ABSTRACT From this experiment, our objectives are to examine the effect of pulse input in a tubular flow reactor

and to construct a residence time distribution (RTD) function for the tubular flow reactor. First of all, the equipment is set up before we can run the experiment. After that, we set up the flowrate that is 700mL/min. After the conductivity for inlet and outlet we collected are reaching to a constant value, the experiment is stopped. The conductivity for inlet and outlet after 5 minutes are 0.2mS/cm and 0.1mS/cm. The outlet conductivity, C(t) then is calculated and the value we get is 2.60. Then, we are able to determine the distribution of exit time, E(t). The E(t) is calculated for each 30 seconds until it reach 5 minutes interval. The sum of E(t) we get is 1.00 which is the residence time distribution. The mean residence time, tm for this experiment is 0.7652 minute. The variance, 2 and the skewness, s3 are also then calculated. The value we get for 2 is 1.5112 and for the s3 is 4.1752. Graphs for outlet conductivity, C(t) against time and distribution of exit time, E(t) against time is plotted. The graphs we get from this experiment are just the same with the graphs in the theory. The value of E(t) is depends on the value of C(t).

INTRODUCTION In the tubular reactor, the reactants are continually consumed as they flow down the length of the reactor. Flow in tubular reactor 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 conveniently long reactors or may require unacceptable high feed rates. However, many tubular reactors that are used to carry out a reaction do not fully conform to this idealized flow concept. In an ideal plug flow reactor, a pulse of tracer injected at the inlet would not undergo any dispersion as it passed through the reactor and would appear as a pulse at the outlet. The degree of dispersion that occurs in a real reactor can be assessed by following the concentration of tracer versus time at the exit. This procedure is called the stimulus-response technique. The nature of the tracer peak gives an indication of the nonideal that would be characteristic of the reactor. For most chemical reactions, it is impossible for the reaction to proceed to 100% completion. The rate of reaction decreases as the percent completion increases until the point where the system reaches dynamic equilibrium (no net reaction, or change in chemical species occurs). The equilibrium point for most systems is less than 100% complete. For this reason a separation process, such as distillation, often follows a chemical reactor in order to separate any remaining reagents or by products from the desired product. These reagents may sometimes be reused at the beginning of the process, such as in the Haber process. Tubular flow reactors are usually used for this application which are: 1. Large scale reactions 2. Fast reactions 3. Homogeneous or heterogeneous reactions 4. Continuous production 5. High temperature reactions

Residence Time Distribution (RTD) analysis is a very efficient diagnosis tool that can be used to inspect the malfunction of chemical reactors. It can also be very useful in modelling
2

reactor behaviour and in the estimation of effluent properties. This technique is, thus, also extremely important in teaching reaction engineering, in particular when the non-ideal reactors become the issue. The work involves determining RTDs, both by impulse and step tracer injection techniques, and applying them to the modelling of the reactor flow and to the estimation of the behaviour of a nonlinear chemical transformation. The RTD technique has also been used for the experimental characterization of flow pattern of a packed bed and a tubular reactor that exhibit, respectively, axially dispersed plug flow and laminar flow patterns (FEUP). The concept of using a tracer species to measure the mixing characteristics is not limited to chemical reactors. In the area of pharmacokinetics, the time course of renal excretion of species originating from intravenous injections in many ways resembles the input of a pulse of tracer into a chemical reactor. Normally, a radioactive labelled (2H, 14C, 32P, etc.) version of a drug is used to follow the pharmacokinetics of the drug in animals and human. Another important field of RTD applications lies in the prediction of the real reactor performance, since the known project equations for ideal reactor are no longer valid. Now the concepts of macro and micro mixing are fundamental. For each macro mixing level, expressed in the form of a specific RTD, there is a given micro mixing level, which lies between two limiting cases, complete segregation and perfect micro mixing.

OBJECTIVES The objectives of this experiment are: 1. To examined the effect of pulse input in a tubular flow reactor. 2. To construct a residence time distribution (RTD) function for the tubular flow reactor.

THEORY In a tubular flow reactor, the feed enters at one end of a cylindrical tube and the product stream leaves at the other end. The long tube and the lack of provision for stirring prevent complete mixing of the fluid in the tube. Hence the properties of the flowing stream will vary from one point to another, namely in both radial and axial directions. It is often not necessary to know details of the entire flow fluid but rather only how long fluid elements reside in the reactor (i.e. the distribution of residence times). This information can be used as a diagnostic tool to ascertain flow characteristics of a particular reactor. The age of a fluid element is defined as the time it has resided within the reactor. The concept of a fluid element being a small volume relative to the size of the reactor yet sufficiently large to exhibit continuous properties such as density and concentration was first put forth by Danckwerts in 1953. In order to analyze the residence time distribution of the fluid in a reactor the following relationships have been developed. Fluid elements may require differing lengths of time to travel through the reactor. The distribution of the exit times, defined as the E(t) curve, is the RTD of the fluid. The outlet conductivity of a tracer species C(t) can be used to define E(t). That is: ( )
( ) ( )

Based on the data collected, a graph of conductivity versus time could be draw to obtain the C(t) curve and data of the integral C(t) could be calculate. ( )

Figure 1: Theory of graph with its formula area under the graph

Other things that are needs to be determined in this experiment are: Mean Residence Time =

t E(t).dt

= tiEi(t)

Second moment Variance, 2 = Third Moment Skewness, s3 =

(t - tm)2 E(t).dt = (t - tm)2 E(t) (t - tm)3 E(t).dt = (t - tm)3 E(t)

If the RTD function, E(t), is very broad, however, it may be difficult to inject an amount of tracer that is sufficiently large so as to keep the outlet concentration sufficiently high to be measured accurately.

Figure 2: Example of graph when distribution exit time is very abroad

APPARATUS 1. Soltec Tubular Flow Reactor instrument 2. Clock watch 3. Solution 0.025M Sodium Chloride and De-ionized water.

Figure 3: Soltec Tubular Flow Reactor instrument

EXPERIMENTAL PROCEDURES General Start-Ups 1. 2. 3. 4. 5. All valves are initially closed except valves V7. 20Liters of salt solution is prepared Feed tank B2 is filled with the sodium chloride solution. The ON power button is turn. The water De-ionizer is connected to the laboratory water supply. Valve V3 is opened and the feed tank B1 is allowed to feed with the water. Valve V3 is closed as the water level reached the tank mark. 6. Valve V2 and V10 is opened and pump P1 is switched on. From observing the flow meter F1-01 value, The P1 pump is adjusted by controlling the flow controller to obtain a flow rate of approximately 700mL/min. 7. V6 and V12 are opened and pump 2 P2 is switched on. From observing the flow meter F1-02 value, The P2 pump is adjusted by controlling the flow controller to obtain a flow rate of approximately 700mL/min. Then the valve V12 is closed and pump P2 is turn off. 8. The experiment can now be carried out.

Experiment 1:0.0486 Pulse input in a Tubular Flow Reactor. 1. Valve V9 is opened and pump P1 is switched on. 2. The P1 pump is adjusted by controlling the flow controller to obtain a flow rate of approximately 700mL/min of de-ionized water into the reactor R1. 3. The de-ionized water is allowed to continue flowing through the reactor until the inlet (Q1-01) and outlet (Q1-02) conductivity values are stable at low levels. Both conductivity values is recorded. 4. Valve V9 is closed and pump P1 is switched off. 5. Valve V11 is opened and pump P2 is switched on. The timer is simultaneously started. 6. Pump P2 flow controller is adjusted to give a constant flow rate of salt solution into the reactor R1 at 700mL/min at F1-02. 7. The salt solution is allowed to flow for 1minute, the timer is reset and restarted. This will start the time at the average pulse input. 8. Valve V11 is closed and pump P2 is switched off. Valve V9 is quickly opened and pump P1 is switch on. 9. By adjusting pump P1 flow controller, the de-ionized water flow rate is always maintained at 700mL/min. 10. The inlet (Q1-01) and outlet (Q1-02) conductivity values are recorded at regular interval of 30 seconds. 11. The conductivity values are recorded until all readings are almost constant and approach stable low level values.
7

RESULTS Experiment 1: Pulse Input in a Turbular Flow Reactor Flow rate Input type = 700 mL/min = De-ionized Water

Time (min)

Conductivity (mS/cm) Inlet Outlet

C(t) Cit

E(t) Ci(t) Ci(t) 0.0000 0.0000 0.0000 0.0000 0.0000 0.0213 0.0000 0.0000 0.2979 0.4255 0.2127 0.0426 0.0000 1.0000 Table 1

tm t*E(t)/

2 (t - tm) 2 * E(t)/ 0.0000 0.0000 0.0000 0.0000 0.0000 0.0556 0.0000 0.0000 1.5466 2.4589 1.8717 0.5287 0.0000 6.4615

s3 (t - tm) 3 * E(t)/ 0.0000 0.0000 0.0000 0.0000 0.0000 0.1378 0.0000 0.0000 5.4021 9.0618 8.5112 2.8549 0.0000 25.9678

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0

0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.1 0.2 0.0 0.1 0.0 0.1 1.4 0.0 2.0 0.0 1.0 0.0 0.2 0.0 0.0 SUMMATION

0.00 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.70 1.00 0.50 0.10 0.00 2.35

0.0000 0.0000 0.0000 0.0000 0.0000 0.0227 0.0000 0.0000 0.5071 0.8148 0.4526 0.0997 0.0000 1.8969

0.45 0.4

Outlet conductivity, Cout(t)

0.35 0.3 0.25 Series1 0.2 0.15 0.1 0.05 0 -0.05 0 1 2 3 4 5 6 7

Time (min)
Graph 1: outlet conductivity against time

0.45 0.4 0.35 0.3 0.25 Series1

E(t)

0.2 0.15 0.1 0.05 0 0 1 2 3 4 5 6 7

-0.05

Time (min)
Graph 2: distribution of exit time, E(t) against time

Experiment 2: Step Change Input in a Turbular Flow Reactor Flow rate Input type = 700 mL/min = De-ionized Water 2 (t - tm) 2 * E(t)/ 0.0000 0.0000 0.0000 0.0000 0.0002 0.0014 0.0024 0.0035 0.0046 0.0058 0.0071 0.0091 0.0108 0.0127 0.0154 0.0176 0.0201 0.0236 0.0264 0.0307 0.0340 0.0391 0.0429 0.0486 0.0548 0.0595 0.0666 0.0718 0.0801 0.0887 s3 (t - tm) 3 * E(t)/ 0.0000 0.0000 0.0000 0.0000 0.0004 0.0036 0.0073 0.0122 0.0183 0.0260 0.0357 0.0499 0.0648 0.0824 0.1074 0.1321 0.1604 0.2005 0.2380 0.2912 0.3396 0.4103 0.4717 0.5590 0.6579 0.7437 0.8655 0.9692 1.1216 1.2862
10

Time (min)

Conductivity (mS/cm) Inlet Outlet

C(t) Cit

E(t) Ci(t) Ci(t) 0.0000 0.0000 0.0000 0.0000 0.0033 0.0140 0.0165 0.0173 0.0173 0.0173 0.0173 0.0182 0.0182 0.0182 0.0190 0.0190 0.0190 0.0198 0.0198 0.0206 0.0206 0.0215 0.0215 0.0223 0.0231 0.0231 0.0239 0.0239 0.0248 0.0256

tm t*E(t)/

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 14.5

0.0 3.5 3.6 3.6 3.6 3.6 3.6 3.6 3.7 3.6 3.6 3.6 3.6 3.7 3.7 3.6 3.7 3.7 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6

0.0 0.0 0.0 0.0 0.4 1.7 2.0 2.1 2.1 2.1 2.1 2.2 2.2 2.2 2.3 2.3 2.3 2.4 2.4 2.5 2.5 2.6 2.6 2.7 2.8 2.8 2.9 2.9 3.0 3.1

0.00 0.00 0.00 0.00 0.20 0.85 1.00 1.05 1.05 1.05 1.05 1.10 1.10 1.10 1.15 1.15 1.15 1.20 1.20 1.25 1.25 1.30 1.30 1.35 1.40 1.40 1.45 1.45 1.50 1.55

0.0000 0.0000 0.0000 0.0000 0.0001 0.0006 0.0008 0.0010 0.0011 0.0013 0.0014 0.0017 0.0018 0.0020 0.0022 0.0024 0.0025 0.0028 0.0029 0.0032 0.0034 0.0037 0.0039 0.0042 0.0046 0.0048 0.0051 0.0053 0.0057 0.0061

15.0 15.5 16.0 16.5 17.0 17.5 18.0 18.5 19.0 19.5 20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5

3.6 3.1 3.6 3.1 3.6 3.1 3.7 3.2 3.6 3.2 3.6 3.2 3.6 3.2 3.6 3.3 3.6 3.4 3.6 3.4 3.6 3.4 3.6 3.4 3.6 3.5 3.6 3.5 3.6 3.5 3.6 3.5 3.6 3.5 3.6 3.5 SUMMATION

1.55 1.55 1.55 1.60 1.60 1.60 1.60 1.65 1.70 1.70 1.70 1.70 1.75 1.75 1.75 1.75 1.75 1.75 60.6

0.0256 0.0256 0.0256 0.0264 0.0264 0.0264 0.0264 0.0272 0.0281 0.0281 0.0281 0.0281 0.0289 0.0289 0.0289 0.0289 0.0289 0.0289 1.0005

0.0063 0.0065 0.0068 0.0072 0.0074 0.0076 0.0078 0.0083 0.0088 0.0090 0.0093 0.0095 0.0100 0.0103 0.0105 0.0107 0.0110 0.0112 0.2328

0.0950 0.1014 0.1081 0.1185 0.1258 0.1333 0.1410 0.1535 0.1672 0.1762 0.1853 0.1947 0.2101 0.2202 0.2306 0.2412 0.2520 0.2631 3.8945

1.4239 1.5711 1.7281 1.9544 2.1375 2.3317 2.5374 2.8381 3.1761 3.4335 3.7044 3.9893 4.4102 4.7328 5.0707 5.4244 5.7941 6.1803 71.2929

11

2 1.8

Outlet conductivity, Cout(t)

1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 -0.2 0 5 10 15 20 25 Series1

Time (min) Graph 1: outlet conductivity against time

0.035 0.03 0.025 0.02

E(t)

0.015 0.01 0.005 0 0 -0.005 5 10 15 20 25

Series1

Time (min)

Graph 2: distribution of exit time, E(t) against time

12

SAMPLE OF CALCULATION ()

Area = (0.10X0.0)+(0.10X0.5) +(0.20X0.5)+(2.0X0.5)+(1.90X0.5)+ (0.40X0.5)+(0.20X0.5) +(0.10X0.5)+(0.10X0.5)+ (0.10X0.5) +(0.10X0.5) Area = 2.35 ()

( )

( )

13

DISCUSSIONS By doing this experiment, we are able to examine the effect of pulse input in a tubular flow reactor. At the end of the experiment, we are also able to construct a residence time distribution (RTD) function for the tubular flow reactor. The experiment was run at flowrate of 700mL/min. The conductivity for the inlet and outlet was recorded from time equal to t0=0 until them both reaching a constant value for itself. In the end, the conductivity we get for the inlet is 0.2mS/cm and meanwhile for the outlet conductivity is 0.1mS/cm. The age of a fluid element is defined as the time it has resided within the reactor. The concept of a fluid element being a small volume relative to the size of the reactor yet sufficiently large to exhibit continuous properties such as density and concentration. Fluid elements may require differing lengths of time to travel through the reactor. The distribution of the exit times, defined as the E(t) curve, is the RTD of the fluid. The outlet conductivity of a tracer species C(t) can be used to define E(t). The value of E(t) is calculated for every single of time that is for each 30seconds until reached 5 minutes where the outlet conductivity reach to its constant value. The residence time distribution we get in the end is 1.00minutes. From the result obtain, there are 2 graphs that needed to be plot. They are graph of outlet conductivity, C(t) against time and graph of distribution of exit times, E(t) against time. From the graph we get, they are just the same with the graphs that are in the theory. The distribution of exit time is depends on the outlet conductivity. In the same time, it shows that residence time distribution is depends on the outlet conductivity. Variance is defined as the average value of the quantity (distance from mean)2. This average is taken over the whole distribution. (The reason for the square is that we would not like values to the left and right of the mean to cancel out). In this experiment, we are needed to determine the value of the second moment (variance), 2. The value for variance we get in this experiment is 6.4615. Skewness is a measure of the asymmetry of the probability distribution of a real-valued random variable. The skewness value can be positive or negative or even undefined. Qualitatively, a negative skew indicates that the tail on the left side of the probability density function is longer than the right side and the bulk of the value lie to the right of the mean. A positive skew indicates that the tail on the right side is longer than the left side and the bulk of the values lie to the left of the mean. A zero value indicates that the values are relatively

14

even distributed on both sides of the mean, typically but not necessarily implying a symmetric distribution.

Figure 4: Graph of negative skewness and positive skewness We are also needed to calculate the value of the third moment (skewness), s3. The value of skewness we get in this experiment is 25.9678. it is definitely a positive value. Therefore, tail on the right side is longer than the left side and the bulk of the values lie to the left of the mean. In this experiment also we insist to calculate the mean residence time, tm. The value we get for the mean residence time is 0.7652 minute.

15

CONCLUSIONS From this experiment, we are able to examine the effect of pulse input in a tubular flow reactor and to construct a residence time distribution (RTD) function for the tubular flow reactor. The conductivity for inlet and outlet after 5 minutes are 0.2mS/cm and 0.1mS/cm. The outlet conductivity, C(t) is then calculated and the value we get is 2.35. The distribution of exit time, E(t) is calculated for each 30 seconds until it reach 5 minutes interval. The sum of E(t) we get is 1.0000 which is the residence time distribution. The mean residence time, tm for this experiment is 0.7652 minute. The variance, 2 and the skewness, s3 are also then calculated. The value we get for 2 is 6.4615and for the s3 is 25.9678. Graphs for outlet conductivity, C(t) against time and distribution of exit time, E(t) against time is plotted. The graphs we get from this experiment are just the same with the graphs in the theory. The value of E(t) is depends on the value of C(t). This experiment was a success.

16

RECOMMENDATIONS There are several recommendations that can be taken in order to get more accurate result that are: 1. The flowrate of fluid in the reactor must constant all the time during the experiment. This is because the flow rate is always reset when we switch on and off the pump. 2. All the flow valves need to be examine and testing need to be done before the experiment is carried out so that all the data needed for the experiment can be obtained. 3. Make sure that only one person doing the reading. This is due to the fluctuation of the inlet and outlet conductivity reading panel. 4. Make sure that certain valve need to be open and closed rapidly, so one person must handle this valve with efficiently to get more accurate reading. 5. And also make sure in the storage tank is always with a solution and not it will be empty. It will cause error the whole experiment when it carried out.

17

REFERENCES 1. Fogler, H.S (2006). Elements of Chemical Reaction Engineering, 4th Edition, New Jersey:Prentice Hall 2. Schmidt, L.D. (2005), The Engineering of Chemical Reactions, 2nd Edition, Oxford University Press, New York . Chapter 8.3.2. 3. P.V. Danckwerts, (1958) The effect of incomplete mixing on homogeneous reactions, Chem. Eng. Sci., 8, pp. 93-99 4. www.ijee.dit.ie/articles/Vol18-6/IJEE1328.pdf at 5.60pm 19 Feb 2011 5. http://caltechbook.library.caltech.edu/274/9/FundChemReaxEngCh8.pdf at 8.10pm at 19 Feb 2011 6. http://www.ugrad.math.ubc.ca/coursedoc/math101/notes/moreApps/moments.html 1.00am 24 Feb 2011 at

18

APPENDICES

Figure 3: Soltec Tubular Flow Reactor instrument

19

Figure 5: Structure of reactor in plug flow reactor

20