TABLE OF CONTENT

TITLE Abstract / Summary Introduction Objectives Theory Apparatus Procedures Results Sample calculation Discussion Conclusion Recommendation Reference Appendix

PAGES 2 3 5 6 10 11 14 18 21 23 24 25 26

ABSTRACT

Reactors are used in the chemical industry for the millions processes. One of many different type of reactors is tubular reactor. 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 this experiment, the tubular reactor (Model: BP 101-B) is used. This experiment is divided into two which are to examine the effect of pulse input in a tubular reactor and the other is to examine the effect of step change input in a tubular reactor. The other objective is to compare the residence time distribution (RTD) graph for these two experiments. For pulse input, RTD graph is increased until 0.3587 min-1 and then decreased to the value zero. However, the RTD graph for step change input is increase and at time 2 min the graph is constant. The mean residence time, variance, and skewness are also calculated for both experiments.

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.

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.

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 rates1.

Tubular reactors are used for kinetic performance reasons in a large number of chemical processes. The design of systems with tubular reactors involves recognition of the many important differences between continuous stirred-tank reactors (CSTR) and plug-flow tubular reactors (PFR). The most important distinction is the importance of the feed conditions in tubular reactor systems, particularly the reactor inlet temperature. Reactor feed preheating becomes an important design parameter, which typically involves
1

Tubular reactor, http://www.metal.ntua.gr/~pkousi/e-learning/bioreactors/page_07.htm

trade-offs between steady-state economics and dynamic controllability. Reactor inlet concentrations are also more critical in tubular reactor systems, because of parametric sensitivity and the potential for complex dynamics2.

Douglas, J. M. Conceptual Design of Chemical Processes, McGraw -Hill: New York, 1988.

OBJECTIVE

Experiment 1: 1. To examine the effect of a pulse input in tubular flow reactor. 2. To construct a residence time distribution (RTD) function for the tubular flow reactor.

Experiment 2: 1. To examine the effect of a step change input in a tubular flow reactor. 2. To construct a residence time distribution (RTD) function for the tubular flow reactor.

THEORY

Residence-Time Distribution (RTD) Function The idea of using the distribution of residence times in the analysis of chemical reactor performance was apparently first proposed in a pioneering paper by MacMullin and Weber.3 However, the concept did not appear to be used in extensively until the early 1950s, when Prof. P.V. Danckwerts4 gave organization structure to the subject of RTD by defining most of the distributions of interest. The residence time distribution (RTD) of a reactor is a characteristic of the mixing that occurs in the chemical reactor. No axial mixing in a plug flow reactor (PFR). The continuous stirred tank reactor (CSTR) is thoroughly mixed. Actually, different reactors can display identical RTD. However, the RTD exhibited by a given reactor yields distinctive clues to the type of mixing. The RTD is determined by experimentally by injecting an inert chemical called a tracer into the reactor at some time t = 0 and measuring the tracer concentration, C in the effluent stream as a function time. There are two types method of injection which are pulse input and step input.

R.B. MacMullin and M.Weber, Jr., Trans. Am. Inst. Chem. Eng., 31, 409 (1935).

Pulse Input

An amount of tracer No is suddenly injected in one shot into the feed stream entering the reactor in as short time as possible in pulse input. The outlet concentration is then measured as a function of time. The effluent concentration vs. time curve is referred to as the C(t) curve in the RTD analysis.

The amount of tracer C(t) exiting between time t and (t + t) is N = C(t)vt where v = the effluent volumetric flow rate

If it divided by the total amount of material that was injected into the reactor, N0, N vC(t) = t N0 N0 which represents the fraction of material that has residence time in the reactor between time t and (t + t).

For a pulse injection, E(t) = vC(t) N0 N = E(t)t N0 E (t) called as the residence time distribution function. It is describes how much time different fluid elements have spent in the reactor. (1)

It can be obtained from the outlet concentration measurements by summing up all the amounts of materials if N0 is not known directly. N between time t=0 and infinity. dN = C(t)vdt
4

P. V. Danckwerts, Chem. Eng. Sci., 2, 1 (1953) th H.Scot Fogler, Elements of Chemical Reaction Engineering, 4 edition, Prentice Hall International Series (USA), 1999

By integrating, N0 = vC(t)dt
0

(2)

By assuming v is constant, substitute (2) into (1) E(t) = C(t)

0 C(t)dt

The integral in the denominator is the area under the C(t) curve.

Step Input A more general relationship can be developed between a time -varying tracer injection and the corresponding concentration in the effluent by understanding the pulse input. The below show the output concentration from the vessel is related to the input concentration by the convolution integral,

Cout (t) = Cin (t t )E(t )dt

0

By considering a constant rate of tracer addition to a feed in order to analyze a step input in the tracer concentration with constant volumetric flow rate that is initiated at time t=0. 0 t0 C0 (t) = { (C )constant t 0 0

Because the inlet concentration is constant with time, C0, it can be taken outside the integral sign, Cout (t) = C0 E(t )dt
0 t

By dividing with C0 yields,

t Cout (t) [ ] = E(t )dt = F(t) C0 step 0

The expression differentiated to obtain the RTD function E(t), E(t) = d C(t) [ ] dt C0 step

Formula for other calculation,

()
0

E(t) =

()
0 ()

Mean residence time, tm = 0 () Second moment, Variance, 2 = 0 ( )2 () Third moment, Skewness, 3 = 3/2 0 ( )3 ()
1

APPARATUS AND MATERIALS

APPARATUS: Tubular flow reactor (Model: BP 101-B)

MATERIALS: Sodium chloride solution, NaCl (0.025M) Deionised water, H2O

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PROCEDURES
General Start-Up Procedures

1. All valves were ensured initially closed except valve V7. 2. 20 liter 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.

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. 11

EXPERIMENT 1: Pulse Input in a Tubular Flow Reactor

1. The general start-up procedures are performed. 2. Valve V9 is opened and pump P1 is switched. 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 FI-01. 4. The de-ionized water is left to continue flowing through the reactor until the inlet (Q1-01) and outlet (Q1-02) conductivity values are stable at lows levels. The both conductivity 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 stared 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 FI-02. 8. The salt solution is left to flow for 1 minute, and then the timer is reset and restarted. The time is start at the average pulse input. 9. Valve V11 is closed and pump P2 is switch off. Then, quickly valve V9 is opened and pump P1 is switch on. 10. The de-ionized water flow rate is making sure to always maintain at 700 mL/min by adjusting the P1 flow controller. 11. Both the inlet (QI-01) and outlet (QI-02) conductivity values is recorded at regular intervals of 30 seconds. 12. The conductivity values is continue recorded until all the 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 switched on. 3. Pump P1 flow controller is adjusted to give a constant flow rate of de-ionized water 12

into the reactor R1 at approximately 700 ml/min at FI-01. 4. The de-ionized water is left to continue flowing through the reactor until the inlet (QI-01) and the outlet (QI-02) conductivity values are stable at low levels. Both conductivity values are recorded. 5. Valve V9 is closed and pump P1 is switched off. 6. Valve V11 is opened and pump P2 is switched on. The timer is started simultaneously. 7. Both the inlet (QI-01) and outlet (QI-02) conductivity values are recorded at regular intervals of 30 seconds. 8. The conductivity values are continued recorded until all readings are almost constant.

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RESULTS

Experiment 1:

Flow rate Input type

= 700 mL/min = Pulse Input

TIME (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

CONDUCTIVITY (mS/cm) INLET 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 OUTLET 0.0 1.5 1.9 2.1 2.2 1.8 0.5 0.1 0.0

Outlet Conductivity vs Time

2.5
Outlet Conductivity Values, mS/cm 2 1.5 1 0.5 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 Time, min

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The C curve From the calculation, 0 C(t)dt = 6.1333 mS min/cm

TIME, min OUTLET CONDUCTIVITY, mS/cm E(t), min-1

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0.0

1.5

1.9

2.1

2.2

1.8

0.5

0.1

0.0

0.0

0.2446 0.3098 0.3424 0.3587 0.2935 0.0815 0.0163

0.0

E(t) vs Time
0.4 0.35 0.3 E(t), min-1 0.25 0.2 0.15 0.1 0.05 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 Time, min

The E curve (RTD function plot)

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Experiment 2:

Flow rate Input type

= 700 mL/min = Step Change Input

TIME

CONDUCTIVITY (Ms/cm) INLET OUTLET 0.0 0.8 1.3 1.9 2.0 2.0 2.0 2.0 2.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

0.0 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5

Outlet Conductivity vs Time

2.5 Outlet Conductivity Values, mS/cm

1.5

0.5

0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 Time, min

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The C curve From the calculation, 0 C(t)dt = 6.6667 mS min/cm

TIME, min OUTLET CONDUCTIVITY, mS/cm E(t), min-1

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0.0

0.8

1.3

1.9

2.0

2.0

2.0

2.0

2.0

0.0

0.12

0.194

0.285

0.30

0.30

0.30

0.30

0.30

E(t) vs Time
0.35 0.3 0.25 E(t), min-1 0.2 0.15 0.1 0.05 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 Time, min

The E curve (RTD function plot)

17

SAMPLE CALCULATION Experiment 1:

By using the numerical integration formula, which is in this calculation the Simpsons one third rule formula is used.

*Simpsons One Third Rule Formula for N+1 points, where is N is even;
1

() =

( + 41 + 2 ) 3 0

Where

(A 25)

1 0

Therefore, the value of the integral 0 C(t)dt,

4.0 0.0 2

= 2.0

0 () =

2.0 3

(0 + 4(2.3) + 0) = 6.1333 . /

Calculate E(t), min-1 for each C(t) from the formula:

E(t) = =

()
() 0

() 6.1333 ./

18

Calculate the following:

Mean residence time,

tm = 0 ()

Use *Five-Point Quadrature Formula for N+1 points, where is N is even;

() =

( + 41 + 22 + 43 + 2 4 + + 4 1 + 3 0

Where

(A 25)

=
=
4 0 4

= 1.0

tm

= 0 () = 3 + 41 + 22 + 43 + 4 = 3 0 + 4(0.3098) + 2(0.7174) + 4(0.2445) + 0 = 3.652 min

1

Second moment variance: 2 = 0 ( )2 () =

3 1

+ 41 + 22 + 43 + 4

= 3 [0 + 4(2.1788) + 2(0.9789) + 4(0.0346) + 0] = 3.6038 = 1.899 min2 19

Third moment Skewness: 3 = 3/2 0 ( )3 ()

3 1 3 1

0 ( t m )3 . () = =

+ 41 + 22 + 43 + 4 [0 + 4(5.7784) + 2(1.617) + 4(0.0226)]

= 231139 s3 = -88325.43 s = -44.53 min5/2

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

0 C(t)dt = 6.6667 mS min/cm E(t) = 6.6667 ./ Mean residence time =16.5867 min Second moment variance = 13.967 min2 Third moment Skewness = -1.272 min5/2
()

20

DISCUSSION

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 tubes6. There are two experiments for tubular reactor which are pulse input in a tubular reactor and step change input in a tubular reactor. For first experiment, the objective to achieve is to examine the effect of a pulse input in a tubular reactor. However, for next experiment is to attain the effect of a step input in a tubular reactor. From the result for these two experiments, the residence time distribution (RTD) function which is E(t) as a function of time is plotted. From the both graph that has been plotted, the trend for this two graphs are different. The trend for residence time distribution (RTD) graph for first experiment for pulse input is increase and then for a few minute is decreased until the value is zero. However, the graph for second experiment the graph is increase and at time 2 min, the value of E(t) is constant. In these experiments, the mean residence time, second moment (Variance), and third moment (Skewness) are also calculated. For experiment 1, the mean residence time is 3.652 min, second moment (variance) is 1.899 min2 and third moment (Skewness) is = 44.53 min5/2. On the other hand, the mean residence time for experiment 2 is 16.5867 min. Then, the second moment (variance) is 13.967 min2 and the third moment (Skewness) is 1.272 min5/2. This experiment shows that there are the differences between pulse input and step
6

Levenspiel, Octave (1999). Chemical Reaction Engineering (3 . Edition), John Wiley & Sons.

rd

21

change input in tubular reactor method. One of the differences is the tracer of the input. In a pulse input, an amount of tracer substance is suddenly injected in one shot into the feed stream entering the reactor in as short times as possible. However, for step input, it consider a constant rate of tracer addition to a feed is initiated at time t = 0. Before this time no tracer was added to the feed7. The tubular reactor is usually used in some of the following application which are large scale reactions, fast reactions, homogeneous or heterogeneous reactions, continuous production, and high-temperature reactions8.

7 8

Expt. MT 401, Residence Time Distribution - http://www.che.iitb.ac.in/courses/uglab/cl431/ms401-rtd.pdf http://en.wikipedia.org/wiki/Plug_flow_reactor_model#Applications

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CONCLUSION

In this experiment, the objectives of the experiment were achieved. As a conclusion, there are differences for pulse input and step change input in a tubular reactor. The residence time distribution (RTD) function is one of the differences for pulse input and step change input. For RTD graph for pulse input experiment, the graph is increase and then decrease to the value zero. However, the RTD graph for step change input, the graph is increase then constant at certain value. Hence, the experiment was successful.

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RECOMMENDATION

There are few suggestions to get more accurate results for this experiment, which are: Ensure that no leakage at the valve on the unit. This to prevent the result will affect. Make sure that the valve is open or close, follow as the general start -up procedure carefully. For both experiments, do more trial to get average of conductivity for both inlet (Qi 01) and outlet (QI-02) conductivity values in order to get more accurate results.

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REFERENCES

Books:
1. Douglas, J. M. Conceptual Design of Chemical Processes, McGraw -Hill: New York, 1988. 2. H. Scott Fogler, Elements of Chemical Reaction Engineering, 4th Edition, Pearson International Edition (2006). 3. Levenspiel, O., Chemical Reaction Engineering (3rd edition). John Wiley & Sons, USA (1999).

Internet:
1. http://www.scribd.com/doc/29195386/Plug-Flow-Reactor 2. Expt. MT 401, Residence Time Distribution http://www.che.iitb.ac.in/courses/uglab/cl431/ms401-rtd.pdf 3. http://en.wikipedia.org/wiki/Plug_flow_reactor_model#Applications

Others: 1. R.B. MacMullin and M.Weber, Jr., Trans. Am. Inst. Chem. Eng., 31, 409 (1935). 2. P. V. Danckwerts, Chem. Eng. Sci., 2, 1 (1953)

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APPENDIX

Conductivity meter

Plug flow reactor (Model: BP 101)

26

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