DISTILLATION

LORENZ JOHN T. CHU

Department of Chemical Engineering, College of Engineering and Architecture,

Cebu Institute of Technology - University,

N. Bacalso Ave., Cebu City, 6000 Philippines

Distillation is a method for separating mixtures based on differences in their volatiles in a boiling
liquid mixture. It is a unit operation or a physical separation process and not a chemical reaction.
The objective of this experiment is to determine the reflux ratio, required to recover ethanol of
desired specification from ethanol-water mixture. At a steam pressure of 30 psig, the time of
collection is recorded and the reflux ratio is 0.0377 while the density of the old solution is 0.9168
g/mL, new solution is 1.0202 g/mL, and the density of the distillate is 0.8668 g/mL.
1. Introduction

Distillation is the process of separating the components or substances from a

liquid mixture by selective boiling and condensation. Distillation may result in
essentially complete separation (nearly pure components), or it may be a partial separation
that increases the concentration of selected components of the mixture. In either case the
process exploits differences in the volatility of the mixture's components. In industrial
chemistry, distillation is a unit operation of practically universal importance, but it is a
physical separation process and not a chemical reaction. (Harwood & Moody, 1989)

One of the main variables encountered in a large scale fractional distillation is the
Reflux ratio which can be defined as the weight of the liquid retained as reflux divided by
the weight removed as overhead product. At total reflux, reflux ratio is equal to infinity,
the separation desired is achieved with the smallest packed height. This condition can be
realized by returning all the overhead condensed vapor from the top of the tower back to
the tower as reflux, i.e., total reflux, Also, all the liquid in the bottoms is reboiled. Hence,
all the products distillate and bottoms are reduced to zero flow, as is the fresh feed to the
tower. This condition of total reflux can also be interpreted as requiring infinite sizes of
condenser, reboiler, and tower diameter for a given feed rate.

In simple distillation, the vapor is immediately channeled into a condenser.

Consequently, the distillate is not pure but rather its composition is identical to the
composition of the vapors at the given temperature and pressure. That concentration
follows Raoult's law. As a result, simple distillation is effective only when the liquid
boiling points differ greatly (rule of thumb is 25 °C)[25] or when separating liquids from
non-volatile solids or oils. For these cases, the vapor pressures of the components are
usually different enough that the distillate may be sufficiently pure for its intended
purpose. (Gildemeister & Hoffman, 1913)

Industrial towers use reflux to achieve a more complete separation of products.

Reflux refers to the portion of the condensed overhead liquid product from a distillation or
fractionation tower that is returned to the upper part of the tower as shown in the
schematic diagram of a typical, large-scale industrial distillation tower. Inside the tower,
the downflowing reflux liquid provides cooling and condensation of the upflowing vapors
thereby increasing the efficiency of the distillation tower. The more reflux that is provided
for a given number of theoretical plates, the better the tower's separation of lower boiling
materials from higher boiling materials. Alternatively, the more reflux that is provided for
a given desired separation, the fewer the number of theoretical plates required. Chemical
engineersmust choose what combination of reflux rate and number of plates is both
economically and physically feasible for the products purified in the distillation column.

For the case of total reflux, the number of plates is a minimum, but the tower diameter
is infinite. This corresponds to an infinite cost of tower, steam, and cooling water. This
one limit in the tower operation. Also, for minimum reflux ratio, the number of trays is
infinite, which again gives an infinite cost. These are the two limits in operation of the
tower. (Perry & Green, 2007)

The actual operating reflux ratio to use is in between these two limits. To select the
proper value of R requires a complete economic balance on the fixed costs of the tower
and operating costs. The optimum reflux ratio to use for the lowest total cost per year is
between the minimum and total reflux.
2. Materials and Method

2.1 Materials and Apparatuses

• Water

• Ethanol

• Glass distillation apparatus

• Thermocouple

• 25-mL pycnometer

• 1-L beaker

• 250-mL beaker

• 20-liter plastic pail

2.2 Methods

2.2.1 Preparation of Feed

Industrial grade ethanol was prepared. Using the pycnometer, the density was
determined. A 30 weight percent solution was prepared by mixing ethanol and
water. The density of the resulting solutions is measured using a pycnometer.

2.2.2 Charging of Feed and Distillation Operation

All the vent lines are checked and opened. The overhead condenser cooling
water supply is turned on. The spherical vessel is charged up to the equator with
the ethanol-water mixture solution prepared. By-pass around the steam trap is
opened. Then the main steam supply is carefully open or turned when initial surge
condensate cleared, steam trap by-pass valve is closed. Steam pressure is set to a
pressure of 30 psig and the reflux divider is set for total reflux by closing the
product off. Reboiler steam pressure is adjusted to a value which gives adequate
loading on the packed column which is 30psig. After a few minutes, the column is
allowed to settle. The drain valve on the lower product receiver is closed. Vents
and valves are rechecked and if product receiver and overflow still open. Fully
open the product line valve by the reflux adapter and allow liquid to drain. The
 recycle valve is closed and the time to half fill the upper product receiver is
recorded. The product line valve is closed and the level of the liquid collected is
marked on the side of the receiver. The product recycle valve is closed and the
time to half fill the upper product receiver is measured. The temperature and
specific gravity of the product is measured through the lower receiver. The
product cycle valve is reopened and the steps are repeated with a higher reflux
ratio by slightly closing the product line valve.

2.2.3 Shutdown

The reflux ratio control was set to total reflux. The steam supply was turned
off. The residual steam was carefully vented through the condensate drain valve.
The condenser cooling water was turned off. Liquid in the boiler was drained to a
suitable receiver.

3. Results and Discussion

Table 3.1 Data for time and reflux ratio

Steam pressure T1 T2 R

30 psig 24.13 min 25.04 min 0.0377

Table 3.1 shows the T1 as the time for the distillate to reach half of the upper product
receiver while T2 refers to the time for the distillate to reach half of the upper product
receiver after doing a reflux. Both of these values are taken at constant pressure.

It is a common misconception that in a liquid mixture at a given pressure, each

component boils at the boiling point corresponding to the given pressure and the vapors of
each component will collect separately and purely. This, however, does not occur even in
an idealized system. Idealized models of distillation are essentially governed by Raoult's
law and Dalton's law, and assume that vapor–liquid equilibria are attained.

An implication of one boiling point is that lighter components never cleanly "boil
first". At boiling point, all volatile components boil, but for a component, its
 percentage in the vapor is the same as its percentage of the total vapor pressure.
Lighter components have a higher partial pressure and thus are concentrated in the
vapor, but heavier volatile components also have a (smaller) partial pressure and
necessarily vaporize also, albeit being less concentrated in the vapor. So in order to
increase the towers efficiency, it is needed to use a reflux to achieve a more complete
separation of products. Reflux refers to the portion of the condensed overhead liquid
product from a distillation or fractionation tower that is returned to the upper part of
the tower as shown in the schematic diagram of a typical, large-scale industrial
distillation tower. Inside the tower, the downflowing reflux liquid provides cooling
and condensation of the upflowing vapors thereby increasing the efficiency of the
distillation tower.

For this experiment the packed height is fixed and must be operated at a reflux
ratio below the total reflux. An increase in the reflux ratio will improve the separation
achieved and consequently increases the proportion of ethanol in the overhead
product.

Table 3.2 Data for density

DENSITY PYCNOMETER MASS VOLUME ρ (g/mL)

(SOLUTION) (SOLUTION) (PYCNOMETER)

Old Solution 48.64 g 25.72 g 0.9168

New Solution 85.54 g 34.53 g 25 mL 1.0202

Distillate 49.79 g 28.12 g 0.8668

The group used the solution made by the previous group so the density of the old
solution and the new solution is calculated.

The density of the old solution is found to be 0.9168 g/mL and the density of the new
solution is 1.0202 g/mL. The density of the distillate is found to be 0.8668 g/mL.
4. Conclusion

Reflux ratio calculated at 30 psig is 0.0377. The density calculated for the old solution
is 0.9168 g/mL, new solution is 1.0202 g/mL, and the density of the distillate collected is
0.8668 g/mL.
APPENDIX A

1 1
-
t1 t2
Equation 1. R =
1
t2

Equation 2. density = mass solution/volume pycnometer

APPENDIX B

Distillation Column

Figure B.1
 Figure B.2 Figure B.3

References:

[1] Chemical Engineering Department Laboratory Manual, Chemical Engineering

Laboratory 2

[2] Perry, R. H., & Green, D. W. (2007). Perry's Chemical Engineers' Handbook .
McGraw-Hill.
[3] Harwood, L., & Moody, C. (1989). Experimental organic chemistry: Principles and
Practice. Oxford: Blackwell Scientific Publications.
[4] Gildemeister, E., & Hoffman, F. (1913). The Volatile Oils. New York: Wiley.