5-Non-Ideal Reactors: Introduction

Non-ideal reactors- how to characterize

Residence time distribution- importance

Pulse Input Experiment

Ideal reactors

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 Learning outcomes covered

A2.4.5 - Be able to apply their knowledge of chemical

engineering principles to complex and/or novel unit operations,
process equipment, and substances with complex behaviour;

A.4.2.8- Have a comprehensive understanding of design

processes and methodologies and an ability to apply and adapt
them in unfamiliar situations.

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 Objectives for this section are:

Understanding non-ideal reactor behaviour

How to characterize/analyze a real reactor

Why residence time is important for chemical reactors

Describing residence time distribution (RTD) function E(t)

3
 So far you modelled ideal reactors:

Reality?

Discuss the assumptions with the person next to you for 2 min.

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 Assumptions:

Perfectly mixed batch

The plug flow (PFR)

The ideal packed bed (PBR)

The perfectly mixed continuous tank (CSTR)

reality

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 Flow characteristics contributing to
non-ideal behavior:

Short circuiting/bypass/channeling

Dead spot/volume

Non-ideal inlet/outlet conditions

Diffusion from concentration gradient

Dispersion from turbulent transport

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 Nonideal Flow in a CSTR

• Ideal CSTR: uniform reactant concentration throughout the

vessel
• Real stirred tank
• Relatively high reactant concentration at the feed entrance
• Relatively low concentration in the stagnant regions, called
dead zones (usually corners and behind baffles)
Short Circuiting

Dead Zone

Dead Zone 7
 Nonideal Flow in a PBR

• Ideal plug flow reactor: all reactant and product molecules at any given
axial position move at same rate in the direction of the bulk fluid flow
• Real plug flow reactor: fluid velocity profiles, turbulent mixing, &
molecular diffusion cause molecules to move with changing speeds and
in different directions

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 Real Plug Flow Reactor: back mixing & axial
dispersion occurs

Plug flow reactor Real tubular reactor

Concentration profile Concentration profile

Plug flow reactor:

• Constant velocity of flow in every part of a system.
• The time is the same for every streamline, since velocity is
constant and the channel length is the same for all streamlines.

Real tubular reactor:

• Some molecules will diffuse forward ahead of the molar average
velocity while others will lag behind.

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 What are the consequences of
non-ideality in a reactor?
• Xideal  Xreal (exit)

• Cideal  Creal (exit)

• Product quality is affected. Especially with polymer

production, molecular weight distribution is varied.

• Reactor volume and length will be bigger/longer.

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 How to study non-ideal reactors:

Non-ideal reactors do not follow the models developed for ideal

CSTRs, PFRs, and PBRs

Part I: Characterize non-ideal reactors with Residence time

distribution (RTD) data and mean (average) residence time
Ideal reactors as a reference point
Examples for diagnosing real reactors
Dead volume
Bypassing
……..
……..

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 How to study non-ideal reactors?

Part II: How to use the residence time data and functions to make
predictions of conversion and exit concentrations.
The residence time distribution is not unique for a given reaction
system
Use new models if one wants to predict the conversion in nonideal
reactor with mixing behavior.
The five most common models to predict conversion:
Dispersion (non-first order, good mixing)
Segregation (first order, complete mixing)
Two-parameter models

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 Residence time distribution-introduction

In non-ideal reactors: Not all molecules spend the same time in the
reactor.
Flow through a reactor is characterized by:
1. The amount of time molecules spend in the reactor, called
the RTD
2. Quality of mixing

Different residence time means different reaction times. Product

distribution’s is affected by the RTD.
One example: polymerization reaction, product selectivity, polymer
molecular weight distribution can be significantly affected by RTD.
So, RTD for real reactors must be determined.

RTD can be determined by experimentally with a tracer technique.

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 Pulse Input Experiment- response from a
detector

in reactor out

Inject a tracer at t= 0
Inject a tracer into the feed side of the reactor.
Tracer can be a dye, radioactive or electrolyte-Similar properties to the
actual feed to the reactor.
A detector measures the concentration of the tracer leaving the reactor.
Inject the tracer at t=0
Measure the tracer amount with the detector at the outlet stream.
Question: What are we expecting from the reactor when we inject a
tracer:

C,
mol/m3

t=0 time 14
 Pulse Input Experiment- tracer amount

• So the outlet detector is going to get some tracer spread out in time
because different molecules spend different times in the reactor.

• The area under these curves are proportional with the …amount of
tracer if there is no hold up/no leak/ adsorbing on catalyst etc.

• This means area of the two curves are equal.

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 Pulse Input Experiment- tracer amount calculation
Area for the small time difference = number of the
moles of the tracer:

C
= volumetric flow rate (m3/s)
= thickness
𝑡 𝑡+ Δ𝑡
time

Total moles of tracer=amount of tracer injected

It should be normalized, because the properties of the reactor shouldn’t depend

on the amount of tracer is used.
Fraction of molecules spending t and t+ t in the reactor [E(t) t] :
E(t) dt= E(t) t as t is very small. E(t) is residence distribution function
E(t) t E(t)

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 Pulse Input Experiment- RTD function, E(t)

•
• E(t) Probability of a molecule will reside in the reactor for time t

• That molecule spend that time to react in the reactor.

• fraction of material that has residence time between t and t+dt.

• because it’s a fraction

RTD can be calculated for ideal reactors, but must be measured for
real reactors!!!

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 Example 1. Construct residence time
distribution E(t) plot for a non-ideal reactor:

A tracer measurement for a pulse input is shown in the Figure 1.

What is the average residence time for this non-ideal reactor?
0.5 Figure 1. Pulse input response from a
non-ideal reactor
C(t)
mol.m-3 is given

5 10 15
Time
Answer: (min)

Figure 2. RTD for a non-ideal reactor

E(t)
min-1

5 10 15
Time 18
(min)
 Figure 1 needs to be normalized for RTD:

So, integrate and find the area under the triangle:

∞
(15 − 5 ) ( 0.5 −0 )
∫ 𝐶 ( 𝑡 ) 𝑑𝑡=𝑎𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑡h𝑒 𝑐𝑢𝑟𝑣𝑒 ( 𝑡𝑟𝑖𝑎𝑛𝑔𝑒 𝑎𝑟𝑒𝑎 ) = 2
=2.5
0

• Divide the Figure 1 plot with total area value and plot Fig 2.

0.5/2.5= 0.2
Figure 2. RTD for a non-ideal
E(t) reactor
min-1

5 10 15
Time
(min)
• But how to find the E(t) function??

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 E(t) function:

Intersectio
n 0.2

E(t) = a t + b
b Figure 2. RTD for a non-ideal reactor
E(t)

a is the …slope……………
min-1

b is the …intersect……………..

5 10 15
Time
(min)

Slope= tan()

To find b, use data points from the graph. At t=15 min E(t)=0
0=-0.02(15)+b  b= 0.3
E(t) = -0.02 t + 0.3
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 Mean Residence Time, tm

• For an ideal reactor, the space time  is defined as V/u0

• The mean residence time tm is equal to  for a perfectly mixed
reactor

0 tE t dt V
tm   0 tE t dt   tm

0 E t dt 0

By calculating tm, the reactor V can be determined from a tracer

experiment 2  2
The spread of the distribution (variance):  0 t  tm  E t dt

Space time t and mean residence time tm would be equal if the

following two conditions are satisfied:
• No density change
• No backmixing

In practical reactors the above two may not be valid, hence there
will be a difference between them 21
 Mean (average) residence time

E(t) = -0.02 t + 0.3

 tm =
tm =  t E tm =
( t )dt
0

0.5

C(t)
mol/m3

5 10 15
Time
Average residence time= 8.33 min
(min)
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 Example 2: Constructing the C(t) and E(t)
Curves
A sample of tracer hytane at 320 K was injected as a pulse to a reactor, and the
instantaneous effluent concentration was measured as a function of time.

t 0 1 2 3 4 5 6 7 8 9 10
C (t) 0 1 5 8 10 8 6 4 2.6 1.4 0

1. Construct the C(t) and the E(t) Functions.

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C(t) (g/min)
6
C( t
E(t)
E t  ) 4
function,
 2

0
0 2 4 6 8 10
t (min)
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 Example 2. Constructing the C(t) and E(t) Curves

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 C( t )dt  46 g. min/
0.2
3
m
0

E(t) (min-1)
0.1

0
0 2 4 6 8 10
t (min)

t 0 1 2 3 4 5 6 7 8 9 10
C (t) 0 1 5 8 10 8 6 4 2.6 1.4 0
E(t) 0 0.02 0.1 0.17 0.2 0.17 0.13 0.08 0.06 0.03 0

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 Example 3- Mean Residence Time

Calculate the mean residence time of the reactor characterized in

Example 2.
∞
Mean (average) residence time:𝑡 𝑚 = ∫t E( t ) 𝑑𝑡
0

C( t ) 10
E(t) 3
function,
E t   C( t )dt  46 g. min/ m
 0

t 0 1 2 3 4 5 6 7 8 9 10
C (t) 0 1 5 8 10 8 6 4 2.6 1.4 0
E(t) 0 0.02 0.1 0.17 0.2 0.17 0.13 0.08 0.06 0.03 0
t E(t) 0 0.02 0.2 0.51 0.8 0.85 0.78 0.56 0.48 0.27 0

t. E(t) 4.47 min

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 PFR (Ideal)

Fig 1. Pulse input in ideal PFR

A pulse input in an ideal PFR becomes a pulse input and defined by Dirac Delta
Function. This function has the following properties:

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 CSTR (Ideal)

A pulse input
Fig 2. Pulse input
leads to a sharp
in ideal CSTR peak with a tail

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 Study Question: Finding the RTD by experiment

The concentration readings in the Table represent a continuous response to a pulse

input into a closed vessel which is to be used as a chemical reactor.

1- Calculate the mean residence time of fluid in the vessel, tm,

2- Tabulate and plot the RTD function, E(t).

t (min) 0 5 10 15 20 25 30 35
C (g/l) 0 3 5 5 4 2 1 0

Solution:


C( t
E(t) function,
E t  )
 tE 

t m  ( t )dt
  tE
  C( t ) 0 ( t )dt
0dt
0 0

E( t )dt 28
 What did you learn?

• Not all molecules spend the same time in the reactor.

• Different residence time means different reaction times. Product
distributions is affected by the RTD.
• I can describe and calculate E(t), which is residence time
distribution function

• I know an ideal PFR pulse input response

is a sharp peak

• A pulse input leads to a sharp peak

with a tail

• RTD can be calculated for ideal reactors, but must be measured

for real reactors!!! 29