RE 302

BATCH REACTIVE DISTILLATION

Date of experiment: 17th January, 2012

Date of submission: 20th January, 2012

Group A1 (b)
Aditya Lalwani (09D02004) – Presentation
Aditya Telang (09D02012) – PowerPoint slides
Yamini Krishnan (09D02035) – Report

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INTRODUCTION:
The combination of a batch reactor with a batch distillation column is called batch
reactive distillation. It is used to increase the equilibrium conversion of reversible reactions such
as esterification and etherification reactions. This method can reduce costs significantly when
compared to the conventional approach of reaction followed by distillation when the products
have similar volatilities and separation by distillation is difficult. In this experiment, we study the
enhancement of conversion (obtained by batch reactive distillation compared to batch reaction
only) of the reaction of acetic acid with n-butanol to produce butyl acetate.

THEORY:
For a reversible reaction,

aA + bB cC + dD

the equilibrium constant, K, is fixed for a given temperature. When






= K,

equilibrium is attained and the net rate of reaction is zero. According to Le Chaelier’s principle,
at this point if some amount of reactant is added, or if some product is removed, the reaction will
proceed in the forward direction.

In the experiment, the reaction being carried out is:

CH3COOH + C4H9OH CH3COOC4H9 + H2O

This is an esterification reaction. It is reversible and is catalysed by acids. If acetic acid and n-
butanol are allowed to react in stoichiometric quantities, the equilibrium conversion is nowhere
close to 100%. All the four components in the final reaction mixture have very close boiling
points and similar volatilities. So isolation of butyl acetate by distillation is difficult. We apply
Le Chatelier’s principle to increase conversion. By removing water in batch reactive distillation,
the reaction moves forward and almost 100% conversion is achieved. Water can be separated
because it forms a heterogeneous ternary azeotrope with butanol and butyl acetate. In
heterogeneous azeotropes, the components are immiscible as liquids and form two separate
phases. In the experiment, two liquid layers are formed. The lower layer contains 97% water and
only traces of butanol and ester. This layer is removed. The upper layer contains mostly organic
components and is sent back to the reactor.

TITRATION:

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In the experiment, we follow the concentration of acetic acid, using which we calculate the
conversion. Samples are titrated against 1N NaOH solution. NaOH neutralizes acetic acid, and
acetate is formed.

CH3COOH + NaOH CH3COO- + Na+ + H2O

The equivalence point of the titration is between pH 8 and 9. Phenolphthalein starts to change
colour at pH 8.2 and is used to detect the end point. The concentration of acetic acid in the
sample is given by:
   

Cacetic acid = … (1)

Using this concentration, the conversion in the reactor can be calculated as:
 

X= … (2)

The above formula can be used only when the total volume does not change. In reactor R1, water
is being removed and hence we use the following formula:
     
  
X= = … (3)

The enhancement of conversion obtained by using a batch reactive distillation system is:
 ! "
 "
Enhancement = … (4)

PROCEDURE:
There are two reactors, R1 and R2. R1 is a batch reactive distillation system, while R2 is
just a batch reactor. In each reactor, 210 ml of acetic acid and 340 ml of n-butanol are taken.
Acetic acid and butanol are in stoichiometric ratio. 50 grams of Amberlyst 15 (dry) catalyst is
added to each reactor. Amberlyst 15 dry is a bead form, strongly acidic ion exchange resin. The
advantage is that the acid catalyst is in an immobilized form and can be easily separated from the
reaction mixture by filtration. Samples are taken from both reactors and are titrated against
NaOH. Heating and water supply to condensers is started and the stirrer is also started. When the
reaction mixtures start boiling, samples are taken and the stirrer speed is set to approximately
1000 rpm. In reactor R1 the condensate starts collecting in the Dean Stark apparatus. It forms
two layers with the bottom layer being water. Care should be taken that water does not re-enter
the reaction mixture. Once every 10 minutes, samples are collected from reactors 1 and 2. Water
and organic layer samples are also collected. These four samples are titrated against NaOH. The
amount of water removed from the reaction mixture of R1 is noted down. The temperatures are
3
also noted down. This is to be continued until saturation is reached (indicated by no change in
acid content and by constant temperature).

210 ml acetic acid, 340 ml alcohol and 50 g amberlyst catalyst are

taken in R1 (batch reactive distillation) and R2 (batch reactor).

Heating, stirrer and condenser water supply are started.

When the reaction mixture starts boiling, samples are taken for
titration from R1 and R2.

The stirrer speed is set to 1000 rpm.

After every 10 min, samples are taken from R1, R2, and the organic
and water layers. Amt of H2O removed ,T1, and T2 are noted down.

The four samples are titrated against NaOH. The above procedure is
continued until the reaction reaches saturation.

FIGURE 1: PROCESS FLOW DIAGRAM

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SCHEMATIC :

FIGURE 2

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OBSERVATIONS:
Initial quantity of acetic acid used = 210 ml = 220 g = 3.7 mol

Initial quantity of n – butanol used = 340 ml = 275 g = 3.7 mol

Quantity of Amberlyst 15 dry in each reactor = 50 g

TABLE 1

START OF BOILING (time = 0 min)

REACTOR TEMPERATURE (oC) TITRATION READING (ml)

R1 101.7 6.8
R2 99.0 6.2

TABLE 2

OBSERVATIONS FOR R1 (BATCH REACTIVE DISTILLATION)

S.No TIME REACTOR TITRATION READING WATER CUMULATIVE

(min) TEMPERATURE (ml) REMOVED WATER
(oC) organic water R1 (ml) REMOVED (ml)
1 10 101.1 0.1 0.0 5.6 9 9
2 20 101.4 0.2 0.1 4.6 12 21
3 30 103.4 0.1 0.2 3.7 9.5 30.5
4 40 106.6 0.2 0.1 3.0 9.5 40
5 50 108.8 0.1 0.0 2.5 8 48

TABLE 3

OBSERVATIONS FOR R2

S.No TIME (min) TEMPERATURE TITRATION

(oC) READING (ml)
1 10 97.8 5.1
2 20 97.3 4.8
3 30 97.0 4.7
4 40 96.8 4.7
5 50 96.8 4.6

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CALCULATIONS:
For each reading, the concentration of acetic acid is calculated using equation 1. From this
concentration, we can directly calculate the conversion in reactor R2 using equation 2. For reactor
R1, water is being removed. Thus the volume of the reactor, V, is calculated by subtracting the
cumulative water removed from the initial volume, V0. Then, using equation 3, the conversion is
calculated. The enhancement in conversion obtained by using a batch reactive distillation system
instead of a batch reactor alone is calculated using equation 4. The errors in all the quantities are
calculated according to the formulae below.

ERROR ANALYSIS:

There are errors when measuring the volumes of acetic acid and butanol to be taken in each
reactor. There is also an error associated with reading the amount of NaOH used in the titration.
While preparing the NaOH solution, an electronic balance having a least count of 0.0001 g was
used and the solution was prepared in a standard flask. Thus, the concentration of this solution
can be considered to be exact. The propagation of error is given by the following formulae.

Error in initial volume of acetic acid = Least count of measuring cylinder/2 = ±2.5 ml.

Error in initial volume of butanol = Least count of measuring cylinder/2 = ±2.5 ml.

Error in total initial volume = ±5 ml.

Error in amount of volume of water removed = Least count of measuring cylinder/2 = ±0.5 ml.

Error in cumulative amount of volume of water removed = 0.5*#$ ml (n is number of readings).

Error in each titration reading of NaOH = Least count of burette/2 = ±0.05 ml.

Error in volume of acetic acid taken for each titration = Least count of syringe/2 = ±0.1 ml.

The concentration of NaOH is taken to be exact. Therefore, the error in concentration of acetic
acid calculated by titration is given by:

" "
- ./ 1'23 4 5 6
%&'()*+('(+, %0 %0
; …(5)
7'89:)
&'()*+('(+, 0 1'23 0 7'89:)

For reactor 2, the error in conversion is given by:

%&? " "

- >/
%<= %&
<= &?
4 5 / & ? 4 … (6)
?

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Volume of reactor (V) = Total volume (VT) – Cumulative amount of water removed (VC)

∆V = @ABCD E" 5 ABC& E" …(7)

Error in conversion of reactor 1 is:

%&? " " " %0 "

- >/
%<F %& %0
<F &?
4 5 / & ? 4 5 / 0 G4 5 / 0 4 … (8)
? G

Error in enhancement of conversion is:

%<F " "

- >/
%H %<
H <F
4 5 / < =4 …(9)
=

Calculate the concentration of acetic acid for each titration

using eqn 1.

Calculate the conversion in R2 using eqn 2.

Calculate reactor volume for R1 by subtracting cumulative

volume of water removed from initial volume.

Calculate conversion in R1 using eqn 3.

Calculate the enhancement in conversion and errors in all

quantities.

FIGURE 3: CALCULATIONS FLOW DIAGRAM

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RESULTS AND DISCUSSIONS:
TABLE 4

CALCULATIONS FOR R1

TIME (min) CUMULATIVE ERROR IN CONVERSION ERROR IN Acetic

WATER CUMULATIVE X1 X1 acid lost
REMOVED WATER (ml) (mmol)
(ml)
10 9.0 0.5 0.59 0.04 0.1
20 21.0 0.7 0.67 0.05 0.8
30 30.5 0.9 0.74 0.05 1.05
40 40.0 1.0 0.79 0.06 0.68
50 48.0 1.1 0.83 0.06 0.1

As time passes, the conversion in R1 keeps increasing. At 50 minutes, approximately 80%

conversion is achieved. When the experiment was run for the first time, there were problems
with the sample withdrawal system for R1. Due to this, the experiment was restarted on a
separate rig. Due to these delays, there was a shortage of time and we could not wait until
saturation was reached (which would have been indicated when no more water came out and
temperature became constant). The total amount of acetic acid is 2.73 mmol which is one-
thousandth the amount present in the reactor. This is even less than the experimental error. Thus,
it does not have any effect on calculated conversion.

TABLE 5

CALCULATIONS FOR R2 AND ENHANCEMENT OF CONVERSION

TIME (min) CONVERSION ERROR IN X2 ENHANCEMENT ERROR IN

X2 OF ENHANCEMENT
CONVERSION
10 0.62 0.04 -0.057 0.006
20 0.64 0.05 0.036 0.004
30 0.65 0.05 0.13 0.01
40 0.65 0.05 0.21 0.02
50 0.66 0.05 0.26 0.03

The conversion and the temperature in R2 are approximately the same for the last three readings.
This indicates that equilibrium has been attained in R2. For the first reading, the enhancement in
conversion seems to be negative, i.e. the conversion in R2 is more than in R1, which is
counterintuitive. But as seen in the following graph, this is within experimental error.

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 FIGURE 4

Initially, both reactors show the same levels of conversion. But as time passes, water (which is a
product) is removed from R1. According to Le Chatelier’s principle, the forward reaction is
favored and the conversion continues to increase. On the other hand, nothing is added to or
removed from R2. The reaction attains equilibrium and the conversion attains a constant value.

In the graph below, the temperatures of both the reactors is plotted against time. It is observed
that the temperature of R1 increases with time while that of R2 slightly decreases. The boiling
points of acetic acid, butanol, water and butyl acetate are 118 oC, 117.7 oC, 126.3 oC and 100 oC
respectively. Butyl acetate has the highest boiling point. In R1, water is being removed
continuously and butyl acetate is enriched. Due to this change in composition, the boiling
temperature of the mixture increases. In R2, water is not removed and it serves to keep the
temperature down.

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 FIGURE 5

FIGURE 6

The enhancement for the last reading is 0.26. If the reaction had been allowed to go to
completion, even more enhancement would have been seen.

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 FIGURE 7

FIGURE 8

The total amount of water removed varies linearly with time. The rate of water removal is
approximately 1 ml per minute.

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SAMPLE CALCULATION:
Volume of 1M NaOH required to titrate 2 ml sample from R1 at the end of 10 minutes = 5.6 ml

Error in this volume = ±0.05 ml

Error in volume of acetic acid sample = ±0.1 ml.

From eqn 1, concentration of acetic acid CA = 5.6*1/2 = 2.8 M

" "
Error in CA = CA*./
%01'23 %0
4 560 ; = 0.14 M
7'89:)
0 1'23 7'89:)

Cumulative volume of water removed = 9 ml

Error in this volume = ±0.5 ml

Volume of R1(V) = VT – VC = 550 -9 = 541 ml

Error in V = @ABCD E" 5 ABC& E" = 5.02 ml

Conversion in R1 (X1) = (CA0V0 – CAV)/(CA0V0) = (3.7 – 1.51)/3.7 = 0.59

%&? " " " %0 "

Error in X1 = X1* >/
%& %0
&?
4 5 / & ? 4 5 / 0 G4 5 / 0 4 = 0.04
? G

Volume of 1M NaOH required to titrate 2 ml sample from R2 at the end of 10 minutes = 5.1 ml

Error in this volume = ±0.05 ml

From eqn 1, concentration of acetic acid CA = 5.1*1/2 = 2.55 M

"
%01'23 "
Error in CA = CA*./
%07'89:)
01'23
4 560 ; = 0.13 M
7'89:)

From eqn 2, conversion in R2 (X2) = ( CA0 – CA)/( CA0) = 0.62

%&? " "

Error in X2 = >/
%&
&?
4 5 / & ? 4 = 0.04
?

Enhancement in conversion = (0.59 – 0.62)/0.62 = -0.057

%<F " "

Error in enhancement = Enhancement* >/
%<
<F
4 5 / < =4 = 0.006
=

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