ABSTRACT

In tubular flow reactor 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. The equipment is set up and to run the experiment. In pulse input experiment, let the deionized water to flow continuously through the reactor until the inlet and outlet conductivity values are stable at low levels. We need to maintain flow rate of deionized water at approximately 700mL/min. Then, let the salt solution to flow for 1 minute. After that, both the inlet and outlet conductivity values at the regular intervals of 30 seconds are recorded. Both conductivity values for inlet and outlet after 5 minutes are 0. 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 RTD value is 0.9936. The values of mean residence time, variance and the skewness are 2.3687, 0.0579 and 0.6967 respectively. 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).

The step change experiment, our aims are to examine the effect of step change in tubular flow reactor and we have constructed a residence time distribution (RTD) function for the tubular flow reactor. Only the deionized water is allowed to continue flowing until the inlet and outlet conductivity values are stable at low levels. We continued record the conductivity values until all readings are almost constant. The values of conductivity is at the peak; 2.7 (mS/cm). RTD value is 0.0885. At this time, the values of mean residence time, variance and the skewness are 0.0319, 0.1735 and 0.9388 respectively.

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 non-ideal 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 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

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

THEORY

From figure above let say, v0= FAo To develop the tubular flow reactor (TFR) design equation, then reactor volume shall be divided into a number of subvolumes so that within each subvolume , the

reaction may be considered spatially uniform. Assuming that subvolume is located a distance y from the entrance of the reactor, then FA(y) is the molar flow rate of A into volume and FA(y + ) is the molar flow rate of A out of the volume. In spatially

uniform subvolume

For tubular reactor at steady state, the general mole balance is reduced to,

FA(y) - FA(y +

)+r

=0

eq(1)

In the above expression, rA is an indirect function of y.That is, rA is a function of reactant concentration, which is a function of the position, y down the reactor. The volume, is the product of the cross- sectional area, A of the reactor and the reactor length , y. eq(2) Substituting equation (2) into equation (1) yields,

( )

] = -ArA

Taking the limit as y approaches zero, ( ) ( )

It is usually most convenient to have the reactor volume, V rather than the reactor length, y as the independent variable. Accordingly, the variables Ady can be changed to dV to obtain this form of the design equation for a TFR. Note that for reactor a reactor in which the cross- sectional in which the crosssectional area, A varies along the length of the reactor, the design equation remains unchanged. This means that extent of reaction in a plug flow reactor does not depend on its shape, but only on its total volume. If FAO is the molar flow rate of species A fed to a system operated at steady state, the molar flow rate at which species A is reacting within the entire system will be [FAOX].The molar feed rate of A to the system minus the rate of reaction of within the system equals the molar flow rate of A leaving the system, F A. This shown in mathematical form to be, FA.= FAO - FAOX = FAO (1-X) The entering molar flow rate FAO is just the product of the entering concentration CAO and the entering volumetric flow rate Vo FAO = CAOVo Combining above equations yields the design equation with conversion term for the TFR, FAO Rearranging and integrating above equation with the limit V=0 and X=0, we obtain the plug flow reactor volume necessary to achieve a specified conversion X,

V=FAO The residence time distribution (RTD) of reactor is a characteristic of the mixing that occurs in the chemical reactor. There is no axial mixing in a plug flow reactor (PFR), and this omission is reflected in the RTD which is exhibited by this class of reactors. The continuous stirred tank reactor (CSTR) is thoroughly mixed and possesses a far different kind of RTD than the PFR. Not all RTDs are unique to a particular reactor type; markedly different reactors can display identical RTDs. Nevertheless, the RTD exhibited by a given reactor yields distinctive clues to the type of mixing occurring within it and is one of the most informative characterizations of the reactor. The RTD is determined experimentally by injecting an inert chemical called a tracer into the reactor at some time t=0 and then measuring the tracer concentration, C in the effluent stream as function of time. The two most methods of injection are pulse input and step input. Pulse input In a 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. The outlet concentration is then measured as function of time. The effluent concentration vs. time is referred to as C(t) curve in RTD analysis. Consider the injection of a tracer pulse for single input and single output system in which only flow (no dispersion) carries the tracer material across system boundaries. For a small time increment t (sufficiently small so that the concentration of tracer is essentially constant during that time period), the amount of tracer C(t) exiting between time t and (t + t) is, N= C(t)vteq(3) where v is the effluent volumetric flow rate. In other words, N is the amount of material that has spent an amount of time between t and (t + t) in the reactor. If it is divided by total amount of material that was injected into the reactor, No

( )

which represent the fraction of the material that has residence time in the reactor between time t and (t + t). For pulse injection, E(t) =
( )

eq(4) ( )

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 fluids elements have spent in the reactor.

If No is not known directly, it can be obtained from the outlet concentration measurement by summing up all the amounts of materials, and infinity. Equation (3) can be written in differential form, dN= C(t)vdteq (5) Integrating equation (5) gives No = ( ) between time t = 0

The volumetric flow rate, v is usually constant, so that by substituting eq(5) into eq(4) we can define E(t) as, E(t) =
( ) ( )

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

APPARATUS SOLTEQ Tubular Reactor (Model: BP 101-B), Conical flask, Calibration meter, Sodium hydroxide, NaOH (0.1M) Sodium Acetate, Na(Ac) (0.1M) Deionised water, H2O

METHODOLOGY

1.1

General Start-Up procedures for Experiments 1 & 2 1. Ensured that all valves are initially closed except valve V7. 2. A 20 litre of salt solution was prepared. 3. The tank B2 was filled with the NaCl solution 4. The power for the control panel was turned on 5. The water deionizer was connected to the water supply. Valve V3 was opened and tank B1 was filled up with the de-ionized water. 6. Valves V2 and V10 was opened. Switched off pump P1. P1 flow controller was adjusted to obtain a flow rate of approximately 700 mml/min at flow meter F1-01. 7. Valves V6 and V12 was opened. Switched on pump P2. P2 flow controller was adjusted to obtain a flow rate of approximately 700ml/min. Valves V12 was closed and pump P2 was switched off.

1.2

Experiment 1: Pulse Input in a Tubular Flow Reactor

1. The general start-up procedures were performed as in 6.1. 2. Valve V9 was opened and pump P1 was on. 3. Pump P1 flow controller was adjusted to give a constant flow rate of deionized water into the reactor R1 at approximately 700 ml/min at F1-01.

4. The de-ionized water was continued to flow through the reactor until the inlet (QI-01) and outlet (QI-02) conductivity values are 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 start 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. The salt solution was flowed for 1 minute, the timer was reset and restart. 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 opened quickly and pump P1 was switched on. 10. The de-ionized water flow rate was maintained at 700 ml/min by adjusting p1 flow controller. 11. The inlet (QI-01) and outlet (QI-02) conductivity values was recorded at regular of 30 seconds. 12. The conductivity values were continued to record until all reading s are almost constant and approach the stable low level values.

1.3

Experiment 2 : Step Change Input in a Tubular Flow Reactor

1. The general start-up procedures were performed as in 6.1. 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 deionized water into the reactor R1 at approximately 700ml/min at FI-01. 4. The de-ionized water was continued to flow through the reactor until the inlet (QI-01) and outlet (QI-02) conductivity values are stable at low levels. 5. Valve V9 was closed and pump P1 was switched on. 6. Valve V11 was opened and pump P2 was switched. The timer was started simultaneously. 7. Both inlet (QI-01) and outlet (QI-02) conductivity values was recorded at regular intervals of 30 seconds. 8. The conductivity values was recorded until all reading are almost constant.

RESULTS

Flow rate = 700 ml/min Input type = Salt solution

Experiment 1: Pulse Input in a Tubular Flow Reactor Time (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 Inlet 0.0 0.8 0.3 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Conductivity (mS/cm) Outlet 0.0 0.0 0.0 0.0 2.1 2.6 1.0 0.1 0.0 0.0 0.0

Conductivity (ms/cm) against Time (min)

3 2.5 2.6 2.1

Conductivity (mS/cm)

2 1.5 1 0.5 0 0 -0.5 0 0 1 0

0.1 2 3

0 4

0 5 6

Time (min)

Graph 1: conductivity for pulse input experiment

E (t) agains time (min)

1.2 1 0.8 0.6 0.4 0.2 0 0 -0.2 0.5 1 1.5 2 2.5 3 3.5 4

E (t)

time (min)

Graph 2 : RTD grapgh for pulse input experiment

1.4

Experiment 2 : Step Change Input in a Tubular Flow Reactor

Time (min) 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 0.0 4.3 4.3 4.3 4.3 4.2 4.2 4.2 4.2 4.1 4.1 4.1 4.1 4.0 Inlet

Conductivity (mS/cm) Outlet 0.0 0.0 1.6 2.4 2.6 2.6 2.7 2.6 2.7 2.6 2.6 2.7 2.7 2.7

Conductivity (ms/cm) Vs Time (min)

3 2.5 2.6 2.4 2.6 2.7 2.6 2.7 2.6 2.6 2.7 2.7 2.7

Conductivity (mS/cm)

2 1.5 1 0.5 0 0 -0.5 0 1 2 3 4 5 6 7 1.6

Time (min)

Grapgh 3: conductivity of step change experiment

E (t) Vs time (cm)

0.1

0.08

0.06

E(t)

0.04

0.02

0 0 -0.02 1 2 3 4 5 6 7

time (min)

Graph 4: RTD for step change experiment

SAMPLE OF CALCULATIONS Pulse input

( )

( )

( )

( )

( )

( )

( ))

( )

( )

Example of calculation: ( ) ( ) ( )

t=0, C(t)=0 ( ) t=0.5, C(t)=0 ( ) t=1.0, C(t)=0 ( ) t=1.5, C(t)=0

( ) t=2.0, C(t)=2.1 ( ) t=2.5, C(t)=2.6 ( ) t=3.0, C(t)=1.0 ( ) t=3.5, C(t)=0.1 ( )

time (min) 0 0.5 1 1.5 2 2.5 3 3.5 4

Outlet conductivity E(t) (mS/cm) 0 0 0 0 2.1 2.6 1.0 0.1 0 0 0 0 0 0.8025 0.9936 0.3822 0.0382 0 0 0 0 0 1.6050 2.4840 1.1466 0.1337 0 0 0 0 0 3.2100 6.2100 3.4398 0.4680 0 0 0 0 0 6.4200 15.5250 10.3194 1.6378 0 tE(t) t^2 E(t) t^3 E(t)

Mean residence time, ( ) ( ) ( ( (

) (

( ) ( ) ) ( )) 2.0891

( ))

Second moment, Variance, 2= ( ( ) ( ) ( ( ( ) ( ( ) )

) (

( ) )) = 4.7833

( ))

2= (4.7833+0.8853)-

= 0.0579 min2

Third moment, Skewness, s3= S3=( ( ) ( ) ( ( ) ( )

( ( ) )

( ) ( ))

11.1750

( )

Step change Time (min) Conductivity (mS/cm) Cit Ci(t)/ Ci(t) (t - tm) 2 * E(t)/ Ci(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 TOTAL 0.0 4.3 4.3 4.3 4.3 4.2 4.2 4.2 4.2 4.1 4.1 4.1 4.1 4.0 0.0 0.0 1.6 2.4 2.6 2.6 2.7 2.6 2.7 2.6 2.6 2.7 2.7 2.7 0.0 0.0 0.80 1.20 1.30 1.30 1.35 1.30 1.35 1.30 1.30 1.35 1.35 1.35 15.25 0.0 0.0 0.0525 0.0787 0.0852 0.0852 0.0885 0.0852 0.0885 0.0852 0.0852 0.0885 0.0885 0.0885 0.0 0.0 0.0034 0.0077 0.0112 0.0140 0.0174 0.0196 0.0232 0.0251 0.0280 0.0319 0.0348 0.0377 0.0 0.0 0.0034 0.0115 0.0221 0.0345 0.0516 0.0677 0.0918 0.1119 0.1381 0.1735 0.2065 0.2424 (t - tm) 3 * E(t)/ Ci(t) 0.0 0.0 0.0034 0.0170 0.0432 0.0837 0.1540 0.2355 0.3650 0.5006 0.6867 0.9488 1.2318 1.5662 C(t) E(t) tm 2 s3

Inlet

Outlet

t*E(t)/ Ci(t)

Sample of calculation ()

Area = (0.00X0.00) + (0.00X0.50) + (1.6X0.50) + (2.4X0.50) + (2.6X0.50) + (2.6X0.50) + (2.70X0.50) + (2.60X0.50) + (2.70X0.50) + (2.60X0.50) + (2.60X0.50) + (2.7X0.50) + (2.7X0.50) + (2.70X0.50) Area = 15.25 cm2 Example of calculation at t=0.00min ()

( )

( )

Example of calculation at t=3.5 ()

( )

0.0677 ( ) ( )

0.2355

DISCUSSIONS In this experiment, the effect of pulse input in a tubular flow reactor is examined. A Residence time distribution (RTD) in function for the tubular flow reactor also has been constructed at the end of the experiment. The experiment was run at a flow rate of 700mL/min. The conductivity at the inlet and outlet for both experiment was recorded until both reaching a constant values of conductivity. In the first experiment, pulse input effect is examined. The graph of the outlet conductivity against time is plotted. Based on the graph, at minutes 2.5, the conductivity is at the higher peak and decreases until minutes 3.5, where the conductivity is zero and kept constant until minutes 5. After that, in order to get the residence time, a graph of E(t) against time(min) is plotted to get the residence time distribution. 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 curve of this RTD is affected by conductivity values. It can be seen that in this graph, the highest value of the residence time is at 2.5 minutes which is 0.9936. The values of mean residence time, variance and the skewness are 2.3687, 0.0579 and 0.6967 respectively. For the second experiment, the effect of the step change input in tubular flow reactor is analysed. Again, in the second experiment, both graphs of conductivity and RTD were plotted. In the first graph, it showed that at minutes 5.5, the values of conductivity is at the peak; 2.7 (mS/cm) and started to kept constant. Second graph is RTD graph. It has been analysed at the minutes 5.5, the values start to constant at 0.0885. At this time, the values of mean residence time, variance and the skewness are 0.0319, 0.1735 and 0.9388 respectively.

CONCLUSION From both experiments, the effect of pulse input and step change in a tubular flow reactor and to construct a residence time distribution (RTD) function for the tubular flow reactor has been analysed. In the pulse input experiment, the conductivity reach zero at minutes 4 which similar to the theoretical value. The RTD value is 0.9936. The values of mean residence time, variance and the skewness are 2.3687, 0.0579 and 0.6967 respectively. For the step change experiment, at minutes 5.5, the values of conductivity is the highest which is 2.7 (mS/cm) and started to kept constant. The value of RTD is 0.0885. At this time, the values of mean residence time, variance and the skewness are 0.0319, 0.1735 and 0.9388 respectively.

RECOMMENDATIONS A few adjustments can be made in order to get more accurate result. The recommendations are:
1. Please consult with technician on how to run the equipment before carry out the experiment. 2. For obtained more accurate results, run several trials on tubular flow reactor so we can take the average value from each different molar rates.

3. All of the valve must be fully open to ensure constant flow.

REFFERENCES Robert H.Perry, Don W.Green, Perrys Chemical Engineers Handbook, McGraw Hill, 1998. H. Scott Fogler, Elements of Chemical Reaction Engineering, 4th Edition,

Pearson Education International, 2006. http://solve.nitk.ac.in/dmdocuments/Chemical/theory_plugflow.pdf at 12pm 8

October 2013 http://faculty.kfupm.edu.sa/CHE/aashaikh/papers/LFRNew.pdf retrieved at

3pm at 9 October 2013

APPENDICES