EKC 493 Chemical Engineering Laboratory III (Unit Operation Lab)

EXPERIMENT B1 PLUG FLOW REACTOR (PFR) 1.1 Objectives: Study liquid phase saponification reaction kinetics in a PFR, Tubular Reactor. Determine reaction rate data of saponification reaction at given temperature, by measuring conversion against reaction time data. Evaluate the reaction rate constant for liquid phase saponification reaction between ethyl acetate and sodium hydroxide from the rate data, obtained at different operating conditions such as temperature and retention time at given conversion. Determine activation energy of the reaction from the rate constant obtained at different temperatures.

1.2 Introduction: Plug flow reactor is an ideal tubular reactor with laminar flow behavior. The reactants pass through the tube; the reactants are converted progressively along the length of reactor. The reactants are continuously consumed and the product is formed as the flow preceded the length of the reactor. There is no radial variation in concentration. Consequently, the reaction rate, which is function of concentration for all but zero-order reactions, will also vary axially.

1.3 Theory: Since in plug flow reactor the composition of fluid changes through the length of reactor, material balance is carried out in an element of volume, dV. The material balance can be simplified as follows:

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EKC 493 Chemical Engineering Laboratory III (Unit Operation Lab)

At steady state condition, the rate of accumulation is zero, therefore the right hand side of the following equation (dNA/dt = 0), must be zero

(1)

CAo FAo XAo= 0 vo

FA XA

FA+dFA XA+dXA

CAf FAf XAf= 0 vf

Figure 1.1: Plug flow reactor with inlet and outlet conditions, also with inlet and outlet of differential volume Given -rA as a function of conversion,-rA=f(X), one can size any type of reactor. We do this by constructing a Levenspiel plot. Here we plot either or as a function of

XA. For

vs. XA, the volume of a PFR can be represented as the shaded areas in the

Levenspiel Plots shown below in Figure 1.2 comparing PFR as area under the curve and CSTR the shaded area of the whole rectangle:

Figure 1.2: Plot of inverse rate vs conversion. The shaded area represented the volume of ideal reactors

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(2) Figure 1.3. Graphical solution for calculation of PFR volume

At Steady State : FA0 FAf + ( rA )(dV ) = 0 dFA = d [ FAo (1 X A )] = FAo dX A Material Balance In differential volume FA = ( FA + dFA ) + ( rA )(dV )

(3)

Replace dFA in the material balance, separate variables, then solve the differential equation by integration:
FAo dX A = ( rA )dV
V X Af

dV FAo = 0

dX A rA
X Af

(4)

V = = FAo C Ao

dX A rA dX A rA

X Af

(5)

= C Ao

Note : C Ao = where:

A C A ,t o

CA,t = concentration of reactant A in feed tank vA = volumetric flow rate of A vo =overall volumetric flow rate

= space time.
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EKC 493 Chemical Engineering Laboratory III (Unit Operation Lab)

For constant volume, constant density, XA = 1-(CA/CAo) and dXA = -dCA/CAo P = - dCA/ (- rA) . Figure 1.4 shows the graphical representation of batch reactor equation (6) (6)

1 ( rA )

Area = P

CA

CA0

CA

Figure 1.4: Graphical representation of the performance equations for PFR. The saponification of ethyl acetate is shown in the following reaction: First Order Reaction
CH 3 COOC 2 H 5 + NaOH A + B C
k

CH 3 COONa + C 2 H 5 OH + D

C B = C Bo (1 X B ) = C Bo C Ao X A = C Ao (M X A ) Define molar ratio of M = C Bo C Ao

2

C A = C Ao (1 X A )

rA = kC A C B

(7)

rA = kC Ao (1 X A )C Ao (M X A ) = k (C Ao ) (1 X A )( M X A )

Now plug in the rate equation into PFR design equation 5.

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EKC 493 Chemical Engineering Laboratory III (Unit Operation Lab)

p = C Ao

X Af

dX A kC Ao (1 X A )( M X A ) dX A (1 X A )( M X A )
2

kC Ao =

X Af

(8)

For M 1 kC Ao = M X Af 1 ln M 1 M (1 X Af )
M X Af M (1 X Af ) vs , the slop of the equation will be kCAo(M-1). Since the M is

Plot ln

defined the rate constant can be calculated from the slope of this plot. For M=1 -rA= kCA2 = kCAo2 (1-XA) (9)

= C Ao
kC Ao =

dX A kC Ao (1 X A ) 2 X Af
2

(10)

1 X Af

Reaction rate constant is almost always strongly dependent on temperature:

Arrhenius Law

k (T) = AeE / RT

(11)

Where A = pre-exponential factor of frequency factor E = activation energy, kJ / mole or cal / mol T = absolute temperature, K R = gas constant. k = reaction rate constant

1.4 Part A: Tubular Flow Reaction Kinetics 1.4.1 Introduction:

By studying the saponification reaction of ethyl acetate and sodium hydroxide to form sodium acetate in a tubular flow reactor, students may study the reaction kinetics of a

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plug flow reactor and then compare the predicted results and experimental fraction of conversion. A process flow diagram of the reactor is shown in Figure 1.5 and a view of the experimental unit is shown in Figure 1.6. The Lasera LS-TFR 300 has a total reactor volume of approximately 250 ml.

1.4.2 Reactants Preparation Procedures:

1. 2.

Prepare 0.1 M NaOH and 0.1 M Ethyl acetate solutions in two separate 20-liter feed tanks. Recheck the concentration of your 0.1 M NaOH solution by titration of a small amount of it with standard 0.1 M HCl using phenolphthalein as indicator. Then concentration of ethyl acetate solution, on the other hand, is evaluated in the following manner. First, add enough 0.1 M NaOH solution to a sample of the feed solution such that the 0.1 M NaOH solution is in excess to ensure all of the ethyl acetate is reacted. Let us have this mixture to react over night. On the following day, determine the amount of un-reacted NaOH ( the excess sodium hydroxide we used) by direct titration (back titration with acid) with standard 0.1 M HCl. Record the ethyl acetate real concentration.

3.

Prepare 1 liter of quenching solutions of 0.25 M HCl and l liter of 0.1 M NaOH for back titration.

1.4.3 Tubular Flow Reactor Experimental Procedures:

1.

Start pumping the 0.1 M ethyl acetate and the 0.1 M NaOH simultaneously. Adjust the pump to give a minimum flow rate (flow meter reading: 10). Wait for at least 10 minutes before starting to collect sample.

2. 3.

In the mean time, measure 25 ml of the 0.25 M HCl in a flask. When reaction time reaches 10 minutes, collect a 100 ml of sample by opening the sampling valve and immediately add to the 25 ml of 0.25 M HCl prepared in step 3 and mix. The HCl will quench the reaction between ethyl acetate and sodium hydroxide.

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4.

Titrate the mixture with 0.1 M NaOH to evaluate the amount of un-reacted HCl; this will provide you with the information to determine the amount of NaOH in the feed solution which has reacted in your main course of saponification reaction.

5.

Repeat the procedure for reaction times of 15 and 20 minutes and each time record the amount of NaOH needed to titrate the un-reacted HCl. If the amount of NaOH need to titrate the mixture are almost the same at different reactions times, then the system has reached a steady state. This means you have full conversion enough longer retention time has no effect on conversion.

6.

Repeat steps 2 to 6 for different residence times i.e. by adjusting the reed rates to the reactor. Your choice in this case would be higher flow rate. Select the flow meter readings: 20 60.

7.

Switch off all switches on the control panel if you are finished with the experiment.

1.5 Part B: Effect of Reactants Concentration on the kinetics of Tubular Flow Reactor.

The same saponification reaction of the ethyl acetate the sodium hydroxide is used to study the effect of the reactants concentration on the kinetics of the reactor. Prepare 0.2 M NaOH solution in the 20 liter feed tank. Repeat the experiment with the same procedure used before, with the same 0.1 M NaOH solution in the 20 liter feed tank. Also use the same procedure, with the same reactant 0.1 M ethyl acetate. In another run prepare 0.2 M ethyl acetate solution in the 20 liter feed tank. experimental runs. Again repeat the experiment using a 0.1M NaOH. Compare your results with results obtained in three

1.6 Part C: Effect of reaction temperature

The saponification reaction can be carried out at different reaction temperature. Repeat the Experiment A at two different temperature. The three suggested temperatures are

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400C, 500C and 600C. The rate constant k will be determined at 3 different temperatures. The activation energy (E) can be obtained by the plot of ln K against 1/T using logarithm form of equation (11).

1.7 Maintenance:

1.

After each experiment, make sure that the reactor and tubing are cleaned properly. Since the reactants NaOH and ethyl acetate are corrosive and can cause damage to the tubing and the reaction rig.

2. 3.

Dispose all waste or extra liquids immediately after each experiment. Do not leave any reactants or product in the tank. Wipe off any spillage on the bench. Leave your working area very clean, it would count on you course grade and work skill.

1.8 Safety Precautions:

1. 2. 3. 4.

Plug in all cables into appropriate sockets before switching on the main switch. Inspect all cables for any damage to avoid electric shock. Replace if necessary. Do not switch on the heater unless it is fully submerged in the liquid. Always maintain liquid level above the height of the heater to avoid damage to the heater. Make sure that the stirrer assembly is secured properly to avoid any damage to the mechanical seal. Inspect all tubing periodically for leakage and worn out. Leakage might cause damage to the equipment by corrosive reactants. Replace any worn out tubing in the pump, to avoid inconsistent flow rates.

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Figure 1.5: Process flow diagram.

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Stirrer

Flow Meter

Pump Reactor Product Sample

Figure 1.6: A view of the experimental unit.

DATA SHEET (Tubular Flow Reaction, PFR)

Reactants Quenching HCl Sample

Conc. of NaOH = Conc. of Ethyl Acetate= Conc. of HCl = Volume of HCl = Volume of sample =

CNaOH moles/liter CEA moles/liter CHCl moles/liter VHCl ml Vs ml

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EKC 493 Chemical Engineering Laboratory III (Unit Operation Lab)

Flow meter Readings

Time (min) (A)

Volume of Titrating NaOH (ml) (B) From buret readings

Volume of Quenching HCl Unreacted with NaOH in Sample (ml) (C) =

Volume of HCl Reacted with NaOH in Sample (ml) (D) = VHCl (C)

10

10 15 20 10 15 20 10 15 20 10 15 20 10 15 20 10 15 20

C NaOH (B) C HCl

Volume of NaOH Unreacted with Ethyl Acetate (ml) (E) = C HCl (D) C NaOH

Volume of NaOH Reacted with Ethyl Acetate (ml) ,(F)

Concentratio n of NaOH Reacted with Ethyl Acetate (mole/liter) (G) = ( F ) C NaOH VS

Steady state Fraction Conversion of NaOH (H)

1 CA (I)

= VS (H)

= VHCl (C)

1 (G )

20 30 40 50 60

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