ABSTRACT

There are two experiment carried out for Tubular Plug Flow Reactor which are pulse input in
tubular flow reactor and step change input in a tubular flow reactor .The purposes of Tubular
Plug Flow Reactor are to examine the effect of a pulse input in a tubular flow reactor , the step
change input in a tubular flow reactor are to examine the effect of a step change input in a
tubular flow reactor and to construct a residence time distribution (RTD) .For the pulse input
experiment ,the flow rate was set up to 700 ml/min then let the salt solution flow for one minute
and take reading of conductivity interval 30 seconds until reading are almost constant and
stable at low values. After that for step change input again flow rate was set at 700 ml/min and
recorded conductivity at intervals of 30 seconds until reading also almost constant. The
observation throughout the experiment are for pulse input the mean residence time is 1.5045
minute, while the peak is at around 1 minute. This should indicate positive skewness. This is
consistent with the value of cubic s which is positive. The variance is 5.0942, and this is
rightfully so. The high value indicates that the data is distributed widely, and is deviated far
from normal distribution while for step change experiment the mean residence time does not
signal anything significant. The graph is also positively skewed and this is rightfully shown by
the graph. The variance is 1.8848, which is lower than that of pulse input. This is seen from the
fact that 62.5% of the whole experiment operates at constant reading. This experiment is a
success. It is found that be it through step change or pulse change, the time taken for the reactor
to experience complete change of material is the same. Both graph exhibits positive skewness,
and has rather marginally different value of variance.

1
1.0 INTRODUCTION

A plug flow reactor (PFR) consists in a long, straight pipe in which the reactive fluid
transits at steady state (no accumulation). The main assumptions of this model are that the fluid
is completely mixed in any cross section at any point, but it experiences no axial mixing, i.e.
contiguous cross-sections cannot exchange mass with each other (1). Plug flow reactors, also
known as tubular reactors, consist of a cylindrical pipe with openings on each end for reactants
and products to flow through (2).

FIGURE 1.0

Reactants are continually consumed as they flow down the length of the reactor. Plugs of
reactants are continuously fed into the reactor. As the plug flows down the reactor the reaction
takes place, resulting in an axial concentration gradient. Products and unreacted reactants flow
out of the reactor continuously. The flow can be laminar and greatly deviate from ideal plug-
flow behaviour, or turbulent, as with gases.

There is a technique which is called as stimulus - response technique. The technique is

applied by injecting a pulse of tracer at the inlet. However, it does not disperse and appear as
pulse at the outlet. The concentration of tracer versus time at the exit should be followed in
order to obtain the degree of dispersion that would occur in the real reactor.

Faulty operation caused by malfunction of chemical reactors can be effectively diagnosed

by Residence Time Distribution (RTD) analysis. RTD shall be used to characterize existing
(i.e. real) reactors and then use it to predict exit conversions and concentrations when reactions
occur in these reactors (3). Firstly, the non-reactive or inert tracer will be injected at the inlet.
The concentration of the tracer is changed according to a known function and the response is
found by measuring the concentration of the tracer at the outlet. The hydrodynamics condition
and the physical characteristic of the fluid should not be altered by the selected tracer. The
quantity E(t) is called the residence-time distribution function. It is the function that describes
in a quantitative manner how much time different fluid elements have spent in the reactor. The

2
quantity E(t) dt is the fraction of fluid exiting the reactor that has spent between time t and t +
dt inside the reactor (4).

FIGURE 1.1

2.0 OBJECTIVE

The two objectives for this experiment are:

To examine the effect of a pulse input and step change input in a tubular flow reactor.
To construct a residence time distribution (RTD) function for the tubular flow reactor.

3.0 THEORY

Let consider the chemical reaction as

+ +

Residence time, is the average amount of time that a particle spends in a particular system.
The is a representation of how long it will takes for the concentration to significantly change
in the sediment.

=
0

Where is the reactor volume and 0 is the total feed flow rate. In this experiment, the
pump was adjusted until the flow rate become constant. The flow rate for each experiment is
variable but the reactor volume remain constant for every experiment.

3
Conversion is a way of determining how far has the reaction is done, or how many moles of
products are formed for every mole of A has consumed. Conversion is the number of moles
of A that have reacted per mole of A fed to the system.

moles of A reacted
=
moles of A fed

A reaction rate constant, quantifies the rate of a chemical reaction. The reaction rate is often
found to have the form

Where CA and CB are the concentration of the species A and B respectively, each has the powers
and , while is the reaction rate constant. The power of and are the partial reaction
orders. In this experiment, we can calculate the reaction rate constant, by the following
formula.

0
= ( )
1

Where, is the reaction rate constant, 0 the total inlet flow rate of solutions, is the reactor
volume, 0 is the inlet concentration of reactant NaOH in the reactor, and is the percentage
of conversion.

From definition, rate of reaction is defined as the rate of disappearance of reactant or rate of
formation of product. Rate of reaction of each species corresponds respectively to their
stoichiometric coefficient.

= = =

The negative sign indicates reactants while the positive sign indicates products.

A usual equation for rate of reaction is

Where CA and CB are the concentration of the species A and B respectively, each raised to the
powers and , while kA is the reaction rate constant. The exponents and are the partial
reaction orders. The overall order of reaction is given by the following:

= +

4
Tubular flow reactors are one type of flow reactors. It has continuous inflow and outflow of
materials. In the tubular reactor, the feed enters at the one end of a cylindrical tube and the
product stream leaves at the other end. The lack stirring in the long tube prevent the fluid from
mixing completely in the tube.

Assumptions that was made was there is no mixing in axial direction, complete mixing in radial
direction and an uniform velocity profile across the radius.

4.0 APPARATUS AND MATERIAL

APPARATUS
1. Burette
2. Dropper
3. Conical flask
4. Measuring cylinder

MATERIALS
1. Hydrochloric acid (HCI)
2. Sodium Hydroxide (NaOH) FIGURE 4.0 SOLTEQ (BP101-B)
3. Ethyl Acetate

5.0 PROCEDURES

5.1 General Start-Up Procedures

1. All valves were initially closed except valves 7.

2. Solution was prepared for the experiment.
3. The power for the control panel was turned on.
4. Water jacket B4 and pre-heater B5 were filled with clean water.
5. Stirrer motor was switched on and the speed of motor was set about 200 rpm.
6. Valve V2 and V10 were opened. Switch on the pump P1 and P1 was adjusted to
flowrate of 700 mL/min at flow meter F1-01. Valve 10 was closed and pump P1 was
switched off.

5
 7. Valve V6 and V12 were opened. Switch on the pump P2 and P2 was adjusted to
flowrate of 700 mL/min at flow meter F1-02. Valve 12 is closed and pump P2 is
switched off.
8. The unit was ready for experiment.

5.2 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 switched on.
3. Pump P1 flow controller was adjusted to give a constant flow rate of de-ionized water
into the reactor R1 at approximately 700 ml/min at FI-01.
4. Let the de-ionized water 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 was 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 taken
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. Let the salt solution to flow for 1 minute, then reset and restart the timer. 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 quickly
opened and pump P1 was switched on.
10. The de-ionized water flow rate was always maintained at 700 ml/min by adjusting P1
flow controller.
11. Both the inlet (QI-01) and outlet (QI-02) conductivity values at regular intervals of 30
seconds were recorded.
12. The conductivity values were continually recorded until all readings were almost
constant and approach the stable low level values.

6
5.3 EXPERIMENT 2 : Step Change Input In A Tubular Flow Reactor

1. The general start-up procedures was performed.

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

5.4 General Shut-Down Procedures

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

7
6.0 RESULT AND CALCULATION

TABLE 6.0 Data Obtained For Conductivity

Solution Mixtures Concentration Conductivity,
Conversion 0.1 M 0.1 M
H2 O of NaOH (M) (mS/cm)
NaOH Na(Ac)
0% 100 mL - 100 mL 0.0500 11.45
25% 75 mL 25 Ml 100 mL 0.0375 7.52
50% 50 mL 50 mL 100 mL 0.0250 5.83
75% 25 mL 75 mL 100 mL 0.0125 1.95
100% - 100 mL 100 mL 0.0000 0.1195

Conductivity vs Conversion
14

12

10
Conductivity(mS/cm)

4
y = -0.1129x + 11.02
R = 0.9832
2

0
0 20 40 60 80 100 120
-2
Conversion(%)

FIGURE 6.0 Graph Of Conductivity Versus Conversion

8
Calculation :
TABLE 6.1 Calculated Value From The Conductivity
2 2
0 11.95 0 0 131.1025
0.25 7.52 0.0625 1.88 56.5504
0.5 5.83 0.25 2.915 33.9889
0.75 1.95 0.5675 1.4625 3.8025
1.00 0.1195 1 0.1195 0.0143
TOTAL 2.5 26.8695 1.875 6.377 225.4586

0
[ ] [ ] = [ ]
2 1

0 1
[ ] = [ ] [ ]
1 2

1
=[ ] [ ]
2
5 2.5 -1 26.8695
=[ ] [ ]
2.5 1.575 6.377
11.0201
=[ ]
11.2927
= 11.0201 11.2927
5(6.377) (2.5)(26.8695)
= =
( 2 ( )2 ( 2 ( )2 ) 9.375 6.75)(1127.293 721.9700)

35.2888
= | 35.5898 | = 0.9915

Therefore, since R2 = 0.9832, the calibration curve is still reliable as it suffers only 1.6843%
deviation from perfect unity.
From the table above also, conversion and concentration are related by equation
C = 0.0125 + 0.062

9
EXPERIMENT 1 : Pulse Input In A Tubular Flow Reactor

Flow Rate = 700 mL/min

Input Type = Step change
TABLE 6.2 Data Obtained for the Conductivity
Conductivity, (mS/cm) Outlet Outlet
Time(min) Conversion, Concentration,
Inlet Outlet
C (M)
0.0 0.2 0.0 0.9759 0.050301
0.5 0.1 0.4 0.9404 0.050745
1.0 0.1 0.5 0.9316 0.050855
1.5 0.1 0.4 0.9404 0.050745
2.0 0.0 0.2 0.9581 0.050524
2.5 0.0 0.0 0.9759 0.050301
3.0 0.0 0.0 0.9759 0.050301
3.5 0.0 0.0 0.9759 0.050301
4.0 0.0 0.0 0.9759 0.050301
4.5 0.0 0.0 0.9759 0.050301
5.0 0.0 0.0 0.9759 0.050301

FIGURE 6.1 Graph Of Outlet Conductivity Versus Time

10
 FIGURE 6.2 Graph Of Concentration Against Time

() =
0

(1 ) + ( )
= (1 ) [ ]
2

Sample calculation, for time between 0 to 0.5 minutes,

0.050301 + 0.050745 mol min
= (0.5 0.00) ( ) = 0.252615
2 m3

Time interval (minute) Area ( )

0.00-0.50 0.025262
0.50-1.00 0.025400
1.00-1.50 0.025400
1.50-2.00 0.025317
2.00-2.50 0.025206
2.50 3.00 0.025151
Total area 0.151736

11
Total Area,
4
mol min
() = 0.151736
0 m3
Next is the calculation of E(t) or residence time distribution function. The following is the
formula to calculate
()
() = (min1 )
0 ()

Sample calculation,

0.050301 molm3
At = 0.00, C = 0.050301 molm3 . () = = 0.331504 min1
0.151736 mol minm3

Time(min) Concentration (M) E(t) (min-1)

0.0 0.050301 0.331504
0.5 0.050745 0.334431
1.0 0.050855 0.335156
1.5 0.050745 0.334431
2.0 0.050524 0.332974
2.5 0.050301 0.331504
3.0 0.050301 0.331504
3.5 0.050301 0.331504
4.0 0.050301 0.331504
4.5 0.050301 0.331504
5.0 0.050301 0.331504

FIGURE 6.3 Residence Time Distribution (RTD) Function For Plug Flow Reactor

12
Next we calculate the mean residence time by computing the area under the graph, and
multiplying it with . This is mathematically shown as:

0 ()
= = ()
0 () 0

From the expression above, 0 () is expected to be equal to 1. () is dimensionless.
Integrating it with respect to gives a value of time. This is the mean residence time.
Sample calculation, for time interval between 0.0 0.5 minutes,
0.331504 + 0.334431
= (0.5 0.00) ( ) = 0.166484
2

Time interval (minute) Area

0.00-0.50 0.166484
0.50-1.00 0.167397
1.00-1.50 0.167397
1.50-2.00 0.166851
2.00-2.50 0.166120
2.50 3.00 0.165752
Total 1.000001

As expected,

() = 1.000001 min1
0

() () () ( ) ( ) () ( ) ()
0 0.050301 0.331504 0 -1.504535 0.750401 -1.129004
0.5 0.050745 0.334431 0.167215 -1.004535 0.337471 -0.339002
1.0 0.050855 0.335156 0.335156 -0.504535 0.085316 -0.043045
1.5 0.050745 0.334431 0.501647 -0.004535 0.000007 -0.00000003119
2.0 0.050524 0.332974 0.665948 0.495465 0.081740 0.040499
2.5 0.050301 0.331504 0.82876 0.995465 0.328504 0.327014
3.0 0.050301 0.331504 0.994512 1.495465 0.741381 1.108709

0.5
= 0 () = (0 + 4(0.167216) + 2(0.355156) + 4(0.501647) +
3
2(0.665948) + 4(0.828760) + 0.994512) = 1.504535 minutes

Second moment, variance, 2 = 0 ( )2 () . By polynomial regression, the data in
the sixth column needed to find the second moment could be related with using function
() = 0.3313 2 0.9974 + 0.7515, with value of 2 = 1.00. Thus,

13
 5
= ( () = 0.3313 2 0.9974 + 0.7515 = 5.0942
2 )2
0 0
1
Third moment, skewness, 3 = 1.5 0 ( )3 () . By polynomial regression, the data
in the seventh column needed to find the skewness could be related with using function
() = 0.3307 3 1.4926 2 + 2.2475 1.1295, with value of 2 = 1.00. Thus,

1
= 1.5 ( )3 ()
3
0
5
1
= 0.3307 3 1.4926 2 + 2.2475 1.1295
0.74791.5 0
= 1.0373

Result of calculations
= 1.504535 minute
2 = 0.7479
3 = 0.017741

EXPERIMENT 2 : Step Change Input In A Tubular Flow Reactor

TABLE 6.3 Data Obtained for the Conductivity

Conductivity (mS/cm) Outlet Outlet
Time(min) conversion concentration
Inlet Outlet
(M)
0.0 0.0 0.0 0.975861 0.050302
0.5 3.6 0.0 0.975861 0.050302
1.0 3.7 0.0 0.975861 0.050302
1.5 3.7 0.2 0.958150 0.050523
2.0 3.8 0.3 0.949295 0.050634
2.5 3.8 0.4 0.940440 0.050745
3.0 3.8 0.4 0.940440 0.050745
3.5 3.8 0.4 0.940440 0.050745
4.0 3.8 0.4 0.940440 0.050745
4.5 3.8 0.4 0.940440 0.050745
5.0 3.8 0.4 0.940440 0.050745
5.5 3.8 0.4 0.940440 0.050745
6.0 3.8 0.4 0.940440 0.050745
6.5 3.8 0.4 0.940440 0.050745
7.0 3.8 0.4 0.940440 0.050745
7.5 3.9 0.4 0.940440 0.050745
8.0 3.9 0.4 0.940440 0.050745

14
 Outlet conductivity vs time
0.45

0.4

0.35
Outlet conductivity(mS/cm)

0.3

0.25

0.2

0.15

0.1

0.05

0
0 1 2 3 4 5 6 7 8 9
-0.05
Time(min)

FIGURE 6.4 Graph of outlet conductivity versus time

FIGURE 6.5 Concentration versus time

15
Stepwise notation of the concentration would be,
0 for t < 0
0 () {
(0 ) for t 0
Because we assume inlet concentration to be constant from the point where inlet conductivity
stays constant, we take 0 = 0.0545.
Time (min) Conductivities, Outlet () ()
(mS/cm) concentration, ()
Inlet Outlet () (M) =
()
0 0 0 0.050302 0 0
0.5 3.6 0 0.050302 0.025151 0.047212
1.0 3.7 0 0.050302 0.050302 0.094623
1.5 3.7 0.2 0.050523 0.075785 0.142559
2.0 3.8 0.3 0.050634 0.101268 0.190495
2.5 3.8 0.4 0.050745 0.126863 0.238642
3.0 3.8 0.4 0.050745 0.152235 0.286369
0.531604 0.999999

Next the moments are calculated.

() () ( )
() ( ) () ( ) ()
0 0.050302 0 0 -0.8574 0 0
0.5 0.050302 0.047212 0.023606 -0.3574 0.006030613 -0.002155341
1.0 0.050302 0.094623 0.094623 0.1426 0.001924136 0.000274382
1.5 0.050523 0.142559 0.2138385 0.6426 0.058867566 0.037828298
2.0 0.050634 0.190495 0.38099 1.1426 0.248697844 0.284162157
2.5 0.050745 0.238642 0.596605 1.6426 0.643888275 1.057650881
3.0 0.050745 0.286369 0.859107 2.1426 1.314644122 2.816756497

= 0 (). By polynomial regression, () can be related to by equation () =
0.0959 2 0.0014 + 0.0002. Thus,
3
= 0 0.0959 2 0.0014 + 0.0002 = 0.8574 minutes

Second moment, variance, 2 = 0 ( )2 () . By polynomial regression, the data in
the sixth column needed to find the second moment could be related with using function
() = 0.0956 3 0.164 2 + 0.0703 , with value of 2 = 1.00. Thus,
3
2 = ( )2 () = 0.0956 3 0.164 2 + 0.0703 = 0.7763
0 0
1
Third moment, skewness, 3 = 1.5 0 ( )3 () . By polynomial regression, the data
in the seventh column needed to find the skewness could be related with using function
() = 0.0953 4 0.2447 3 + 0.2088 2 0.0592, with value of 2 = 1.00. Thus,

16

1
3 = ( )3 ()
1.5 0
3
1
= 0.0953 4 0.2447 3 + 0.2088 2 0.0592
0.77631.5 0
= 1.8848

7.0 DISCUSSIONS
The numerical methods adopted in evaluating the result obtained are Simpsons Rules of
Numerical Integration, and linear and polynomial regressions. The reason why linear and
polynomial regressions are used because in evaluating the moments, the variables and its
relations are ascended in degree, from = 1 to = 3 for pulse change, and = 4 for step
change. Accuracy is also much higher when regression is utilized to come with the relationship
between the variables, and hence integrations ensuing are also much accurate.

Also, while the instruction requires us to only plot a curve of conductivity vs time, a graph of
concentration vs time is still plotted nonetheless. This is because:

1. To show how each quantities are brought to their units.

2. To utilize the calibration curve.

Experiment 1 : Pulse Input In A Tubular Flow Reactor

In essence this experiment works in the following ways:

1. A tubular reactor is passed through with deionized water until it is homogenously filled
with it. This is indicated by low conductivity values at both ends.
2. Salt solution is then passed through for one minute.
3. Deionized water is then passed through again, and the outlet concentration of the salt
solution with respect to every point of time is recorded and plotted.

A few observation and conclusion can be made.

1. The graph is shaped like bell.

a. This indicates that as water is passed through the reactor, salt solution is
gradually pushed out.
b. From zeroth to first minute we see gradual increase of salt concentration,
indicating that the amount of salt pushed out is increasing.

17
 c. Eventually the concentration decreases as the tubular flow reactor has water as
its resident. The concentration perpetually decreases until eventually the
concentration goes to roughly zero.
2. Analyzing the E(t) curve, if we are to take any two point in time, say from = 1 to =
2.5, Calculating the area under the graph by numerical integration,

3 1.5
= (1 + 32 + 33 + 4 ) = (1 + 31.5 + 32 + 2.5 )
8 8
= 0.1875(2.668875) = 0.5004

a. This means that 50.04% of the salt leaving the reactor spends time in the reactor
between 1 to 2.5 minutes. That is the meaning of E(t).
b. E(t), according to Fogler, is the fraction of material leaving the reactor that has
resided in the reactor between any two point in time. (Fogler, 2008).
3. In its totality, we find that from zeroth minute to third minute, the area under the graph
is equal to 1.
a. Thus, all salt spent only three minutes in the reactor before they leave.
b. That is why the experiment is required to run until the reading of conductivity
stays constant at low value, to show that all salt has left the reactor.
4. The mean residence time is 1.5045 minute, while the peak is at around 1 minute. This
should indicate positive skewness. This is consistent with the value of cubic s which is
positive. The variance is 5.0942, and this is rightfully so. The high value indicates that
the data is distributed widely, and is deviated far from normal distribution.

Experiment 2: Step Change Input In A Tubular Flow Reactor

In essence, the experiment is done to see the time taken for salt solution to replace deionized
water in the tubular reactor. Several observations are made.

1. It takes three minutes of the reactor to be filled with salt solution.

a. This is deduced from the fact that the graph started to stay horizontal from t = 3
minutes.
b. This brings a significant meaning because with both experiments run at flow
rate 700 ml/min, both experiment took 3 minutes for complete discharge of salt
solution (in pulse input experiment) and water (in step input experiment).

18
 2. There is slight fluctuation between 2.6 minutes to 2.75 minutes. This may be due to
clogging/accumulation of salt that causes slight jump in reading.
3. The mean residence time does not signal anything significant. The graph is also
positively skewed and this is rightfully shown by the graph. The variance is 1.8848,
which is lower than that of pulse input. This may be due to the fact that narrower
distribution is observed in this experiment. This is seen from the fact that 62.5% of the
whole experiment operates at constant reading.

8.0 CONCLUSION

This experiment is a success. It is found that be it through step change or pulse change, the
time taken for the reactor to experience complete change of material is the same. Both graph
exhibits positive skewness, and has rather marginally different value of variance. The theories
are also proven to be true, where E(t) is dependent on time, and that residence time is also
affected by concentration.

9.0 RECOMMENDATIONS

Below are some recommendations that can help to get better and accurate results for the
experiment.

1. Make sure to open and close the right valve according to the procedure.
2. The readings should be taken twice or thrice to and average is calculated to obtain
more accurate and precise data.
3. Make sure the equipment is in good condition and throughout the experiment, make
sure there are no leakages happen.
4. Perform the general start-up procedures correctly and make sure to also perform the
general shut-down procedures before ending the experiment.
5. Always run the experiment after fully understand the unit and procedures.

19
10.0 REFERENCES

1. Foglers. (n.d.). Retrieved from

http://www.umich.edu/~essen/html/byconcept/chapter13.pdf
2. Gurmen, F. &. (n.d.). Distribution of Residence Times for Chemical Reactors.
Retrieved from
http://www.umich.edu/~elements/fogler&gurmen/html/course/lectures/thirteen/index
.htm#top3
3. Stenstrom, M. (n.d.). Fundamentals of Chemical Reactor Theory. Retrieved from
http://www.seas.ucla.edu/stenstro/Reactor.pdf
4. Visual Encyclopedia of Chemical Engineering. (n.d.). Retrieved from
http://encyclopedia.che.engin.umich.edu/Pages/Reactors/PFR/PFR.html

11.0 APPENDICES

-see next page-

20