CKB 20104-Reaction Engineering: Experiment 3a

Effect of Residence Time on the Reaction in a PFR

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Page

SUMMARY
In this experiment , a saponification reaction between NaOH and Et(Ac) in a PFR can

be carried out. The reaction rate constant can be determined. Other than that, the effect of
residence time on the conversion in a PFR was also determined.The highest conversion for
250 flowrate is 40.68% while the highest conversion for 100 flowrate is 48.34%. The
chemical reactors are crucial and important in a chemical industries. It is the most important
things as it is the place for the reaction to happen. The type of reactor must be suited with the
reaction that we seek for. One of the example of the reactors is Plug Flow Reactor(PFR) The
Plug Flow Reactor (PFR) was used for reaction in continuous, flowing systems in a shape of
cylinder. The solution that flow in the reactor are describe as Plugs. An ideal plug flow reactor
has a fixed residence time: Any fluid (plug) that enters the reactor at time t will exit the
reactor at time,, where t is the residence time of the reactor. Residence time, is the average
amount of time that a particle spends in a particular system. The residence time, is a
representation of how long it takes for the concentration to significantly change in the
sediment. In this experiment, we adjust the pump two value of flowrate which is 250 L/s and
100 L/s. The flow rate for each experiment is variable but the reactor volume remain constant
for every experiment. Conversion is an improved way of quantifying exactly how far has the
reaction moved, or how many moles of products are formed for every mole of NaOH has
consumed. Rate of reaction is defined as the rate of disappearance of reactants or the rate of
formation of products. Rate of reaction can describe about how fast a number of moles of one
chemical species reaction to form another species. There are also some errors obtained
because the result for the conductivity is not constant. This is due to the wrong measuring of
ethyl acetate and sodium hydroxide. Besides that. The tank of the equipment was polluted.
This is due to the residue left in the tank.

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DATA AND RESULTS

Reactor volume
Temperature =

Time
(min
)

Temperatur
e (C)

1.5 L

Flowrate

= 100_____ mL/min

_____ oC

Flow
rate of
NaOH,
FNAOH
(mL/mi
n)

Flow
rate of
Et(Ac),
FET
(mL/mi
n)

Total flow
rate of
solutions,
F0
(mL/min)
= FNAOH +
FET

Residenc
e time,
(min)
(Selfcalculate)

Inlet
conductiv
ity
(mS/cm)

(Selfcalculate)

Inlet
concentrat
ion of
NaOH,
CNaOH (M)

Outlet
Conductiv
ity

Outlet
concentra
tion of
NaOH,
CNaOH (M)

(from
calibration
curve)

(mS/cm)

(from
calibration
curve)

Conversi
on,
X (%)
(Selfcalculate)

Inlet

Outle
t

29.9

29.4

100

101

201

0.0075

12.15

0.0568

12.29

0.0574

-1.0563%

30.2

29.6

110

103

213

0.007

11.90

0.0556

8.73

0.0408

26.62%

10

30.4

29.7

110

90

200

0.0075

12.47

0.0583

8.08

0.0378

35.16%

15

30.4

29.9

108

100

208

0.0072

12.23

0.0571

7.22

0.0337

40.98%

20

30.6

30.1

108

99

207

0.0072

11.62

0.0543

6.72

0.0314

42.17%

25

30.7

30.2

107

99

206

0.0073

11.61

0.0543

6.25

0.0292

46.22%

30

30.8

30.3

107

97

204

0.0074

11.59

0.0542

6.00

0.028

48.34%

35

31

30.5

106

99

205

0.0073

11.57

0.0541

6.00

0.028

48.24%

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40

31.2

30.6

108

97

205

0.0073

11.53

0.0539

6.05

0.0283

47.5%

45

31.4

30.7

110

98

208

0.0072

11.20

0.0523

5.98

0.0279

46.65%

50

31.5

30.9

109

97

206

0.0073

11.23

0.0525

5.87

0.0274

47.81%

F0,avg =
205.73

avg
=0.0073

NOTE:
1. Obtain the concentration of NaOH for each of the reaction time from the measured conductivity value based on the
calibration curve (Appendix B).

Inlet concentration of NaOH Outlet concentration of NaOH

100%
Inlet concentration of NaOH

2. Formula to calculate conversion, X

RESULTS FOR EXPERIMENTS

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Reactor volume
Temperature =

Time
(min
)

Temperatur
e (C)

1.5 L

Flowrate

_250__ mL/min

_____ oC

Flow
rate of
NaOH,
FNAOH
(mL/mi
n)

Flow
rate of
Et(Ac),
FET
(mL/mi
n)

Total flow
rate of
solutions,
F0
(mL/min)
= FNAOH +
FET

Residenc
e time,
(min)
(Selfcalculate)

Inlet
conductiv
ity
(mS/cm)

(Selfcalculate)

Inlet
concentrat
ion of
NaOH,
CNaOH (M)

Outlet
Conductiv
ity

Outlet
concentra
tion of
NaOH,
CNaOH (M)

(from
calibration
curve)

(mS/cm)

(from
calibration
curve)

Conversi
on,
X (%)
(Selfcalculate)

Inlet

Outle
t

31.5

31.9

24.5

24.8

49.3

0.0304

12.36

0.0578

8.43

0.0394

31.83%

31.6

31.1

24.5

24.7

49.2

0.0305

12.39

0.0579

7.71

0.036

37.82%

10

31.7

31.2

24.8

24.8

49.6

0.0302

12.48

0.0583

7.68

0.0359

38.42%

15

31.8

31.3

25.4

25.0

50.4

0.0298

12.77

0.0597

7.68

0.0359

39.87%

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20

31.8

31.4

25.6

25.1

50.7

0.0296

12.64

0.0591

7.69

0.0359

39.26%

25

31.8

31.5

26.0

24.8

50.8

0.0295

12.65

0.0591

7.65

0.0357

39.59%

30

32.1

31.8

26.4

24.9

51.3

0.0292

12.63

0.059

7.48

0.035

40.68%

35

32.2

31.8

25.8

24.0

49.8

0.0301

12.41

0.058

7.40

0.0346

40.34%

F0,avg = 50.14

avg
=0.0299

NOTE:
1. Obtain the concentration of NaOH for each of the reaction time from the measured conductivity value based on the
calibration curve (Appendix B).

X
2. Formula to calculate conversion, X

Inlet concentrat ion of NaOH Outlet concentrat ion of NaOH

100%
Inlet concentrat ion of NaOH

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Conversion , X vs. Reaction Time, t

60

50

40

Conversion, X

30

Flowrate 100 ml/min

20

10

10

15

20

25

30

35

40

45

50

Reaction Time, t

Figure 1 Conversion,X versus Reaction Time,t for 100 mL/min

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Conversion, X vs. Reaction Time, t

45
40
35
30
25

Conversion, X

Flowrate 250 ml/min

20
15
10
5
0

10

15

20

25

30

35

Reaction Time, t

Figure 2 Conversion,X versus Reaction Time,t for 250 mL/min

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For 250 ml/min flowrate,

k=

FF
Vpfr Cao

205.73
( 1.5 )( 0.0568)

[ ]
X
1 X

0.4834
1.0 .4834

= 2259.49 mol/L.min

-rA = kCa2

-rA = (2259.49) (0.028)2

-rA = 1.7714
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For 100 ml/min flowrate,

k=

FF
Vpfr Cao

50.14
( 1.5 )( 0.0568)

[ ]
X
1 X

0.4068
1.0 .4068

= -0.0589 mol/L.min
-rA = kCa2

-rA = (-0.0589) (0.035)2

-rA = -0.000072
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3.0

ANALYSIS AND DISCUSSION

A saponification reaction between NaOH and Et(Ac) were carried out using pilot Plug

Flow Reactor (PFR). The main objective is to study the effect of residence time, on the
conversion in a PFR. Another objective is to determine the reaction rate constant,k.
The reaction between NaOH and Et(Ac) is allowed to occur and mixed in the tank of
PFR called SR1. The flow rates were set with constant flow rates for both feed vessel, B1 and
B2 which is 100 mL/min for initial value. The solutions were mixed until it reached a steady
state. The data which appeared on screen were taken to determine the concentration of NaOH
in the reactor and extent of conversion. The step was repeated by using different flow rates of
250 mL/min.
From the calculation, the residence time for each flow rates was calculated and
tabulated. The residence time were increasing inversely with decreasing flow rates. The result
shown that at flow rate 100 mL/min, the residence time is 0.0073 min. The residence time is
0.0299 min at flow rate of 250 mL/min. The conversion for 100 mL/min is 47.81 %. The
conversion were 40.34 % for 250 mL/min. The data collected is tabulated.
A graph Conversion,X (in %) versus Residence Time,t (in min) was plotted and shows
that the conversion is directly proportional to the residence time. The percentage of
conversion decreases with increasing residence time. There might be an error during this
experiment was occurred which is the flow rates is difficult to maintain for both of flow rates
so that the flow rates fluctuated during the experiment which caused the residence time,t
decrease during experiment.
. Theoretically, the conversion,X will increase when residence time,t increase. The
flow rate is also effect the conversion and the residence time. If the flowrate increase the
conversion can be faster because the reaction between NaOH and Et (Ac) became more faster
and this will increase the conversion of the process. Residence time is said to be directly
proportional to system capacity but inversely proportional to the flow rate of the substance
through the system.If the size of the system is changed, the residence time of the system will
be changed as well. The larger the system, the larger the residence time, assuming the inflow
and outflow rates are held constant. The smaller the system, the shorter the residence time will
be, again assuming steady-state conditions.From this statement we can conclude that the
bigger the system the lower the value of conversion for that reactor.

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Rather than that, in this experiment the rate of reaction between NaOH and Et(Ac) were also
calculated. The result shown that the rate of reaction (mol/L.min) for 100 mL/min flow rate is
-0.0589 mol/L.min. The rate of reaction for 250 mL/min flow rate is 2259.49 mol/L.min. The
rate of reaction were deacreasing respectively with decreasing flow rates.
Hence, it can be conclude that the conversion is more efficient when the residence
time is higher in the PFR. In the longer the residence time will make the mixture in the
reaction mix better. More products will be formed from the reaction. On the other hand, the
experiment was fast reaction and the reading of both conductivity are a little difficult to get
constant which is the reading became fluctuated. So, any trapped air in the pipeline need to be
bleeds to get accurate result.

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This experiment is being conducted to study about plug flow reactor when conducting
saponification reactionand the effect of temperature on rate of conversion in PFR. The
chemicals that being used are sodium hydroxide (NaOH) and ethyl acetate. Both of the
chemicals were put in a tank and pump into PFR, with a constant flowrate, 100mL/min. The
thermostat is then being set to 40,50 and 60c. The results were then collected, and tabulated
in table 1,2,3. Then, the conversion value was calculated.
From this experiment of effect of residence time on the reaction in a PFR, the main
objective is to determine the effect of residence time on the conversion in a PFR. In order to
start this experiment 50L Sodium Hydroxide (0.1M) and 50L Ethyl Acetate (0.1M) was mixed
in receiving vessel B3 to prepare the general solutions to start the experiment. The experiment
then was proceed to fulfill the objectives which to carry out a saponification reaction between
NaOH and Et(Ac) using Plug Flow Reactor to compare the reaction conversion between this
types of reactors (PFR) and to determine the reaction rate constant.
Residence time is said to be directly proportional to system capacity but inversely
proportional to the flow rate of the substance through the system.If the size of the system is
changed, the residence time of the system will be changed as well. The larger the system, the
larger the residence time, assuming the inflow and outflow rates are held constant. The
smaller the system, the shorter the residence time will be, again assuming steady-state
conditions.From this statement we can conclude that the bigger the system the lower the value
of conversion for that reactor. As can been shown from the experimental result which the PFR
has higher conversion compared to single stage of CSTR.

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From the experiment that has been conducted, the value for the conversion, X % for each
reactors have been identified. For single stage CSTR reactor the conversion obtained is
62.9834% at which the inlet and outlet conductivity (mS/cm) are at 6.53 and 4.94.From the
calculation that have has been done the residence time (min) obtained is 0.011.For the 3
stage CSTRs the conversion, X % obtained is 99.99949% at which the inlet and outlet
conductivity is at 9.12 and 4.92.The value of residence time (min) calculated is 0.005.For
reactor type of PFR, the inlet and outlet conductivity are 11.64 and 0.0030 at which the
conversion recorded is 94.5055%.From the PFR reactor, the value for residence time (min)
obtained is 0.008.
Based from the result, 40c has a higher conversion compared to 60c. According to
theory, as temperature increase, the rate of reaction should also increase, hence the rate of
conversion of NaOH and ethyl acetate will also increases. For reaction to occurs, it need to
have an effective collision between two particles. So, by adding more heat, the particles will
vibrate more vigorously and the collision frequency will increase. Once the collison frequency
has increased, the effective collision will occurs more regularly.
In this experiment, 40c has a higher conversion when compared to 60c. Higher
conversion means higher rate of reaction. The result is not according to theory. The results
may contain some error. 60c should have a higher conversion compared to 40c. The error
may occurs when setting the thermostat temperature. Students may set the temperature higher
or lower to the actual temperature.

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Graph 1 showed the graph of conversion,X against reaction time,t for different flow
rates. The graph showed when the residence time increased, the conversion also increased.
Graph 2 showed the graph of conversion VS residence time at 60C which the graph initially
shows that the conversion and time was parallel. Graph 3 showed the graph of conversion VS
residence time at 70C and it give the decreasing result of conversion when the time
increased. This PFR experiment was done under steady state condition. In the tubular reactor,
the reactants are continually consumed as it flows down the length of the reactor. The plug
flow need to fix with the residence time as this residence time is used to characterize the
mixing and flow within reactors. Theoretically, when the residence time distribution is
increase, the conversion also increases. The flow rate is also effect the conversion and the
residence time. If the flowrate increase the conversion can be faster because the reaction
between NaOH and Et (Ac) became more faster and this will increase the conversion of the
process.
When reaction rate constant has being calculated, graph ln k against 1/T was plotted.
The highest reaction rate constant is 20396.90 at 40c, while thelowest is 21415.84 at 60c.
The gradient for the graph is -0.464 and y-int is 10.01. By knowing the value of gradient and
y-int, the value of activation energy and frequency factor for this saponification energy is
obtained. The activation energy is 3.78 J/mol.K while the value for frequency factor is
1

3 1

22247.84 mol m s

From this result, it can be said that inconsistency of the flow rate reading
affected to its value of reading. The flow rate must be constant at the rate of 100mL/min and
250mL/min. This flow rate value can be controlled by using both V7 and V8 valves. Both
flow rate need to be constant and same. As it is manually controlled, to get exact reading of
100mL/min and 200mL/min is quite impossible so the value is set approximately to the value.
Thus, the flow rate must be always adjusted to get the same value for both valves to overcome
the overshoot in the experiment. On the other hand, the experiment was fast reaction and the
reading of both conductivity are a little difficult to get constant which is the reading became
fluctuated. So, any trapped air in the pipeline need to be bleeds to get accurate result.
the conversion in a reactor depends on the average reaction rate as well as the residence
time.A CSTR is well mixed, and the average reaction rate will be that of the conditions of the
bulk mixture. The composition of the reactor product is also the same as that in the reactor.

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For most reactions (especially equilibrium reactions) the rate of reaction decreases with
increasing concentrations of final product (and decreasing concentrations of reagent).In a plug
flow reactor, the rate is not constant. In the first section of the reactor, the rates are high (high
concentration of feed and low concentration of product). As the material goes through the
reactor the rates drop. The average rate is still higher and hence the conversion for a given
reactor volume is also better.
The ideal heat transfer conditions can be achieved by varying the surface to volume ratio
or the cooling/heating flux. Thus stages where process heat output is very high either use
extreme heat By tackling the problem as a series of stages, extreme cooling/heating conditions
to be employed at the hot/cold spots without suffering overheating or overcooling elsewhere.
The significance of this is that larger flow channels can be used. Larger flow channels are
generally desirable as they permit higher rate, lower pressure drop and a reduced tendency to
block.

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4.0

CONCLUSIONS AND RECOMMENDATIONS

As a conclusion, it can be seen that the effect of RTD on the reaction in a PFR affect

the saponification reaction between NaOH and Et(Ac), residence time on the extent of
conversion and the reaction rate constant. Based from the result obtained, the higher the flow
rate the shorter the time taken for the reaction to occur until it reached a constant conductivity
value. At 200L/min, the k value is 0.32mol/dm.min. The conversion is the highest at
400L/min, 61.9% and lowest at 200L/min, 34.78%. The average residence time is highest at
200L/min compared to other flow rates. The residence time increase as the conversion
increase.
There are some recommendations that are needed for improvement in order to increase
the efficiency of the result obtained. During the experiment, make sure the solution used is
measured correctly. The eyes must be perpendicular to the measuring scale to avoid parallax
error. The mixture of the reaction might not be stirred evenly as the reaction just started at that
time. Lastly, check the flow rate constantly as it needs to approximately reach 200 L/min for a
better value of conductivity. Make sure the feed stock is sufficient so that the experiment can
be conduct until the conductivity is constant.

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5.0

TUTORIAL
A. Discuss the advantages and disadvantages of using PFR reactors in chemical
reaction. Describe an example of industrial applications that utilized PFR
reactors in its process
Answer:
There are several advantages and disadvantages of using plug flow reactors
(PFR). The advantages of using PFR are it is easy to maintain as there is no agitator or
moving part in the reactor. Moreover, PFR have a high volumetric unit conversion per
unit of reactor of any of the flow reactors. Furthermore, PFR was running for long
periods of time without maintenance and has low pressure drop. Next, PFR tubes are
easy to clean and it was mechanically simple and unvarying product quality. The last
but not least is heat transfer rate of PFR can be optimized by using more, thinner,
fewer and thicker tubes in parallel. Instead of having advantages, PFR also have theirs
disadvantages. The disadvantages of PFR are, it is difficult to control the temperature
within the reactor and can caused in undesirable temperature gradients. Next, PFR
maintenance is also more expensive than CSTR maintenance and hot spots may occur
within reactor when used for exothermic reactions. The example of industrial
application that utilized PFR reactors in its process is to design and produce 1,016
metric tons/day of ammonia at a feed of 5,500 kmol/hr while maintaining the best
compromise between production and purity. Simulated in ASPEN with an adiabatic
Gibb reactor, optimal production is achieved at 100 bar reactor pressure and a 7.25%
purge stream, resulting in 98.96% product stream purity. The simulated process is
comparable to conventional ammonia synthesis plants. Further economic optimization
is focused on compression costs and reactor efficiency. A new ruthenium based
catalyst with higher activity at lower total pressures can be employed enabling the
process to run at significantly lower pressures while maintaining high ammonia
conversion. Installing this catalyst into a multi-bed radial plug-flow reactor results in
an attractive combination of high production and reduced costs that can be custom
made for expansion, retrofit, or grassroots projects.
B. Write a one-paragraph summary of any journal article that studies chemical
reaction in a PFR. The article must have been published within the last 5 years.
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Explain on the PFR reactor used in the study and its significance to the study
done.
Answer:
Summary of journal: This journal proposes RTD studies in plug flow reactor
and comparison of non-ideal reactors using residence time distribution function. The
model also gives a prediction of the number of ideal continuous stirred tank reactors
(CSTR) that could represent the non-ideal plug flow reactor (PFR) in question.
Simulated results reveal that 10 numbers of ideal stirred tanks in series would
represent the non-ideal plug flow reactor under study. The graphical result of all four
reactors is generated directly by polymath. Most of the chemical reactors in the
industries have non-ideal regime. The non-ideal plug flow reactor (PFR) is one whose
attributes deviate from that of the ideal plug flow reactors. Therefore, in depth
knowledge of the residence time distribution (RTD) of components in the reactor is
necessary for its analysis. The residence time distribution indicates how much time
each fraction of a charged material spends in the vessel. The residence time
distribution of reactants or tracers in a flow vessel is a key datum for determining
reactor performance. The significant of the study done to get knowledge of RTD is
directly useful in vessel design, improvement in performance and for the first order
kinetics conversion calculations. Detailed knowledge of residence time distribution
with the understanding of the overall flow pattern helps in development of a model of
the system and this model can be used for the handling complicated kinetic. Moreover,
mixed model approach has gained importance in RTD understanding. According to
this concept, a real reactor is considered as consisting of various flow regimes with
known resistance time distribution such as plug flow regions, perfectly mixed regions
and various types of flow. (Research Journal of Recent Sciences, 2012)

6.0

REFERENCES

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1. Plug Flow Reactor Model. (2005) Wikipedia. [Online]. [Accessed 11th March, 2016].
Available from World Wide Web:
https://en.wikipedia.org/wiki/Plug_flow_reactor_model
2. Lanny D.S., The Engineering of Chemical Reactions, Oxford University Press, New
York, 1998.
3. Plug Flow Reactors. (2013) Encyclopedia Of Chemical Engineering Equipment.
[Online] [Accessed 11th March, 2016]. Available from World Wide Web:
http://encyclopedia.che.engin.umich.edu/Pages/Reactors/PFR/PFR.html
4. Plug Flow Reactors. (2000) University of Michigans Education Portal. [Online]
[Accessed 12th March, 2016]. Available from World Wide Web:
http://www.umich.edu/~elements/5e/asyLearn/bits/pfrfinal/index.htm
5.

7.0

APPENDICES

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