𝑑𝐶𝐴  
- =
= =∫ =∫
 𝐶𝐴 0 − 𝑟 𝐴 𝐶𝐴 0 𝑘 𝐶 𝐴
2
 Varying volume
 For gaseous reactions in a sealed batch reactor
 Reaction is kept constant temperature and pressure
 The progress of the reaction is followed by noting the
movement of the bead with time

A  2R
• Initial 1 mole of A volume = V0 (i.e. 1L) ; CA0 = 1 mol/L
• when XA = 1, A transformed to 2 mole R, total volume = 2 Litres

 If XA = 0.5,
0.5 mole A will become 1 mole R, + the remaining 0.5 mole A
the total number of mole = 1.5L;
so the CA = 1/1.5L = 1/3 mol/L

In this case of varying volume reaction, when XA =0.5, CA  1/2 mol/L

 Linear relationship

  N A
C A= =¿ ¿
V
 Constant density batch and flow systems (e.g. reaction in solution)

A is volume fractional change

 Gases of changing density but T and P constant
Calculation of A
For reaction A + B  R,
For reaction A  2R, Input CA0 = 1 mol/L, CB0 = 3 mol/L,
pure A input, calculate A calculate A

X=0 X=1 XA=0 XA=1

A 1 (mol) 0 (mol) A 1 0
B 3 2

R 0 2 R 0 1

total 1 2 total 4 3
  A =   A =

reaction A  2R,
Input A with 50% inert
gas, what is A ?
Solution reaction A → 3R, -rA = 10-2 CA0.5 [mol/litresec],
Find the space time  for a plug flow reactor which providing 80% conversion with CA0 = 0.0625 mol/L

Answer: in the solution reaction, it is constant density (no volume change, A = 0)

 =

CA -rA 1/rA
0.0625 0.0025 400
0.05625 0.002372 421.637
0.05 0.002236 447.2136
0.04375 0.002092 478.0914
0.0375 0.001936 516.3978
0.03125 0.001768 565.6854
0.025 0.001581 632.4555
0.01875 0.001369 730.2967
0.0125 0.001118 894.4272

By estimating the sections under the curve,  = 27.7 sec

 𝟏
  𝐦𝐨𝐥 −𝟐 𝟐
−𝐫 𝐀 =𝟏𝟎 𝐂 𝐀
𝐥∗𝐬 𝐗 𝐀𝐅 0,5 𝐗 𝐀𝐅
 
𝐕 𝐝 𝐗𝐀 𝐂𝐀0 𝐝 𝐗𝐀
𝛕= =𝐂 𝐀 0 ∫ →𝛕= ∫
You cannot use CA in rate
𝐯0 0.5 1− 𝐗 𝐀
0.5
𝐤 1−𝐗 𝐀
0.5

  𝐍 𝐀
equation to do integration,
use XA instead
0
( )
𝐤 𝐂𝐀 0
1+𝛆 𝐀 𝐗 𝐀
0
( )
1+𝛆 𝐀 𝐗 𝐀
𝐂 𝐀= =¿ ¿
𝐕

0.5
  1− 𝐗𝐀
−𝐫 𝐀 =10
−2
( 𝐂 𝐀0
1+ 𝛆 𝐀 𝐗 𝐀 )
  0.0625 𝒔
0.5 0.8
( 1+ 𝐗 𝐀 ) 0.5 𝒅 𝐗 𝐀
𝛕= −2 ∫ 0.5
10 0 (1 − 𝐗 𝐀 )
 0.5
  𝒎𝒐𝒍

𝛕=
0.0625
0.5
( 𝒍 ) 0.8

∫
( 1+ 𝐗 𝐀 ) 0.5 𝒅 𝐗 𝐀
0.5 0.5
𝒎𝒐𝒍 ( 1− 𝐗 𝐀 )
10 −2
( )
𝒍
/𝒔 0

The area of under curve (AUC) is estimated 1.33

 PFR in series

V1 V2
𝐅𝐀𝟎 𝐅𝐀𝟏 = 𝐅𝐀𝟎 (𝟏 − 𝐗 𝐀𝟏 )
𝐅𝐀𝟐 = 𝐅𝐀𝟎 (𝟏 − 𝐗 𝐀𝟐 )
𝐂𝐀𝟎
𝐗 𝐀=𝟎

V1 Vn
𝐅𝐀𝟎 (𝟏 − 𝐗 𝐧 )
𝐅𝐀𝟎 (𝟏 − 𝐗 𝐋−𝟏 ) 𝐅𝐀𝟎 (𝟏 − 𝐗 𝐢 ) 𝐅𝐀𝟎 (𝟏 − 𝐗 𝐧−𝟏 )

(Rate in ) = (Rate out)+(Rate of consumption)+(Rate of accumulation)

Steady State
𝐅𝐀 𝐅𝐀 + 𝐝𝐅𝐀
𝐂𝐀 𝐂𝐀 + 𝐝𝐂𝐀

𝐅𝐀𝟎 ሺ
𝟏 − 𝐗 𝐀 ሻ = 𝐅𝐀𝟎 ൫
𝟏−ሺ
𝐗 𝐀 + 𝐝𝐗 𝐀 ሻ൯+ ሺ
−𝐫𝐀 ሻ𝐝𝐕 →

𝐝𝐕 𝐝𝐗 𝐀
𝐅𝐀𝟎 𝐝𝐗 𝐀 = −𝐫𝐀 ∗ 𝐝𝐕 → =
𝐅𝐀𝟎 −𝐫𝐀
 𝐕 𝐗 𝐀𝟎 𝐕𝐢 𝐗 𝐀𝐢
𝐝𝐕 𝐝𝐗 𝐀 𝐝𝐕 𝐝𝐗 𝐀
න =න 𝐨𝐫 න =න
𝟎 𝐅𝐀𝟎 𝟎 −𝐫𝐀 𝟎 𝐅𝐀𝟎 𝐗 𝐀𝐢−𝟏 −𝐫𝐀
PFR in parallel
6.1. RECYCLE REACTION
 𝑣2 = ሺ
𝑅 + 1ሻ𝑣𝑓
1) 𝑣2 = 𝑣𝑓 + 𝑣3 = 𝑅𝑣𝑓 + 𝑣𝑓 = (𝑅 + 1)𝑣𝑓 →
𝑣3 = 𝑅𝑣𝑓

𝐹𝐴2 = 𝐹𝐴3 + 𝐹𝐴4 = 𝑅𝐹𝐴4 + 𝐹𝐴4 = (𝑅 + 1)𝐹𝐴4 → 𝐹𝐴2 = ሺ

𝑅 + 1ሻ𝐹𝐴4
𝐹𝐴3 = 𝑅𝐹𝐴4

2) 𝐹𝐴4 = 𝐹𝐴0 (1 − 𝑋𝐴𝑓 )= 𝐹𝐴0 (1 − 𝑋𝐴2 )

𝐹𝐴2 = ሺ
𝑅 + 1ሻ∗ 𝐹𝐴0 (1 − 𝑋𝐴𝑓 )
𝐹𝐴3 = 𝑅 ∗ 𝐹𝐴0 (1 − 𝑋𝐴𝑓 )
31) 𝐹𝐴1 = 𝐹𝐴0 (1 − 𝑋𝐴𝑓 )

𝐹𝐴1 = 𝐹𝐴0 + 𝐹𝐴3 = 𝐹𝐴0 + 𝑅𝐹𝐴4 = 𝐹𝐴0 + 𝑅 ∗ 𝐹𝐴0 (1 − 𝑋𝐴𝑓 )

𝐹𝐴1 = 𝐹𝐴0 (1 + 𝑅(1 − 𝑋𝐴𝑓 )) → 𝐹𝐴1 = 𝐹𝐴0 (1 + 𝑅 − 𝑅𝑋𝐴𝑓 )

𝐹𝐴1 𝐹𝐴0 + 𝐹𝐴3 𝐹𝐴0 + 𝑅 ∗ 𝐹𝐴0 (1 − 𝑋𝐴𝑓 ) 𝐹𝐴0 (1 + 𝑅(1 − 𝑋𝐴𝑓 ))

𝐶𝐴 = = = =
𝑣1 𝑣0 + 𝑅𝑣𝑓 𝑣0 + 𝑅𝑣0 (1 + 𝜀𝐴 𝑋𝐴𝑓 ) 𝑣0 {1 + 𝑅(1 + 𝜀𝐴 𝑋𝐴𝑓 )}

1 + 𝑅൫1 − 𝑋𝐴𝑓 ൯ 𝐶𝐴1 1 + 𝑅 − 𝑅𝑋𝐴𝑓

𝐶𝐴1 = 𝐶𝐴0 ∗ → =
1 + 𝑅൫1 + 𝜀𝐴 𝑋𝐴𝑓 ൯ 𝐶𝐴0 1 + 𝑅 + 𝑅𝜀𝐴 𝑋𝐴𝑓

𝐶𝐴1
1− ൗ𝐶𝐴0
𝑋𝐴1 =
𝐶
1 + 𝜀𝐴 ∗ 𝐴1ൗ𝐶𝐴0
 1+𝑅−𝑅𝑋𝐴𝑓
1− 1+𝑅+𝑅𝜀 𝑋
𝐴 𝐴𝑓 𝑅൫
1+𝜀𝐴 ൯𝑋𝐴𝑓 𝑅൫1+𝜀𝐴 ൯
𝑋𝐴𝑓
𝑋𝐴1 = 1+𝑅−𝑅𝑋𝐴𝑓 →= → 𝑋𝐴1 =
1+𝑅൯
൫ +𝜀𝐴 ൫
1+𝑅൯ 1+𝑅൯
൫ (1+𝜀𝐴 )
1+𝜀𝐴 1+𝑅+𝑅𝜀 𝑋
𝐴 𝐴𝑓

𝑅
𝑋𝐴1 = ( )𝑋𝐴𝑓
𝑅+1
When the recycle rate R is very small, e.g. 0, it is the case of PFR
When the recycle rate R is very large e.g. ∞, it is the case of CSTR
Temperature Effect on reactor

Rate of reaction is affected by T, so to determine the optimum temperature

progression and specify heat exchange
Single reactions
• Heats of reaction
• Temperature progression
• Heat effect - Adiabatic

• Heat liberated / absorbed (depends on)

 The nature of the reacting system
 The amount of material reacting
 The temperature and the pressure of the reacting system

It is calculated by the heat of reaction

• Maximum possible conversion
Heat of reaction from thermodynamics
Can be calculated from: heats of formation or heats of combustion
It is defined at T
The heat transferred to the reacting system from the surroundings when a moles of A
disappear to produce r moles of R and s moles of S, at T.
 𝑇2 𝑟𝑒𝑎𝑑 ∆𝐻𝑟2 𝑎𝑡𝑇2 =? 𝑇2 𝑝𝑟𝑜𝑑

Cool/heat Heat/cool
reactants products

Reactants Products
∆𝐻𝑟1 𝑎𝑡 25
25℃ 25℃

where
IF
In the adiabatic reactor, all the heat liberated or absorbed would be
consumed heat or cool the reaction system
For practical purpose, reaction system specific heat change is negligible
Graph represents energy balance equation for adiabatic
operation. The Lines in the graph are the adiabatic lines, or
operation progression lines
Temperature Effect on reaction rate

irreversible reaction

XA=1
low rA

High rA
XA

T
-1/rA
Adiabatic Equal reaction
progression line rate lines
 Residence time distribution (RTD)
 
• Elements of fluid take different routes through the reactor
• So take different lengths of time to pass through the vessel
• The distribution of these times for the stream of fluid leaving the vessel is called the
residence time distribution (RTD), or the exit age distribution E (unit of time-1).

E
RTD profile

the average residence

time is given:

For the RTD as above, the mean

residence time is given:
 D
For axial dispersion, ( ) is the dimensionless group characterising the spread in the whole vessel,
uL
where D (m2/s) is the dispersion coefficient; u is axial flow velocity and L is the tube length.
3

𝐃
Small Deviation from Plug Flow < 0.01, small deviations from plug flow
𝐮𝐋
6
𝐃
Small Deviation from Plug Flow > 0.01, large deviations from plug flow
𝐮𝐋