EXPERIMENT 2

PLUG FLOW
TUBULAR REACTOR
Introduction
Types of chemical reactors remain a highly discussed in chemical process industries worldwide. The
reactor is the place where chemical reaction takes place. Hence it is arguably the single most
important part of any chemical process design. The design of a reactor must be finely tuned so that its
mechanisms suit the necessities of the process that is to be carried. Depends on the nature of the
materials in both the feed and the products, the reactors may take a wide range forms. Therefore, a full
comprehension of a reactor of particular design as well as its working mechanisms is very much vital to
actually conduct a particular chemical process.
In this experiment, the Plug Flow Tubular Reactor is used as it has been properly designed for
students’ experiment on chemical reactions in liquid phase under isothermal and adiabatic conditions.
Included in the unit is a jacketed plug flow reactor, individual reactant feed tanks and pumps,
temperature sensors and conductivity measuring sensor. By using this unit, students will be capable to
conduct the typical saponification reaction between acetate and sodium hydroxide among the others
reaction.

General Description
 In the form of nylon tubing that has been would spirally on a glass support cylinder.
 The reactor tubing is high temperature and chemical resistance.
 A stirrer motor is mounted on the top of reactor housing frame.
 Stirrer motor is controlled on control panel.
 The inlet for sodium hydroxide and ethyl acetate is provided beside the stirrer motor and the
inlet piping is of the stainless steel.
 The inlet piping after entering the glass support cylinder has been converted into preheat coils
with certain number of turns to increase the residence time of the two chemicals inside the hot
water bath.
 Piping provided with the compression joints at the connection points for proper sealing.
 Reactor coil with reactants is heated by a water bath circulator unit.
 An inlet and outlet line has been provided for the circulation of water into the reactor and water
bath.
 Manual for reactor maintenance, safety and operation along with manuals for various parts in
the reactor is provided.
 Two feeding tanks provided for the reacting chemicals.
 Two dosing pumps have been positioned beside the reactor housing frame for feeding the
liquid into reactor tubing coil.
 Conductivity sensor has been provided to constantly monitor and if necessary control the
conductivity rate of the on-going experiment.
 A probe holder which is connected to the outlet line from the reactor tubing coil in order to
analyse the conductivity of the resulting solutions has been fixed on the reactor housing frame.
 Temperature monitoring and control system has been provided for the logging of water
temperature inside the water bath circulator and the temperature in the product line.
 Temperature transmission to signal conditioners & PC by K-type thermocouples.
 An elaborate control panel has been installed in the frame of reactor to control the equipment in
the reactor and the coordinate the input and the output from the PC.
 Panel designed with the power switch, emergency switch, TIC control switch, water filling,
stirrer and alarm light.
 Panel displays temperature control value and conductivity value.
 A user friendly but detailed software has been custom designed specifically for PFR data
logging.
 Software is loaded completely into PC.
 A CD ROM of the software will be provided to the customer for future reference along with the
appropriate manuals.
 Work sheets for the data acquired are managed and the required graphs between the
constants or values measured are plotted.
Description of Equipment Layout
(1) Reactant Tank
 Size: 450 mm X 300 mm X 360 mm
 Material: Polyvinyl Chloride (PVC)
 Able to contain 2 type of chemical separately
 Install below the reactor

(2) Dosing pump

 Maximum flow rate: 360 ml/min
 Impulse/minute: 118
 Power: 65 W
 Installed beside to the dosing pump 2.

(3) Dosing pump 2

 Maximum Flow Rate: 360 ml/min
 Impulse/min: 118
 Power: 65 W
 Installed the nearest to the reactor housing frame.

(4) Reactor Tubing Coil

 Once the water temperature is higher than desired temperature, solenoid valve will
open automatically to allow water from outside flowing into the water bath circulator for
cooling
(5) Con 10 Conductivity Sensor
 Thread size: ¾ NPT
 Maximum pressure: 1.0 MPa
 Temperature range: 0~100oC
 Used to detect the conductivity of the solutions in the product line.
 Installed above reactor housing frame.

(6) Stirrer
 Speed range: Max. 100 rpm
 Used to mix the water inside glass support cylinder
 Stirrer unit is installed above reactor housing tank and impeller is installed inside the
reactor housing frame.

(7) Glass Support Cylinder

 Size:240 mm X 400 mm
 Material: Stainless steel
 Installed beside both dosing pump

(8) Reactor Housing Frame

 Size: 260 mm X 550 mm
 Material: Stainless steel
 Support: Glass support cylinder and reactor tubing coil
 Installed beside both dosing pump

(9) Overflow tube

 Size: 12 mm X 500 mm
 Used to exhaust the overflow water in the glass cylinder and waterbath circulator
 Installed inside the reactor

(10) Level sensor

 Used to detect and maintain the water level
 Prevent the heater operates in dry condition
 Installed inside the temperature control water bath circulator

(11) Heater
 Power: 240 V
 Maximum temperature: 60oC
 Used to heat the water to reach the desired temperature and maintain the water
temperature
 Installed at the bottom of the water bath circulator

(12) Solenoid valve

 Once the water temperature is higher than desired temperature, solenoid valve will
open automatically to allow water from outside flowing into the water bath circulator for
cooling
(13) Temperature control water bath circulator
 Size: 220 mm X 250 mm X 150 mm
 Material: Stainless steel
 Used to store the water for heating the solutions inside the reactor tubing coil.

(14) Waste tank

 Size: 350 mm X 380 mm X 350 mm
 Material: Polyvinyl chloride (PVC)
 Used to store all solutions coming from reactor
 Install below reactor housing frame.

(15) Air regulator

 Used to regulate the air flowing into the reactor tubing coil for cleaning solutions
remained

(16) Drain valve of reactant tank 1 (V1)

(17) Drain valve of reactant tank 2 (V2)

(18) Drain valve of reactor house tank (V3)

(19) Drain valve of production tank (V4).

(20) Ball valve for air flowing into inlet tubing 1 (V5)

(21) Ball valve for air flowing into inlet tubing 2 (V6)
Electrical Panel Control Description
(1) Temperature Indicator Control (TIC)
 Show the current temperature of water in water bath circulator. (Value in RED colour)
 Set the detailed temperature for the on-going experiment. (Value in YELLOW colour)
a) Press “<<”
b) Press “�” or “�” to set the desired temperature
c) Press “MODE” to save the adjusted temperature
 Unit: Celcius (oC)

(2) Conductivity Monitor

 Show the conductivity value of the solutions inside the reactor tubing coil.
 Unit: mS/cm
(3) Power Switch
 Equipment main power switch
(4) Emergency Stop Button
 Press to cut off the equipment power source
(5) TIC Control Switch
 Switch on/off the heater inside water bath circulator
(6) Water Filling
 Fill up the water inside reactor
(7) Stirrer Switch
 Adjust the stirrer speed for stirring the solutions inside reactor
(8) Alarm Light
 The alarm light would be flashing and ringing when the water level below the level
sensor
Safety Considerations
1. The unit must be operated under the supervision of lab tutors who have been properly trained
to handle the unit.
2. Operation manual supplied with the unit must be carefully read and understood before started
operating the unit.
3. Follow the instruction stated in the operation manual carefully during the experiment.
4. The unit should be in the stable condition without subjected to any shock, sudden impact or
vibration.
5. Always check and rectify any leak.
6. Leaking couplings or fittings should be carefully retightened. Replace any gaskets or seals if
necessary.
7. Do not touch the hot components of the unit.
8. Be careful when handling any chemicals. Wear the gloves if possible.
9. Make sure the system is sufficiently ventilated when working at atmospheric pressure.
10. Only properly trained staffs are allowed to carry out any servicing.
11. Before any servicing, shut down the whole operation and let the system to cool down and be
properly ventilated.
12. Do not operate heater in dry condition.
13. Shut down the unit after used.
14. Stop the experiment and unit immediately when there is any accident happened.
15. Do not set the temperature of heater over limit.
16. After each experiment, drain off any liquids from the reactor and make sure that the reactor and
tubings are cleaned properly. Flush the system with deionized water until no trace of salt is
detected.
17. Dispose all liquids from tanks immediately after experiment. Do not leave any solution or waste
in the tanks over a long period of time.
18. Wipe off any spillage from the unit immediately.
Summary of Theory
Plug Flow Tubular Reactor
This reactor is also known as tubular flow reactor which is usually used in industry complementary to
CSTR. It consists of a cylindrical pipe and is usually operated at steady state. For analytical purposes,
the flow in the system is considered to be highly turbulent and may be modelled by that of a plug flow.
Therefore, there is no radial variation in concentration along the pipe.
In a plug 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 strring prevent complete missing of the fluid in
the tube. Hence, the properties of the flowing stream will vary from one point to another.
In an ideal tubular flow reactor which is called plug flow reactor, specific assumptions are made
regarding the extent of mixing:
(1) No mixing in the axial direction
(2) Complete missing in the radial direction
(3) A uniform velocity profile across the radius
Tubular reactors are one type of flow reactors. It has continuous inflow and outflow of materials. In the
tubular 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 stirring prevent complete mixing of the fluid in the tube.

Rate of reaction and rate law

The rate at which a given chemical reaction proceeds can be expressed in several ways. It can be
expressed either as the rate of disappearance of the reactants, or the rate of formation of products,
In the following reaction,
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷 (1)
A and B are the reactants, while C and D are the products. a,b,c,d are the stoichiometric coefficients for
the respective species.
If species A is considered as the reaction basis, then the rate of reaction can be represented by the rate
of disappearance of A. It is detonated by the symbol –rA. The numerical value of the rate of reaction –rA
is defined as the number of moles of A reacting per unit time per unit volume, and has the typical unit of
mol/dm3.s.
Similarly, the rate of reaction can also be represented by the rate of disappearance of another species,
such as –rB and the rate of formation of a product, such as r C and rD. They can be related in the
following equation:
−𝑟𝐴 −𝑟𝐵 −𝑟𝐶 −𝑟𝐷
= = = (2)
𝑎 𝑏 𝑐 𝑑

The chemical reaction rate is intensive quantity and depends on temperature and concentration. The
reaction rate equation (or rate law) is essentially an algebraic equation involving concentration. It may
be a linear function or concentrations, or may be some other types of algebraic equations. One of the
most common general forms of this dependence is the product of concentration of the individual
reacting species, each of which is raised to a power for example,
 𝛽
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴𝛼 𝐶𝐵 (3)
where
k = rate constant
CA = concentration of A species
CB = concentration of B species
α = stoichiometric coefficient of A
β = stoichiometric coefficient of B
for a given reaction, the particular concentration dependence of the rate law must be determined almost
without exception from experimental observation. Although the functional dependence may be
postulated from theory, experiments are necessary to confirm the proposed form.
The order of a reaction refers to the power to which the concentrations are raised in the reaction rate
law. In equation (3), the reaction is α order with respect to reactant A, and β order with respect to
reactant B, the overall order of the reaction,
𝑛= 𝛼+ 𝛽 (4)
Conversion
Using the reaction shown in equation (1) and taking species A as the basis of calculation, the reaction
expression can be divided through by the stoichiometric coefficient of species A, in order to arrange the
reaction expression in the form,
𝑏 𝑐 𝑑
𝐴+ 𝐵→ 𝐶+ 𝐷 (5)
𝑎 𝑎 𝑎

The expression has now put every quantity on a ‘per mole of A’ basis. A convenient way to quantify
how far the reaction has progressed, or how many moles of products are formed for every mole of A
consumed; is to define a parameter called conversion. The conversion X A is the number of moles of A
that have reacted per mole of A fed to the system,
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝑋𝐴 = (6)
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑓𝑒𝑑

Because the conversion is defined with respect to the basis of calculation (species A), the subscript A
can be eliminated for the sake of brevity and let X= XA.
Mass Balance
In a plug flow reactor, reactants are fed to the reactor at the inlet and the products are removed from
the reactor at the outlet. The reaction takes place within the reactors as the reacting mixtures move
through the pipe. In an ideal plug of reactor the reacting mixture is assumed to move as a plug and its
properties are assumed to be uniformly distributed across the cross section of the reactor.

Differential volume dV

FAo FAF

FA FA+dFaA
Vo
VF

FA = the molar flow rate of A in moles per time

FAo = the molar flow rate of A at the inlet in moles per time
FAf = the molar flow rate of A at the exit in moles per time
Vo = the volumetric flow rate at the inlet in volume per time
Vf = the volumetric flow rate at the exit in volume per time
Design equation for reactant A in the PFR is obtained by writing the mass balance for reactant A over a
differential volume of the reacting mixture dV as follows:

Mass of A entering the volume dV per unit time = mass of A leaving the volume dV per unit time
+ mass A accumulated within the volume dV per unit time + mass of A disappearing by the
reaction within the volume dV per unit time
At steady state, no accumulation takes place. Therefore, at steady state, the above reduces to
𝐹𝐴 𝑀𝐴 = (𝐹𝐴 + 𝑑𝐹𝐴 )𝑀𝐴 + (−𝑟𝐴 )𝑀𝐴 𝑑𝑉 (7)
Where,
FA = the number of moles of A per unit time entering the differential volume dV
(FA + dFA ) = the number of mole of A per unit time leaving the differential volume dV
MA = the molar mass of A
(-rA) = the molar rate at which A is disappearing because of the progression of the reaction

Note that the unit of rA as moles per volume per time and there for rA is multiplied by the molar mass of
A to get the reaction rate in compatible unit for the mass balance given by Equation (7)
Removing MA from Equation (7) and rearranging it, we get the design Equation for reactant A in an
ideal PFR operated at steady-state as follows:
𝑑𝐹𝐴
= 𝑟𝐴 (8)
𝑑𝑣
Working out in terms of the molar flow rate of A, FA:
The volume VPFR is required to reduce the molar flow rate of A in the PFR from F Ao mol/sec at the
entrance of the reactor to FAr mol/sec at the exit of the reactor can be evaluated by integrating Equation
(8) as follows:
𝐹 1 𝐹 1
𝑉𝑃𝐹𝑅 = ∫𝐹 𝐴𝑓 𝑟 𝑑𝑟𝐴 = ∫𝐹 𝐴𝑜 (−𝑟 ) 𝑑𝑟𝐴 (9)
𝐴𝑐 𝐴 𝐴𝑡 𝐴

Where (-rA) should be expressed as a function of FA.

Working out in terms of the concentration of A, CA:
Concentration CA in an ideal PFR is defined as follows:
𝑀𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝐴 𝑎𝑡 𝑐𝑒𝑟𝑡𝑎𝑖𝑛 𝑐𝑟𝑜𝑠𝑠−𝑠𝑒𝑐𝑖𝑜𝑛 𝐹𝐴
𝐶𝐴 = 𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 𝑎𝑡 𝑡ℎ𝑒 𝑐𝑟𝑜𝑠𝑠−𝑠𝑒𝑐𝑡𝑖𝑜𝑛 = (10)
𝑣

Equation (10) gives FA = CA. Substituting which in (8), we get

𝑑(𝐶𝐴 𝑣)
= 𝑟𝐴 (11)
𝑑𝑉

If the volumetric flow rate v is a constant then Equation (11) yield

𝐶 𝑣 𝐶 𝑣
𝑉𝑃𝐹𝑅 = ∫𝐶 𝐴𝑓 𝑟 𝑑𝐶𝐴 = ∫𝐶 𝐴𝑜 𝑟 𝑑𝐶𝐴 (12)
𝐴𝑐 𝐴 𝐴𝑓 𝐴

Where,
CAo = the respective concentration of A at the entrance of the reactor
CAf = the respective concentrations of A at the exit of the reactor
(-rA) should be expressed as a function of CA

Working out in terms of the conversion of A, xA:

Conversion of A in a PFR is defined by
𝐹𝐴𝑜 −𝐹𝐴
𝑥𝐴 = (13)
𝐹𝐴𝑜

Which gives FA = FAo (1-xA). Substituting which in Equation (8), we get

−𝐹𝐴𝑜 𝑑𝑥𝐴
= 𝑟𝐴 (14)
𝑑𝑉

When integrated with conditions xA = 0 at the entrance (where V=0) and xA =xAf at the exit (where V =
VPFR), gives
𝑥 𝐹
𝑉𝑃𝐹𝑅 = ∫0 𝐴𝑓 (−𝑟𝐴𝑜 ) 𝑑𝑥𝐴 (15)
𝐴

XAf = the conversion of A at the exit of the reactor

(-rA) should be expressed as a function of xA
Introduction of Following Experiments
The stoichiometry of the saponification reaction between NaOH and EtOAc is:
NaOH + EtOAc → NaOAc + EtOH
This reaction can be assumed to be second order overall, first order in each reactant, with the following
rate expression:
Rate=k2CNaOHCEtOAc
Where k2 = second order rate constant and CNaOH and CEtOAc are concentrations of NaOH and EtOAc,
respectively. The rate expression has the units [moles/(litre)(time)]. For these experiments, the unit of
time should be minutes.
The apparatus in this experiment is:
1. Plug flow tubular reactor
The apparatus of Black Titration:
1. Conical flask
2. Measuring cylinder
3. pH indicator
4. Beakers
5. Burette
6. Retort stand
7. Stopwatch
8. Droplet
Chemicals to be used are:
1. 0.1 M Sodium Hydroxide, NaOH
2. 0.1 M Ethyl Acetate, Et(Ac)
3. 0.1 M Hydrochloric Acid, HCL (Optional; for titration)
Standard Operation Procedures
General Start-up Procedures
1. Prepare the following solutions:
a) 15 litre of sodium hydroxide, NaOH (0.1M) in reactant tank 1.
b) 15 litre of ethyl acetate, Et(Ac) (0.1M) in reactant tank 2.
2. Ensure that all valves are initially closed.
3. Turn on the power for the control panel.
4. Ensure there is no any liquid inside the reactor tubing. Otherwise, open valve V 5 and V6 and
adjust the air regular as small as possible to pump the air into it as long as there is enough to
clear the remained solutions inside the reactor tubing before closing the valve V5 and V6 again.
5. Connect the plastic water hose between water inlet solenoid valve and tap water which is open
to HALF only.
6. Set the desired temperature for the following experiment on the Temperature Indicator Control
(TIC) panel.
7. Turn the TIC switch and keep pushing the water filling button (green coloured button) to fill up
the water into the reactor until just below the overflow tube.
8. Switch on the stirrer to 100 rpm.
9. Switch on the computer and click the corresponding software.
10. Switch on pump P1 and P2 and adjust both pump to obtain highest possible flow rate into the
reactor by keying in the flow rare value into both black of pumps P1 (360 ml/min) and P2(390
ml/min) into the computer and run it. Switch off them after the chemicals coming into the
reactor tubing coil.
11. The unit is now ready for experiment.

General Shut-Down Procedures

1. Set the temperature lower than that during experiment on the TIC.
2. Keep the cooling water to continue flowing.
3. Switch off pumps P1, P2. Switch off the stirrer.
4. Switch off heater once the reactor cool down to room temperature.
5. Turn off the power for the control panel.
6. Open valve V5 and V6.
7. Open disposal valve V3 to drain any liquid from reactor into waste tank.
8. Keep the solutions for subsequent experiment. Otherwise, open valves V 4 to drain all solutions
from waste tank. And also, open valves V1 and V2 to drain the remained chemicals from
reactant tanks to barrels for storage respectively.
Experimental Procedures

i. Preparation of Calibration Curve for Conductivity vs Conversion

The reaction to be studied is the saponification reaction of ethyl acetate, Et(Ac) and sodium hydroxide,
NaOH. Since this is the second order reaction, the rate of reaction depends on both concentration of
Et(Ac) and NaOH. However, for analysis purposes, the reaction will be carried out by using equimolar
feeds of Et(Ac) and NaOH solutions with the same initial concentrations. This ensures that both
concentrations are similar throughout the reaction.
NaOH + Et(Ac) → Na(Ac) + EtOH
The following procedures will calibrate the conductivity measurements of conversion values for the
reaction between 0.1 M ethyl acetate 0.1 M sodium hydroxide:

Procedures:
1. Prepare the following solutions:
a. 1 litre of sodium hydroxide, NaOH (0.1M)
b. 1 litre of sodium acetate, Na(Ac) (0.1M)
2. Determine the conductivity and NaOH concentration for each conversion values by mixing the
following solution:
a. 0% conversion: 100mL NaOH
b. 25% conversion: 75mL NaOH +25mL Na(Ac)
c. 50% conversion: 50mL NaOH +50mL Na(Ac)
d. 75% conversion: 25mL NaOH +75mL Na(Ac)
e. 100% conversion: 100mL Na(Ac)

Analysis and Discussion:

1. Record all data in the sample table in Appendix A.
2. Plot the calibration curve of conductivity vs conversion. Determine the slope and y-axis
intercept.
 ii. Experiment: Saponification of Et(Ac) and NaOH in Plug Flow Reactor

Title: Determine the effects of residence time on the saponification of NaOH and EtOAc by using
Plug Flow Reactor.

Objective
1. To carry out a saponification reaction between sodium hydroxide (NaOH) and ethyl acetate
(Et(Ac)) in a Plug Flow reactor (PFR).
2. To measure the conversion of ethyl acetate in saponification as a function of design
parameters in a PFR.
3. To determine the reaction rate constant and the rate of reaction of saponification reaction in a
PFR.
4. To observe the effect of residence time on conversion of ethyl acetate.

Procedure
1. Perform the general start-up procedures as in Standard Operation Procedures.
2. Set the temperatures as 30oC on Temperature Indicator Control (TIC).
3. To begin a plug flow reaction experiment, key in the flow rate of 50 ml/min to both blank of
pumps P1 and P2 into the computer and run it. Ensure both flow rates are the same. Record
the flow rate.
4. Start pump 1 and 2 at the same time before starting the timer immediately. (Computer: adjust
the Set Time Record as 60s and click “Start Record”)
5. After 3 minutes, start monitoring the outlet conductivity value until it does not change over time.
This is to ensure that the reactor reaches the steady state. (You can records the outlet
conductivity value at the 5th minute if the value is still not stable).
6. Record the outlet conductivity value. (You can just start monitoring and recording the outlet
conductivity value after 2-3 minutes in order to make the solution remained inside the reactor
tubing coil during previous experiment has been cleared out).
7. Calculate the concentration of NaOH exiting the reactor and extent of conversion from the
calibration curve.
8. Optional. Collect 150 mL of sample near the opening of production line. Carry out the back
titration procedure manually to determine the concentration of NaOH in the reactor and extent
of conversion.
9. Repeat the experiment from step 2 to 8 for different residence times by increasing the feed flow
rates of NaOH and Et(Ac) to about 100, 150, 200, 250 and 300 mL/min. Make sure flow rates
of both pumps to be equal.
10. Perform the general shut-down procedures as in Standard Operation Procedures.