1

1.0 Introduction

In the chemical industry, reactor is used for the millions of processes. There are many
different types of reactors due to many different factors that can control the formation
of product during the reaction. One of many different types of reactors is tubular
reactor.

Plug flow, or tubular, reactors consist of a hollow pipe or tube through which
reactants flow. Figure 1.1 is a plug flow reactor in the form of a tube wrapped around
an acrylic mould which is encased in a tank. Water at a controlled temperature is
circulated through the tank to maintain constant reactant temperature.

Figure 1.1: Plug Flow Reactor

Several assumptions have been made for tubular flow reactor in order to simplify the
problems which are:
Steady state
Constant density
Single reaction occurring in the bulk of the fluid (homogeneously)

A material balance on the differential volumes of fluid elements gives:

in + generation = output + consumption + accumulation
dFj
For steady state reaction, accumulation is 0. Thus, = rj .
dV
 2

The residence time distribution (RTD) of a chemical reactor is a probability

distribution function that describes the amount of time a fluid element could spend
inside the reactor. Chemical engineers use the RTD to characterize the mixing and
flow within reactors and to compare the behaviour of real reactors to their ideal
models. The RTD function, external residence time distribution, E(t), measures the
time that the various fractions of fluid element reside in the reactor (macromixing); it
gives no information about the mixing details at a molecular level (micromixing).

2.0 Objectives

The main objectives of this experiment are to examine the effect of a pulse input and a
step change input in a tubular flow reactor. Besides that, the experiment is conducted
to construct a residence time distribution (RTD) function for the tubular flow reactor.

3.0 Theory

A 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 rather than of time. In the ideal tubular reactor,
the fluids flow as if they were solid plugs or pistons, and reaction time is the same for
all flowing material at any given tube cross section. Tubular reactors resemble batch
reactors in providing initially high driving forces, which diminish as the reactions
progress down the tubes. Tubular reactor are often used when continuous operation is
required but without back-mixing of products and reactants.

Flow in tubular reactors can be laminar, as with viscous fluids in small-

diameter tubes, and greatly deviate from ideal plug-flow behaviour, or turbulent, as
with gases. Turbulent flow generally is preferred to laminar flow, because mixing and
heat transfer are improved. For slow reactions and especially in small laboratory and
pilot-plant reactors, establishing turbulent flow can result in inconveniently long
reactors or may require unacceptably high feed rates.

The theory of residence time distributions generally begins with three

assumptions; 1. The reactor is at steady-state, 2. Transports at the inlet and the outlet
 3

takes place only by advection, and 3. The fluid is incompressible (v = constant).

The residence-time of an element of fluid leaving a reactor is the length of time spent
by that element within the reactor. For a tubular reactor, under plug-flow conditions,
the residence-time is the same for all elements of the effluent fluid.

The RTD is determined experimentally by injecting inert specie, called tracer,

into the reactor at some time and then measuring the tracer concentration, C, in the
effluent stream over time. The tracer must be non-reactive specie, easily detectable
and should have physical properties close to the reacting mixture, in other words, it
should be soluble in the system. In addition, among others, the tracers behaviour
must reflect the material flowing through the reactor. There are, mainly, two used
methods of tracers injection called pulse input and step input. In a pulse input, tracer
is, suddenly, injected in one shot into the feed stream, entering the reactor in as short a
time as possible. Since the step input consider a constant rate of tracer addition from
an initial time, t = 0, before it, there is no tracer been added to the feed. The outlet
concentration is measured over time, in both methods showed.

Figure 3.1: Injection of tracer

 4

In figure 3.1, it can be seen that at beginning the concentration of tracer is low,
however increases with time due to the flux in the reactor. At first, the concentration
of tracer is low, however increases with time due to the flux in the reactor. The fact
that the response step is not equally the same is due to occurrence of dispersions in the
system, which affects the mean residence time in the reactor and consequently, alters
its conversion, yield and capability.

If C0 is the concentration of tracer added to the reactor inlet, the F fraction of the
tracer at the outlet of the reactor will be:
C(t)
F(t) = (1)
C0
The tracer concentration in the reactor outlet is given by:
t
C(t) = C0 E(t)dt (2)
0

Substituting (2) into (1), it follows that:

t
F(t) = E(t)dt (3)
0

df(t)
E(t) = (4)
dt
Thus, the curve of distribution of residence time is obtained in Figure 3.2,

Figure 3.2: RTD curve behaviour

 5

4.0 Apparatus and Materials

Apparatus used in this experiment is:

SOLTEQ BP101-B Tubular Flow Reactor

Materials used in this experiment are:

Deionized water
Sodium hydroxide

5.0 Procedures

General Start-Up Procedures

1. All valves were ensured initially closed except valve V7.

2. 20 litre 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 up.
5. The water de-ionizer was connected to the laboratory water supply. Valve V3 was
opened and feed tank B1 was filled up with the de-ionized 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 F1-01. The
conductivity display was observed at low value then a valve 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 F1-02. A
valve V12 was closed and pump P2 was switched off.
8. The unit was ready for experiment.

Experiment 1: Pulse Input in a Tubular Flow Reactor

1. The general start-up procedures were performed.
2. Valve V9 is opened and pump P1 is switch on.3.
3. Pump P1 flow controller is adjusted to give a constant flow rate of de-ionized water
into the reactor R1 at approximately 700 ml/min at Fl-01.
 6

4. Let the de-ionized water to continue flowing through the reactor until the inlet (Ql-01)
and outlet (Ql-02) conductivity values are stable at low levels. Both conductivities
values are recorded.
5. Valve V9 is closed and pump P1 is switch off.
6. Valve V11 is opened and Pump P2 is switch on. The timer is started simultaneously.
7. Pump P2 flow controller is adjusted to give a constant flow rate of salt solution into
the reactor R1 at 700 ml/min at Fl-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 is closed and pump P2 is switch off. Then, valve V9 is opened quickly and
pump P1 is switch on.
10. The de-ionized were making sure that the water flow rate is always maintained at 700
ml/min by adjusting P1 flow controller.
11. Both the inlet (Ql-01) and outlet (Ql-02) conductivity a value at regular intervals of 30
seconds is start recorded.
12. The conductivity values is continue recording until all readings are 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 is opened and pump P1 is switch on.
3. Pump P1 flow controller is adjusted to give a constant flow rate of de-ionized water
into the reactor R1 at approximately 700 ml/min at Fl-01.
4. Let the de-ionized water to continue flowing through the reactor until the inlet (Ql-01)
and outlet (Ql-02) conductivity values are stable at low levels. Both conductivities
values are recorded.
5. Valve V9 is closed and pump P1 is switch off.
6. Valve V11 is opened and Pump P2 is switch on. The timer is started simultaneously.
7. Both the inlet (Ql-01) and outlet (Ql-02) conductivity a value at regular intervals of
30seconds is start recorded.
8. The conductivity values were being recorded continuously until all readings are
almost constant.
 7

General Shut-Down Procedures

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.

6.0 Results

Experiment 1: Pulse input in Tubular Flow Reactor

Flow rate: 700mL/min
Input type: Pulse input

Time(min) Conductivity (mS/cm)

Inlet Outlet
0.0 2.5 0.0
0.5 0.3 0.4
1.0 0.1 3.5
1.5 0.0 4.4
2.0 0.0 4.4
2.5 0.0 1.5
3.0 0.0 0.1
3.5 0.0 0.0
4.0 0.0 0.0
4.5 0.0 0.0
5.0 0.0 0.0
 8

Outlet Conductivity vs Time

5

Outlet conductivity (mS/cm) 4

0
0 1 2 3 4 5 6
-1
Time (min)

Figure 6.1: Graph of outlet conductivity (mS/cm) versus time (minutes)

C(t)dt = Area under the graph
0

f(t1 ) + ft 2 )
Area = (t1 t 2 ) [ ]
2

For time (0.5-1.0) minutes,

E(t1 + t 2 ) 0.4 + 3.5
Area = (t 2 t1 ) [ ] = (1.0 0.5) [ ] = 0.975 mS. min/cm
2 2

For time (1.0-1.5) minutes,

E(t1 + t 2 ) 3.5 + 4.4
Area = (t 2 t1 ) [ ] = (1.5 1.0) [ ] = 1.975 mS. min/cm
2 2

For time (1.5-2.0) minutes

E(t1 + t 2 ) 4.4 + 4.4
Area = (t 2 t1 ) [ ] = (2.0 1.5) [ ] = 2.2 mS. min/cm
2 2

For time (2.0-2.5) minutes

 9

E(t1 + t 2 ) 4.4 + 1.5

Area = (t 2 t1 ) [ ] = (2.5 2.0) [ ] = 1.475 mS. min/cm
2 2

For time (2.5-3.0) minutes

E(t1 + t 2 ) 1.5 + 0.1
Area = (t 2 t1 ) [ ] = (3.0 2.5) [ ] = 0.4 mS. min/cm
2 2

5
Total area or C(t)dt
0

= (0.975 + 1.975 + 2.2 + 1.475 + 0.4)

= 7.025 mS. min/cm

For t = 0, C(t) = 0.0

0
E(t) = =0
7.025

For t = 0.5, C(t) = 0.4

0.4
E(t) = = 0.0569
7.025

For t = 1.0, C(t) = 3.5

3.5
E(t) = = 0.4982
7.025

For t = 1.5, C(t) = 4.4

4.4
E(t) = = 0.6263
7.025

For t = 2.0, C(t) = 4.4

4.4
E(t) = = 0.6263
7.025

For t = 2.5, C(t) = 1.5

 10

1.5
E(t) = = 0.2135
7.025

For t = 3.0, C(t) = 0.1

0.1
E(t) = = 0.0142
7.025

For t = 3.5, C(t) = 0.0

0
E(t) = =0
7.025

For t = 4.0, C(t) = 0.0

0
E(t) = =0
7.025

For t = 4.5, C(t) = 0.0

0
E(t) = =0
7.025

For t = 5.0, C(t) = 0.0

0
E(t) = =0
7.025

Time (min) Conductivity Outlet (mS/cm) E(t)

0.0 0.0 0.0
0.5 0.4 0.0569
1.0 3.5 0.4982
1.5 4.4 0.6263
2.0 4.4 0.6263
2.5 1.5 0.2135
3.0 0.1 0.0142
3.5 0.0 0.0
4.0 0.0 0.0
4.5 0.0 0.0
5.0 0.0 0.0
 11

E(t) vs Time
0.7

0.6

0.5

0.4
E(t)

0.3

0.2

0.1

0
0 1 2 3 4 5 6
-0.1
Time (min)

Figure 6.2: Residence time distribution (RTD) function for tubular flow reactor

For time (0.-0.5) minutes,

E(t1 + t 2 ) 0.0569
Area = (t 2 t1 ) [ ] = (1.0 0.5) [ ] = 0.0142 mS. min/cm
2 2

For time (0.5-1.0) minutes,

E(t1 + t 2 ) 0.0569 + 0.4982
Area = (t 2 t1 ) [ ] = (1.0 0.5) [ ]
2 2
= 0.1388 mS. min/cm

For time (1.0-1.5) minutes,

E(t1 + t 2 ) 0.6263 + 0.4982
Area = (t 2 t1 ) [ ] = (1.5 1.0) [ ]
2 2
= 0.2811 mS. min/cm

For time (1.5-2.0) minutes

E(t1 + t 2 ) 0.6263 + 0.6263
Area = (t 2 t1 ) [ ] = (2.0 1.5) [ ]
2 2
= 0.3132 mS. min/cm
 12

For time (2.0-2.5) minutes

E(t1 + t 2 ) 0.2135 + 0.6263
Area = (t 2 t1 ) [ ] = (2.5 2.0) [ ]
2 2
= 0.2100 mS. min/cm

For time (2.5-3.0) minutes

E(t1 + t 2 ) 0.0142 + 0.2135
Area = (t 2 t1 ) [ ] = (3.0 2.5) [ ]
2 2
= 0.0569 mS. min/cm

E(t)dt = Total area under the graph
0

= 0.0142 + 0.1388 + 0.2811 + 0.3132 + 0.21 + 0.0569

= 1.0142

Residence time, t m = tE(t)dt = 5(1.0142) = 5.071
0

Time Conductivity E(t) te(t) (t t m )2E(t)dt (t t m )3 E(t)dt

(min) Outlet (mS/cm)
0.0 0.0 0.0 0.0 0.0 0.0
0.5 0.4 0.0569 0.0285 1.1889 -5.4343
1.0 3.5 0.4982 0.4982 8.2567 -33.613
1.5 4.4 0.6263 0.9395 11.9805 -42.7825
2.0 4.4 0.6263 1.2526 11.8133 -36.2787
2.5 1.5 0.2135 0.5338 3.5284 -9.0716
3.0 0.1 0.0142 0.0426 0.1827 -0.3784
3.5 0.0 0.0 0.0 0.0 0.0
4.0 0.0 0.0 0.0 0.0 0.0
4.5 0.0 0.0 0.0 0.0 0.0
5.0 0.0 0.0 0.0 0.0 0.0
= 2.0354 = 3.2952 = 36.9505 = -127.5585
 13

Mean residence time, t m = tE(t)dt = 3.2952
0

Second moment, variance, = (t t m )2 E(t)dt = 36.9505
2
0

1
Third moment, skewness, s 3 = 3
(t t m )3 E(t)dt
2 0
1
= 3 (127.5585)
(6.0787)2
= 8.5112

Experiment 2: Step change input in Tubular Flow Reactor

Flow rate: 700mL/min
Input type: Step change input

Time(min) Conductivity (mS/cm)

Inlet Outlet
0.0 3.3 0.0
0.5 3.5 0.0
1.0 3.5 0.0
1.5 3.6 2.8
2.0 3.6 4.3
2.5 3.6 4.5
3.0 3.6 4.5
3.5 3.6 4.5
4.0 3.6 4.5
 14

Outlet concentration vs Time

5

Outlet conduction (mS/cm)

3

0
0 1 2 3 4 5
-1
Time (min)

Figure 6.3: Graph of outlet conductivity (mS/cm) versus time (minutes)

From the calculation, 0 C(t)dt = 11.425 mS. min/cm

Time(min) Outlet concentration E(t), min-1

(mS/cm)
0.0 0.0 0.0
0.5 0.0 0.0
1.0 0.0 0.0
1.5 2.8 0.245
2.0 4.3 0.376
2.5 4.5 0.394
3.0 4.5 0.394
3.5 4.5 0.394
4.0 4.5 0.394
 15

E(t) vs Time
0.45
0.4
0.35
0.3
0.25
E(t), min-1

0.2
0.15
0.1
0.05
0
-0.05 0 1 2 3 4 5
Time (min)

Figure 6.4: Residence time distribution (RTD) function for tubular flow reactor

7.0 Sample of Calculation

Experiment 1:

C(t)dt = Area under the graph
0

f(t1 ) + ft 2 )
Area = (t1 t 2 ) [ ]
2

For time (0.5-1.0) minutes,

E(t1 + t 2 ) 0.4 + 3.5
Area = (t 2 t1 ) [ ] = (1.0 0.5) [ ] = 0.975 mS. min/cm
2 2

For time (1.0-1.5) minutes,

E(t1 + t 2 ) 3.5 + 4.4
Area = (t 2 t1 ) [ ] = (1.5 1.0) [ ] = 1.975 mS. min/cm
2 2

For time (1.5-2.0) minutes

 16

E(t1 + t 2 ) 4.4 + 4.4

Area = (t 2 t1 ) [ ] = (2.0 1.5) [ ] = 2.2 mS. min/cm
2 2

For time (2.0-2.5) minutes

E(t1 + t 2 ) 4.4 + 1.5
Area = (t 2 t1 ) [ ] = (2.5 2.0) [ ] = 1.475 mS. min/cm
2 2

For time (2.5-3.0) minutes

E(t1 + t 2 ) 1.5 + 0.1
Area = (t 2 t1 ) [ ] = (3.0 2.5) [ ] = 0.4 mS. min/cm
2 2

5
Total area or C(t)dt
0

= (0.975 + 1.975 + 2.2 + 1.475 + 0.4)

= 7.025 mS. min/cm

For t = 0, C(t) = 0.0

0
E(t) = =0
7.025

For t = 0.5, C(t) = 0.4

0.4
E(t) = = 0.0569
7.025

For t = 1.0, C(t) = 3.5

3.5
E(t) = = 0.4982
7.025

For t = 1.5, C(t) = 4.4

4.4
E(t) = = 0.6263
7.025

For t = 2.0, C(t) = 4.4

 17

4.4
E(t) = = 0.6263
7.025

For t = 2.5, C(t) = 1.5

1.5
E(t) = = 0.2135
7.025

For t = 3.0, C(t) = 0.1

0.1
E(t) = = 0.0142
7.025

For t = 3.5, C(t) = 0.0

0
E(t) = =0
7.025

For t = 4.0, C(t) = 0.0

0
E(t) = =0
7.025

For t = 4.5, C(t) = 0.0

0
E(t) = =0
7.025

For t = 5.0, C(t) = 0.0

0
E(t) = =0
7.025

For time (0.-0.5) minutes,

E(t1 + t 2 ) 0.0569
Area = (t 2 t1 ) [ ] = (1.0 0.5) [ ] = 0.0142 mS. min/cm
2 2

For time (0.5-1.0) minutes,

E(t1 + t 2 ) 0.0569 + 0.4982
Area = (t 2 t1 ) [ ] = (1.0 0.5) [ ]
2 2
= 0.1388 mS. min/cm
 18

For time (1.0-1.5) minutes,

E(t1 + t 2 ) 0.6263 + 0.4982
Area = (t 2 t1 ) [ ] = (1.5 1.0) [ ]
2 2
= 0.2811 mS. min/cm

For time (1.5-2.0) minutes

E(t1 + t 2 ) 0.6263 + 0.6263
Area = (t 2 t1 ) [ ] = (2.0 1.5) [ ]
2 2
= 0.3132 mS. min/cm

For time (2.0-2.5) minutes

E(t1 + t 2 ) 0.2135 + 0.6263
Area = (t 2 t1 ) [ ] = (2.5 2.0) [ ]
2 2
= 0.2100 mS. min/cm

For time (2.5-3.0) minutes

E(t1 + t 2 ) 0.0142 + 0.2135
Area = (t 2 t1 ) [ ] = (3.0 2.5) [ ]
2 2
= 0.0569 mS. min/cm

E(t)dt = Total area under the graph
0

= 0.0142 + 0.1388 + 0.2811 + 0.3132 + 0.21 + 0.0569

= 1.0142

Residence time, t m = tE(t)dt = 5(1.0142) = 5.071
0

Mean residence time, t m = tE(t)dt = 3.2952 min
0

Second moment, variance, 2 = 0 (t t m )2 E(t)dt = 36.9505 min2
 19

1
Third moment, skewness, s 3 = 3
(t t m )3 E(t)dt
2 0
1
= 3 (127.5585)
(6.0787)2
5
= 8.5112min2 .

Experiment 2:

The calculation for experiment 2 is same as calculation in experiment 1.

Residence time, t m = 4.0002

Mean residence time, t m = 6.2415 min

Second moment, variance, 2 = 4.4153 min2

5
Third moment, skewness, s 3 = 2.8272 min2

8.0 Discussions

The experiment is conducted to investigate the effect of a pulse input and step change
in a tubular flow reactor. The experiment also is to study the residence time (RTD)
function for the tubular flow reactor. Both inlet and outlet conductivity values were
recorded at intervals of 30 seconds until all the reading almost constant and approach
low level value. Water flow rate of the de-ionized water was maintained at 700
mL/min.
In experiment 1, the graph of outlet conductivity versus time was plotted.
Referring to the graph in Figure 6.1, the outlet conductivity value starts to increase
from 0 to 0.4 mS/cm at the half minute of time and reach its lowest peak at 1.5 to 2.0
minutes before it started to reduce until 0 mS/cm at minute of 3.5 to 5.0. The inlet
conductivity is already at its highest peak during 0 minute. It keeps decreases as time
increases until at 1.5 minutes, the conductivity is 0 mS/cm and stayed at 0 mS/cm
until the end of the 5.0 minutes. This may due to the amount of reactant in the reactor
starts to diminish. In order to obtained the C(t) curve, graph of conductivity value
versus time was plotted. Based on the area under the graph, E(t) is calculated and the
data is tabulated in the table before the graph of E(t) is constructed. In experiment 2,
 20

for the step change experiment with constant flow rate of 700 mL/min, the graph
shows the outlet conductivity increases with time until it become constant starting
from 2.5 minutes. Meanwhile, the inlet conductivity starts to rise until 1.5 minutes; it
started too constantly at 3.6 mS/cm.
The time the materials spend in the reactor is being called as the residence
time. E(t) curve was obtained from the C(t) curve a function of time which show the
residence time distribution (RTD) function for the plug flow reactor.. it describes the
fraction of fluid exiting the reactor. From the calculated value of E(t), the residence
time distribution can be determined. The value will help to calculate the mean
residence, variance and skewness. For experiment 1, the mean residence time, tm was
5.071 min, second moment variance, 2 was 36.9505 min2, and the third moment
5
skewness, s3 was8.5112 min2 . The skewness for the pulse input give a negative
value and it called negative skew.
Meanwhile, for experiment 2, the mean residence time, tm was 6.2415 min,
second moment variance, 2 was 4.4153 min2, and the third moment skewness, s3
5
was2.8272 min2 . Comparing to the graph in the experiment 1, the skewness give a
positive value and it called positive skew compare to pulse input.

9.0 Conclusion

Based on the experiment, the effect of pulse input and step change for tubular reactor
and the residence time distribution (RTD) for both input type can be determined.
From the experimental work and data collected, it is proven that initially high driving
force of the experiment in pulse input will diminish along the process in tubular
reactor which is implied in current situation where the value of the outlet conductivity
is high at certain time and gradually declines until it reaches 0.0 mS/cm. It is also can
be concluded that the residence of time (RTD) is effected by the value of E(t) because
in order to find the RTD, the value of E(t) must be determined first. The second
moment variance, 2 and third moment skewness, s3 are also calculated for both
experiment using the RTD value calculated earlier. Lastly, the graph of distribution
exit time C(t) versus time and outlet conductivity E(t) versus time were plotted to
verify that E(t) depends on the value of C(t).
 21

10.0 Recommendation

To improve the result of this experiment, the general start up and general shut down
procedures need to be done carefully in order there is no leftover substances in the
reactor. In addition, make sure to record the results at exact timing which is every 30
second within 4 to 5 minutes because the result obtained varies with time.
Furthermore, always ensure the flow rate of the de-ionized water is at 700 mL/min.

11.0 References

Ashe, Robert (2012). From Batch to Continuous Processing. Chemical Engineering.

page 34-40.
H.S.Fogler (2014). Elements of Chemical Reaction. 4th Edition, Pearson New
International Edition, page 14-17
L.R.Souza, L.Lorenz (2014). Residence Time Distribution for Tubular
Reactors,University of Brazil.
Mixing in Chemical Reactors (2016). Nob Hill Publishing, LLC. Retrieved 1st
October 2016 from
http://jbrwww.che.wisc.edu/home/jbraw/chemreacfun/ch8/slides-mixing.pdf
Residence Time Distribution of Chemical Reactors (2010). Retrieved 5th October
2016 from https://www.reaction-engineering.tu-
berlin.de/fileadmin/fg133/RTD.pdf

12.0 Appendix