ABSTRACT

This experiment is carried out to examine the pulse and step change input in a
tubular flow reactor, and to construct a residence time distribution function for the
flow reactor. Tubular flow reactor (model: BP-101B) was used as the experiment
equipment and the conductivity or known as the concentration of the tracer in the
reactor was recorded. The reactor was run for 5 minutes at the maintained de-ionized
water flowrate at 700 mL/min. From both experiment, C(t) curve and E(t) curve were
plotted to find the residence time of the fluid inside the reactor. Also, the mean
residence time, second moment (variance) and third moment (skewness) were
calculated from the result obtained from both experiment. All calculated results and
plotted graph were compared. For the first experiment, the mean residence time,
variance and skewness calculated are 0.1400 min, 0.2095 min2 and 0.3407 min5/2
respectively. For the second experiment, the mean residence time is 0.0398 min,
01578 min2 in variance and 0.6617 min5/2 of skewness. For pulse input experiment,
the inlet tracer concentration is suddenly change from zero value to the higher value
and reduces at zero again once it reached the set point. While for the step change
input experiment, the inlet concentration tracer gradually increases with time and stay
constant at same value once it reached it set point.

2.0

INTRODUCTION

Tubular Flow Reactor

Tubular reactor is a vessel through which flow is continuous, usually at steady state
and configured so that conversion of the chemicals and other dependent variables
are functions of position within the reactor than of time. The fluid flows as if they were
solid plugs or piston, and the reaction time is the same for all flowing material at any
given tube cross section are assume to made this reactor as an ideal tubular reactor.
Tubular reactor is resemblance of batch reactor which provides a high initial drive
force and diminishes as it flows through the tube.
The flow inside the tubular reactor can be laminar or turbulent. Turbulent flow is more
preferred compared to laminar flow as the turbulent flow gave out a better mixing and
heat transfer in the reactor. For small-scale lab and pilot plant reactors, the slow
reactions always preferred because the faster reactions establish a turbulent flow
that may cost a longer reactor with unacceptably high feed rate.
Residence Time Distribution
The Residence Time Distribution (RTD) is the time distribution of material which flows
is through the vessel. The channeling of fluid, recycling of fluid or by creation of
stagnant regions in the vessel may divert the flow pattern from the ideal flow
patterns. This type of flow should be avoided in heat exchangers, packed columns,
and reactor because it will lowers the efficiency of the unit.

Figure 2.1: Non-ideal flow patterns which may exist in process equipment
2

By knowing what is happening inside the vessel, the velocity distribution map for the
fluid in the vessel can be know, then we are able to predict the behavior of the vessel
as the reactor. Sadly, this approach cannot be done as it is still impractical. Instead of
the determination of the flow, we can determine the residence time distribution of the
flowing fluid. Residence time distribution can easily and directly determine by using
method of inquiry and the stimulus-response experiment.
E Curve
It is proved that the elements of the fluid taking different routes through the reactor
may take different lengths of time to pass through the vessel. Exit age distribution E
or RTD of fluid is the distribution of these times for the stream of fluid leaving the
vessel. The unit for E is time-1. The simplest method in determining E is by undergo
step and pulse experiment.

Figure 2.2: Early or late mixing affects reactor behavior

Figure 2.3: The exit age distribution curve E for the fluid flowing through a
vessel; also called the residence time distribution

The Pulse Experiment and Step Experiment

As stated above, RDT is a probability of a molecule residing in the reactor for a time
t. This can be found from a tracer experiment in which we inject a tracer of a nonreacting species with concentration into a reactor with fluid flowing at a steady flow
rate and we measure its concentration [C(t)] as it flows out of the reactor.
For pulse input, an amount of tracer is suddenly injected into the feed of a reactor
vessel with flow of steady state. As for step change input, the output concentration
from a vessel is related to the input function by the convolution integral where the
inlet concentration takes the form of either a perfect pulse input, imperfect pulse
injection or step input.

Figure 2.4: Transforming an experimental Cpulse curve to an E curve for pulse

input experiment

Figure 2.4: Transforming an experimental Cstep curve to an F curve for step

input experiment

3.0

AIMS

The objectives of these experiments are to:

Experiment 1 (Pulse input in a tubular flow reactor)

Investigate the effect of a pulse input in a tubular flow reactor.

Form a residence time distribution (RTD) function for the tubular flow reactor.

Experiment 2 (Step change input in a tubular flow reactor)

Analyze the effect of a step change input in a tubular flow reactor.

Form a residence time distribution (RTD) function for the tubular flow reactor.

4.0

THEORY

Residence time is the time the atoms have spent in the reactor and the residence
time distribution is the distribution of the various atoms comin out the reactor with
respect of time. RTD can be determined experimentally by injecting an inert
chemical, molecule, or atom, called tracer, into the reactor at some time t=0 and then
measuring the tracer concentration C in the exit stream as a function of time. Two
types of commonly used methods of injection are pulse and step input.
Pulse input
In a pulse input, an amount of tracer, N0 is suddenly injected in one shot into the feed
stream entering the reactor in as short time as possible. The outlet concentration is
then measured as ta function of time. The effluent concentration-time curve is
referred to as the C curve in the RTD analysis. If we select an increment of time t
sufficiently small that the amount of tracer material, N, leaving the reactor between
time t and t+t is essentially constant, then the amount of tracer material ,N, leaving
the reactor between time t and t+t is

N =C ( t ) v t
Where, v is the effluent volumetric flow rate. In the other words, N is the amount of
material that has spent an amount of time between t and t+t in the reactor. If we
now divide by the total amount of material that was injected into the reactor, N 0 , we
obtain

N vC (t)
=
t
N0
N0
This represents the fraction of the material that has a residence time in the reactor
between time t and t+t.
For pulse injection we define

E(t)=

vC (t)
N0

So that,

N
=E(t) T
N0
This quantity E(t) is called the residence time distribution function. It describes in a
quantitative manner how much time different fluid elements have spent in the reactor.
In terms of ODE,

dN =vC ( t ) dt
Integrate the function,

N 0= vC ( t ) dt
0

The volumetric flow rate v is constant, and so we can define E(t) as:

E (t)=

C (t)

C ( t ) dt
0

The integral in the denominator is the area under the C curve.

Step input
Consider a constant rate of the tracer addition to afeed that is initiated at time t= 0.
Before this time tracer was added to the feed. Thus, we have
C0(t) = 0

t<0

C0(t) = C0

t0

The concentration of the tracer in the feed to the reactor is kept at this level until the
concentration in the effluent is indistinguishable from that in the feed; the test may
then be discontinued. The output concentration from a vessel is related to the input
concentration by the convolution integral:

'

tt
C () E ( t ' ) dt '
t

C out ( t )=
0

Because the inlet concentration is a constant with time, C 0, we can take it outside the
integral sign. Thus,
t

C out ( t )=C 0 E ( t ' ) dt '

0

Dividing by C0 yields
t
C out
[
] = E ( t ' ) dt ' =F (t)
C 0 step 0

Thus, the normalized concentration vs time profile gives the F curve. The relation
between E(t) and F(t) is:

dF( t)
=E(t)
dt
For a laminar flow reactor, the velocity profile is parabolic with the fluid in the center
of the tube spending the shortest time. By using a similar analysis as shown above,
we obtain the complete RTD function for a laminar flow reactor as:
E(t) = 0

t < /2

E(t) = 2 / 23

t /2

We can also determine the dispersion number in the following manner:

tm =

t E ( t ) dt
0

t [ E (t )]

= C t
i

The variance is defined as:

2 =

( tt m )

E(t) =

2
( ttm ) E(t )

Ci t

5.0

APPARATUS

Heater
Control Panel
Tubular flow reactor

Feed Pumps

Product Tank

Figure 5.5: Front View of Tubular Flow Reactor (BP101-B)

Feed Tanks

Figure 5.6: Back View of Tubular Flow Reactor (BP101-B)

10

1. SOLTEQ Tubular flow reactor (Model: BP-101B)

2. Stopwatch
Materials
1. 0.025 M Sodium Chloride (NaCl)
2. De-ionized water

11

6.0

METHODOLOGY

General Start-Up Procedure

1. All valves were ensured initially closed except valve V7.
2. 20 L of salt solution was prepared. For example, sodium chloride, NaCl
(0.025M).
3. The feed tank B2 was filled with the NaCl solution.
4. The power for the control panel was turned on.
5. The water deionizer was connected to the laboratory water supply. Valve V3
was opened and feed tank B1 was filled up with the deionized water. Valve V3
was closed.
6. Valves V2 and V10 were opened. Pump P1 was switched on. P1 flow
controller was adjusted to obtain a flow rate of approximately 700 mL/min at
flow meter FI-01. The conductivity display was observed at low value then a
valv V10 was closed and pump P1 was switched off.
7. Valves V6 and V12 were opened. Pump P2 was switched on. P2 flow
controller was adjusted to obtain a flow rate of approximately 700 mL/min at
flow meter FI-02. A valve V12 was closed and pump P2 was switched off.
8. The unit was ready for experiment.

Shut-Down Procedure
1. Both pump P1, P2 and P3 were switched off. Valves V2 and V6 were closed.
2. The heaters were switched off.
3. The cooling water was kept circulating through the reactor while the stirrer
motor is running to allow the water jacket to cool down to room temperature.
4. All liquid were drained from the unit by opening valves V1 and V16 if the
equipment is not going to be used for long period of time. The feed tanks
were rinsed with clean water.
5. The power for the control panel was turned off.

Experimental Procedures
Experiment 1: Pulse Input in a Tubular Flow Reactor
1. The general start-up procedures were performed.
2. Valve V9 was opened and pump P1 was opened.
12

3. Pump P1flow controller was adjusted to give a constant flow rate of deionized water into the reactor R1 at approximately 700 mL/min at FI-01.
4. The de-ionized water was let to continue flowing through the reactor until the
inlet (QI-01) and outlet (QI-02) conductivity values are stable at low level.
Both conductivity values were recorded.
5. Valve V9 was closed and pump P1 was switched off.
6. Valve V11 was opened and pump P2 was switched on. The timer was
switched on simultaneously.
7. Pump P2 flow controller was adjusted to give a constant flow rate of salt
solution into the reactor r1 at 700 mL/min at FI-02.
8. The salt solution was let to flow for 1 minute, and then timer was reset and
restarted. This will start the time at the average pulse input.
9. Valve V11 was closed and pump P2 was switched off. Then, valve V9 was
opened and pump P1 was switched on quickly.
10. The de-ionized water flowrate was maintained at 700 mL/min by adjusting P1
flow controller.
11. Both inlet (QI-01) and outlet (QI-02) conductivity values were recorded at
regular intervals of 30 seconds.
12. The conductivity values were recorded until the readings were almost
constant and approach the stable low level values.

Experiment 2: Step Change Input in a Tubular Flow Reactor

1. The general start-up procedures were performed.
2. Valve V9 was opened and pump P1 was switch on.
3. Pump P1 flow controller was adjusted to give a constant flow rate of deionized water into the reactor R1 at approximately 700 mL/min at FI-01.
4. The de-ionized water was let to continue flowing through the reactor until the
inlet (QI-01) and outlet (QI-02) conductivity values were stable at low levels.
Both conductivity values were recorded.
5. Valve V9 was closed and pump P1 was switched on.
6. Valve V11 was opened and pump P2 was switched on. The timer was started
simultaneously.
7. Both the inlet (QI-01) and outlet (QI-02) conductivity values were recorded at
regular intervals of 30 seconds.
8. The conductivity values were continued recorded until all readings are almost
constant.

Preparation of Calibration Curve for Conversion vs. Conductivity

1. The following solutions were prepared:
a) 1 L of sodium hydroxide, NaOH (0.1M)
b) 1 L of sodium acetate, Et(Ac) (0.1M)
c) 1 L of deionized water, H2O
13

2. The conductivity and NaOH concentration were determined for each

conversion values by mixing the following solutions into 100 mL of deionized
water:
a)
b)
c)
d)
e)

7.0

0% conversion :
25% conversion :
50% conversion :
75% conversion :
100% conversion :

100 mL NaOH
75 mL NaOH + 25 mL Et(Ac)
50 mL NaOH + 50 mL Et(Ac)
25 mL NaOH + 75 mL Et(Ac)
100 mL Et(Ac)

RESULTS

Calibration Results

Solution Mixtures
Conversio

Concentratio

(mL)

n of NaOH

(M)

Conductivit
y (mS/cm)

0.1 M

0.1 M

NaOH

Et(Ac)

0%

100

100

0.0500

10.140

25%

75

25

100

0.0375

7.010

50%

50

50

100

0.0250

3.790

H2O

14

75%

25

75

100

0.0125

0.897

100%

100

100

0.0000

0.269

Calibration Curve
120
100
f(x) = - 9.3x + 91.14
R = 0.96

80
Conversions (%)

60
40
20
0
0

10

12

Conductivity (mS/cm)

Figure 7: Calibration Curve

Experimental Results
15

Flow rate = 700.0 mL/min

Input type = De-ionized water

Experiment 1: Pulse Input in a Tubular Flow Reactor

Table 7.1: Calculated Results for Experiment 1
Conductivity
(mS/cm)
Time
(min)

E(t)

tm

(t- t m ) 2 [ E ( t ) ]
Ci t

s3

(t- t m ) 3 [ E ( t ) ]
Ci t

Inlet

Outlet

Ci t
Ci t

0.0

0.5

0.0

0.0000

0.0000

0.0000

0.0000

0.5

0.2

0.0

0.0000

0.0000

0.0000

0.0000

1.0

0.0

2.6

0.2396

0.0221

0.0211

0.0207

1.5

0.0

3.5

0.4839

0.0669

0.0916

0.1313

2.0

0.0

1.5

0.2765

0.0510

0.0968

0.1887

2.5

0.0

0.0

0.0000

0.0000

0.0000

0.0000

3.0

0.0

0.0

0.0000

0.0000

0.0000

0.0000

3.5

0.0

0.0

0.0000

0.0000

0.0000

0.0000

4.0

0.0

0.0

0.0000

0.0000

0.0000

0.0000

4.5

0.0

0.0

0.0000

0.0000

0.0000

0.0000

5.0

0.0

0.0

0.0000

0.0000

0.0000

0.0000

1.0000

0.1400

0.2095

0.3407

t [E (t )]
Ci t

16

Outlet Conductivity vs Time

4
3.5
3
2.5
2

Outlet conductivity (mS/min)

1.5
1
0.5
0
-0.5 0

Time, t (min)

Figure 7.8: Graph of Outlet Conductivity Vs Time for Pulse Input

Residence Time Distribution

0.6
0.5
0.4
E(t) (min-1)

0.3
0.2
0.1
0
0

0.5

1.5

2.5

3.5

4.5

Time, t (min)

Figure 7.9: Residence Time Distribution Function for Pulse Input

17

Experiment 2: Step Change Input in a Tubular Flow Reactor

Table 7.2: Calculated Results for Experiment 2

Time
(min)

Conductivity
(mS/cm)

C(t)

E(t)

Ci t
Ci t
Ci t

tm

t [E (t )]
Ci t

s3
2

(t- t m ) [ E ( t ) ]
Ci t

(t- t m ) [ E ( t ) ]
Ci t

Inlet

Outlet

0.0

2.4

0.00

0.0

0.5

2.7

0.00

0.0

1.0

2.7

0.00

0.0

1.5

2.8

2.80

4.2

0.0454

0.0007

0.0011

0.0017

2.0

2.8

3.65

7.3

0.0789

0.0017

0.0034

0.0068

2.5

2.8

3.60

9.0

0.0973

0.0026

0.0065

0.0164

3.0

2.8

3.60

10.8

0.1168

0.0038

0.0113

0.0340

3.5

2.8

3.60

12.6

0.1362

0.0052

0.0180

0.0629

4.0

2.8

3.60

14.4

0.1557

0.0067

0.0268

0.1072

4.5

2.8

3.60

16.2

0.1751

0.0085

0.0382

0.1716

5.0

2.9

3.60

18.0

0.1946

0.0105

0.0524

0.2613

92.5

0.0398

0.1578

0.6617

18

Outlet Conductivity vs Time

4
3.5
3
2.5
2

Outlet conductivity (mS/min)

1.5
1
0.5
0
-0.5 0

Time, t (min)

Figure 7.10: Graph of Outlet Conductivity Vs Time for Step Change Input

Residence Time Distribution

0.25
0.2
0.15
E(t) (min-1)

0.1
0.05
0
0

Time, t (min)

Figure 7.11: Residence Time Distribution Function for Step Change Input

19

8.0

CALCULATIONS

Experiment 1: Pulse Input in a Tubular Flow Reactor

C ( t ) dt
0

, Area under the Graph

Using Simpsons rule:

Area,

C ( t ) dt
0

0.5
( 0+ 4 ( 0 ) +2 ( 2.6 ) + 4 ( 3.5 ) +2 ( 1.5 )+ 4 ( 0 )+ 0 ) = 3.7 m2
3

Sample calculations when t = 1.0 min

a) Mean residence time, tm =

t E ( t ) dt
0

t [ E (t )]

= C t
i

1.0 (0.0454)
3.7

= 0.0007

b) Second moment, Variance, 2 =

( tt m )

E(t)

2
( tt m ) E(t )

( 1.50.0007 )2 (0.0454)
92.5

c) Third moment, Skewness, s3 =

Ci t

1
tt m )3 E(t) =
3/ 2 (
0

( 1.50.0007 )3 (0.0454 )
92.5

= 0.0011

3
( tt m ) E( t)

Ci t

= 0.0017

20

Experiment 2: Step Change Input in a Tubular Flow Reactor

Area,

C ( t ) dt
0

C i t

From table 7.2

= 92.5 m2
Sample calculations when t = 1.5 min

a) Mean residence time, tm =

t E ( t ) dt
0

t [ E (t )]

= C t
i

1.5 (0.0454)
92.5

= 0.0007

2
b) Second moment, Variance, 2 = ( tt m ) E(t)
0

2
( tt m ) E(t )

Ci t

( 1.50.0007 )2 (0.0454)
92.5

c) Third moment, Skewness, s3 =

1
tt m )3 E(t)
3/ 2 (
0

( 1.50.0007 )3 (0.0454 )
92.5

= 0.0011

3
( tt m ) E( t)

Ci t

= 0.0017

21

22

9.0

DISCUSSIONS

There are two experiments that have been done to determine the residence time
distributions which are pulse input experiment and step change experiment. The
result of conductivity of both inlet and outlet of the tubular flow reactor have been
recorded at a constant flow rate of 700 mL/min. The fluid that has been injected into
the reactor is de-ionized water. From the result gain from both experiment, C(t) curve
have been plotted.
Based on the C(t) curve plotted for pulse input experiment on figure 7.2, the
shape of the curve obtain is slightly the same as the predicted C(t) curve that should
be obtain from the experiment as shown in figure 2.4 which can be depicted as the
amount of conductivity rapidly increases from C(t)=0 and vastly decreases at t= 2
minutes. From C(t) curve, residence time distribution graph is obtain and plotted as
figure 7.3. Also, the E(t) curve obtain is followed the predicted experimental E(t)
curve that also shown in figure 2.4. The graph depicted as it kept the same pattern as
the C(t) curve but the amount of E(t) is more lower than C(t) value because the area
of E(t) curve can be calculated as 1.0 m2.
As for step change experiment, the area of C(t) can be calculated from the
table which is the summation of C(t) calculated. The area of C(t) curve obtain is 92.5
m2 which is more higher if compare to the area of C(t) obtain from pulse input
experiment. But, we can observe the area of step change input C(t) curve is more
bigger compare to the pulse input C(t) curve. Thus, it is reasonable that the area of
C(t) curve of step change experiment is higher than the area of C(t) curve from pulse
input experiment. Also, the pattern of the graph can be portrayed as gradually
increasing and once the C(t) reached the set point at 3.6 mS/min, the value of C(t)
stay constant. The graph of C(t) curve is plotted on figure 7.4. As regards of E(t)
curve obtain from the C(t) curve, the pattern slightly differ from the C(t) curve as in
figure 7.5. The value of E(t) increases with time that can defined as the residence
time distribution of fluid inside the reactor for step change experiment increases with
time.
Apart from the graph plotted for the both experiment, the mean residence
time, variance and the skewness of the residence time distribution is calculated and
recorded into table 7.2 and 7.3 respectively. The mean residence time is calculated
to determine average amount of residence time distribution function for the reactor.
For experiment 1, the mean residence time is calculated at 0.14 and for experiment 2

23

is at 0.0398. The average residence time for the reactor in experiment 1 is longer
compared to experiment 2.
Also, the variance of each experiment was calculated and found to be at
0.2095 for experiment 1 and 0.1578 for experiment 2. Variance was calculated to
observe the spread of the distribution in the residence time distribution in the reactor.
Since the variance of experiment 1 is slightly higher than experiment 2 it can
conclude that the data from experiment 1 have greater distributions spread if
compared to experiment 2.
In addition, the skewness of the graph has been calculated using the formula
provided from the theory section. From the calculated value, the amount of skewness
for experiment 1 and 2 are 0.3407 and 0.6617 respectively. The values of skewness
calculate to indicate the direction of the graph toward the mean residence time. It can
be concluded that the skewness for experiment 2 is mow higher than experiment
which indicates the value for experiment 2 is more directed to the mean residence
distribution time compared to experiment 1.
Thus from both experiment performed, it can be observed that the effect of a
pulse input and step change input are differences but the value obtain from the result
can still be compare. For pulse input experiment, the inlet tracer concentration is
suddenly change from zero value to the higher value and reduces at zero again once
it reached the set point. While for the step change input experiment, the inlet
concentration tracer gradually increases with time and stay constant at same value
once it reached it set point.

24

10.0

CONCLUSIONS

The pulse input in a tubular reactor experiment was conducted to investigate the
effect of a pulse input in a tubular flow reactor and to construct a residence time
distribution function for the tubular flow reactor. On the other hand, for the step
change input experiment was conducted to examine the effect of step change input
in the reactor and also to construct residence time distribution function from the result
obtained. From the E(t) curve obtained from experiment 1, it can be observed that
the residence time increases with time and after a few minutes the residence time
gradually decreases until it reach E(t) = 0. Besides that, for step change input
experiment it can be depicted that the residence time is gradually rapidly increases
with time and gradually increases as it reach the set point in C(t) value. Also, the
mean residence time, second moment (Variance) and third moment (Skewness)
were calculate from the E(t) value . For the first experiment, the mean residence
time, variance and skewness calculated are 0.1400 min, 0.2095 min2 and 0.3407
min5/2 respectively. For the second experiment, the mean residence time is 0.0398
min, 01578 min2 in variance and 0.6617 min5/2 of skewness.

25

11.0

RECOMMENDATIONS

In order to obtain maximize the accuracy and the precision of the experiment it is
recommended that:

Do at least two or more trials for both inlet (QI-01) and outlet (QI-02) to obtain

the average value of conductivity and maximize the accuracy of the reading.
Make sure to open and close the valve quickly to minimize the error while
undergo the experiment, thus at least one person need to handle the opening

and closing the valve.

Ensure the valve and the tube does not leak to avoid any error happening to

the conductivity values read.

Check whether feed tanks 1 and 2 are filled with NaCl and de-ionized water

before starting the experiment.

Ensure the flow rate is kept constant at 700 mL/min along the experiment
because the flow rate value can reset by itself whenever the pump is switch
off or on.

26

12.0

REFERENCES

E. B. Nauman and B. A. Buffham. Mixing in Continuous Flow Systems.

John Wiley & Sons, New York, 1983.

Fogler, H. S. (2006). Elements of chemical reaction engineering (4th

ed.). University of Michigan: Prentice Hall.

K. Dane Wittrup, course material for 10.37 Chemical and Biological
Reaction

Engineering,

Spring

2007.

MIT

OpenCourseWare

(http://ocw.mit.edu), Massachusetts Institute of Technology. Retrieved

on (18/10/2016)
Levenspiel, O. (1972). Chemical reaction engineering (3rd ed.). New

York: Wiley.
K. Dane Wittrup, course material for 10.37 Chemical and Biological
Reaction

Engineering,

Spring

2007.

MIT

OpenCourseWare

(http://ocw.mit.edu), Massachusetts Institute of Technology. Retrieved

on (18/10/2016)
S. P. Chauhan, J. P. Bell, and R. J. Adler. On optimum in mixing in
continuous homogeneous reactors. Chem. Eng. Sci., 2:1-13,1953.

27

13.0

APPENDIX

28

29