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Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

1.0 Title of Experiment


Effect of Residence Time for Hydrolysis Reaction of Ethyl Acetate in Tubular Flow Reactor
2.0

Objective

To carry out a hydrolysis reaction of EtAC in a TFR.


To determine the reaction rate constant.
To determine the effect of residence time on the conversion in a TFR.

3.0

Introduction

Catalytic Tubular Reactor has been designed for experiments on chemical reactions in liquid phase
under isothermal and adiabatic conditions. The unit comes complete with a jacketed tubular reactor;
reactant feed tank and pump, temperature sensors and conductivity measuring sensors. The reactor will
enable students to conduct the acid-catalyzed liquid-phase hydrolysis of ethyl acetate (EtAC) to ethanol
(EtOH) and acetic acid (HAc), using an immobilized anion ion-exchange resin as catalyst:
CH3COOC2H5 + H2O CH3COOH + C2H5OH
The tubular flow reactor (TFR) (sometimes called plug flow reactor (PFR)) is also commonly used in
industry in addition to the CSTR and batch reactor. It consists of a cylindrical pipe and is normally
operated at steady state. For analysis purposes, the flow in the system is considered to be highly turbulent
and may be modeled by that of plug flow. Thus, there is no radial variation in concentration along the
pipe. In the tubular reactor, the reactants are continually consumed as they flow down the length of the
reactor. In modeling the tubular reactor, the concentration is assumed to vary continuously in the axial
direction through the reactor. Consequently, the reaction rate, which is a function of concentration for all
but zero order reactions, will also vary axially.

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FKKSA/DKK2771/Module/Rev01/29/08/12

Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

FA(y)

FA(y + y)

FA0
Figure 1: Process flow diagram for the catalytic tubular reactor unit.

Figure 2: Balance on the Tubular flow reactor (TFR)

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FKKSA/DKK2771/Module/Rev01/29/08/12

FA

Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

To develop the TFR design equation, the reactor volume shall be divided into a number of subvolumes
so that within each subvolume V, the reaction may be considered spatially uniform. Assuming that the
subvolume is located a distance y from the entrance of the reactor, then FA(y) is the molar flow rate of A
into volume V and FA(y + y) is the molar flow rate of A out of the volume. In a spatially uniform
subvolume V,

rA dV rA V

(1)

For a tubular reactor at steady state, the general mole balance is reduced to,
dN A
dt

FA ( y ) FA ( y y ) rA V

(2)

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, V is the product of the crosssectional area, A of the reactor and the reactor length, y.
V Ay

(3)

Substituting Equation (3) into Equation (2) yields,


FA ( y y ) FA ( y )
ArA
y

(4)

Taking the limit as y approaches zero,


dF
FA ( y y ) FA ( y )
A ArA

y 0
y
dy

lim

(5)

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,
dFA
rA
dV

(6)

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FKKSA/DKK2771/Module/Rev01/29/08/12

Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

Note that for a reactor in which the cross-sectional area, A varies along the length of the reactor, the
design equation remains unchanged. This means that the extent of reaction in a plug flow reactor does
not depend on its shape, but only on its total volume.
If FA0 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 [FA0X]. The molar feed rate of A to the
system minus the rate of reaction of A within the system equals the molar flow rate of A leaving the
system, FA . This is shown in mathematical form to be,

FA

FA 0 FA 0 X

FA 0 (1 X )

The entering molar flow rate FA0 is just the product of the entering concentration
v
volumetric flow rate 0 ,

FA 0

C A0v 0

(7)

C A 0 and the entering

(8)

Combining Equation [4-7] and Equation [4-6] yields the design equation with a conversion term for the
TFR,
FA 0

dX
rA
dV

(9)

Rearranging and integrating Equation 9 with the limit V = 0 when X = 0, we obtain the plug-flow
reactor volume necessary to achieve a specified conversion X,
V FA 0

X
0

dX
rA

(10)

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FKKSA/DKK2771/Module/Rev01/29/08/12

Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

4.0

Experimental Procedure

4.1

Equipment
1. TFR

2. Beakers

3. Measuring Cylinders

4. Stop Watch

5. Ethyl Acetate
4.3

4.4

General Start-Up Procedures


1.

Ensure that all valves are initially closed.

2.

Prepare a 20 liter of ethyl acetate solution by adding 800 mL of ethyl acetate into 19.2 L of
deionised water.

3.

Turn on the power for the control panel.

4.

Connect the water de-ionizer to the laboratory water supply. Fill up feed tank B1 with the
19.2 L of de-ionized water. Then add in 800 mL of ethyl acetate to prepare the feed solution.

5.

The unit is now ready for experiment.

General Shut-Down Procedures


1.

Switch off the pump.

2.

Switch off the heater.

3.

Keep the cooling water circulating through the reactor while the stirrer motor is running to
allow the water jacket to cool down to room temperature.

4.

If the equipment is not going to be used for long period of time, drain all liquid from the unit.
Rinse the feed tanks with clean water.

5.

4.5

Turn off the power for the control panel.

Experiment Procedures
1.

Perform the general start-up procedures.

2.

Open valves V1 and V4.

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FKKSA/DKK2771/Module/Rev01/29/08/12

Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

3.

Allow EtAC solution to enter the tubular reactor.

4.

Adjust the flow rate controller to give a constant flow rate of 40 mL/min.

5.

Start monitoring the inlet (QI-01) and outlet (QI-02) conductivity values until they do not
change over time. This is to ensure that the reactor has reached steady state.

6.

Record both inlet and outlet steady state conductivity values. Find the concentration of HAC
exiting the reactor and extent of conversion from the calibration curve.

7.

Repeat the experiment (steps 4 to 6) for different residence times by changing the feed flow
rates of EtAC to 30 and 40 mL/min.

5.0

Data Collection
1.
2.

Record data using the Table 1


Plot a graph of conversion vs. residence time. The reactors residence time is defined as the
reactor volume divided by the total feed flow rates.

Residence time,

3.

VTFR
v0

For a first order reaction with initial reactant concentration

C A 0 , the rate law is shown to be:

rA kCA kC A0 (1 X )
rA FA 0
VTFR

where: X

v0
k

dX
dX
v 0C A 0
dV
dV

X
0

v
dX
1
0 ln
(1 X ) k 1 X

= extent of conversion

C A = exit concentration of reactant EtAC [M]

v 0 = inlet flow rate of solution [mL/min]

C A 0 = inlet concentration of reactant in the reactor [M]

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FKKSA/DKK2771/Module/Rev01/29/08/12

Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

Reactor volume

= _____ L

Concentration of EtAC in feed vessel

_____ M

Table 1

No.

Flow rate of
Residence
EtAC
time, (min)
(mL/min)

Inlet
conductivity
(mS/cm)

Outlet
conductivity
(mS/cm)

Exit
concentration of
HAc (M)

Conversion,
X (%)

1
2
3
4
5
6
7
8
9
10

4. For constant TFR volume, flow rate and initial concentrations, the reaction rate
constant is,

v0
1
ln
VTFR 1 X

5. For different reactor residence times, calculate the value of the reaction rate constant, k
and the rate of reaction, r A .

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FKKSA/DKK2771/Module/Rev01/29/08/12

Module 05:

DKK2771 Chemical Reaction Engineering Laboratory

Appendix A : SAMPLE CALIBRATION CURVE


AT 30C

Calibration Curve at 30C


2.50
f(x) = - 0x^6 + 0.01x^5 - 0.12x^4 + 0.67x^3 - 2.06x^2 + 3.29x
2.00R = 1
1.50

Conductivity (mS/cm)

1.00

0.50

0.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

Concentration (mol/liter)

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