EXPERIMENT NO.

7 SPRAY EXTRACTION 08/21/2017

Study of Hydrodynamics of a liquid- liquid spray extraction column and determination

of overall mass transfer coefficient.

Srinidhi Suresh* (14CHE1074), Niranjan Sitapure*(14CHE1037), Abhijeet Subudhi* (14CHE1032)

*Chemical Engineering department, Institute of Chemical Technology, Mumbai, India.

Abstract

The primary objective of this experiment is to provide a fundamental understanding of the spray extraction process in
vertical column by obtaining experimental hydrodynamic data. In this experiment, a spray column is used to extract MIBK
from a stationary solution filled in a column into dispersed phase water. We intend to determine the specific interfacial
area and overall mass transfer coefficient generated and their variation with flow rate of dispersed phase (water). The
effect of water flow rate on dispersed phase hold up is also studied. Acquiring this data may help us identify if an optimum
dispersed phase flow rate exists, that can offer the maximum mass transfer coefficient. This proves to be an important
aspect while designing and scaling of spray columns.

Keywords: Spray Column, interfacial area, MIBK (Methyl Isobutyl Ketone), Mass transfer coefficient

1. Introduction
Liquidliquid extraction is a well-known separation process, which has been largely used by process industries for many
years. The process takes advantage of differences in the chemical properties of the feed components, such as differences
in polarity and hydrophobic or hydrophilic character, to separate them. In this process, a solute is transferred between the
droplets of a dispersed phase and the bulk of an immiscible continuous phase. The study of steady-state movement of
droplets within a liquid phase is the mostly recommended way by researchers to obtain a theoretical basis for the liquid
liquid extraction systems. The spray column is the simplest column among the liquidliquid extraction columns. One of
the major advantages of spray columns is the absence of internals apart from the liquid spray or distributor. This
translates to a much lower capital cost as compared to packed columns.
In a Spray Column, mass transfer is enabled due to contact produced between small droplets of dispersed phase
generated by the spray and a continuous phase that fills the column. The continuous phase may be stationary or counter
current according to the application. The mass transfer coefficient and the rate of mass transfer depend on droplet size
and flow rate of the dispersed phase. Dispersed phase holdup is also determined by the dispersed phase flow rate.
The process is used in both industrial and laboratory spray columns for countercurrent liquid-liquid extraction. This
concept is widely used in deep cleaning of upholstery and carpets. In this process, cleaning solution is sprayed into the
carpet under pressure and picked up again immediately. The dirt is rinsed from deep down out of the carpet pile and not
just from the top. Also, spray extraction can be used for isolation of proteins or enzymes from complex mixture using two-
phase aqueous extraction technique. It offers advantages in terms of process time and ease of scale up. In addition, there
are many applications where more than one theoretical stage is required. Such applications can be fulfilled by column
type of extractors operated in counter current manner.

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The design of such equipment requires knowledge of flow rates, concentrations, and the rate of mass transfer for the
system. One of the most important parameters in liquidliquid extraction columns is the dispersed phase droplet
behaviour, because of its effect on mass transfer coefficient. In this study, a spray column is used to extract MIBK from a
stationary solution filled in a column into dispersed phase water. We intend to determine the specific interfacial area and
overall mass transfer coefficient generated and their variation with flow rate of dispersed phase (water). The effect of
water flow rate on dispersed phase hold up is also studied.

2. Theory
In this experiment, we use MIBK (methyl iso-butyl ketone) as the continuous light phase and we spray water from the
liquid distributor as the dispersed heavy phase. As water droplets move down under the influence of gravity, MIBK will
dissolve in water and depending on turbulence, pressure, temperature, residence time of the dispersed phase, certain
amount of MIBK will dissolve in water. The MIBK concentration can be determined by collecting the sample from bottom
and carrying out further analysis.

To determine the mass transfer coefficients, the volume of a single drop (VF) needs to be calculated so as to find the
interfacial area. Hayworth et al. (1950) proposed a correlation through their experimental findings to determine the
volume of a drop. [1]
2
. 2 . 0.747 . 0.365 . 0.186 1.5
+ 4.11 (104) 3 ( ) = 21 (104 ) ( ) + 1.069 (102 ). ( ) [1]

Where,

VF = volume of single drop (mL)

VN = velocity of dispersed phase through the nozzle (cm/s)

DN = diameter of the nozzle (cm)

= interfacial tension (dynes/cm)

D= density of dispersed phase (g/cc)

C = viscosity of continuous phase (poise)

This equation (Eq. 1) is a non-linear equation and all units are in the CGS system. To avoid repeated iterations, Hayworth
et al. (1950) came up with a graphical solution to Eq. 1 to determine the diameter of the drop directly using (Fig. 1).

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Fig. 1: Graphical Solution of Equation 1

Once we know the volume of a droplet from the above equation, we can find the diameter of the droplet (assuming its
completely spherical) using the equation:
1
6
= (( ) )3 [2]

From the diameter of single drop, we can find interfacial area using following equation:

Total suface area of droplets 6

= Dispersion volume
=
[3]

Here, is the dispersed phase hold - up.

Thus, volumetric rate of mass transfer can be calculated as:

= ( ).
[4]

Here,

QD = volumetric flow rate of dispersed phase (m3 /s)

V = contactor volume (m3)

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C = MIBK concentration in outlet stream (mol/m3)

Ci = inlet concentration of MIBK = 0

Using the above, we can find mass transfer coefficient for dispersed phase as:

=
[5]

Where = log mean concentration gradient

Knowing the rate of mass transfer, the experimental volumetric mass transfer coefficient for dispersed phase can be
calculated (Eq. 5). Also, estimations can be made from correlations for continuous phase mass transfer coefficient () as
reported by Ruby et al. (1955) [2] and dispersed phase mass transfer coefficient () as reported by Handlos et al. (1957).
[3]

0.43 0.58
= 0.725 (
) . ( ) . [ (1 )] [6]
.

0.00375
= [7]
[1 + ]

Here,

UT = slip velocity at =0 (m/s)

Vs = slip velocity (m/s)

Finally, overall mass transfer coefficient for dispersed phase (Kd) can be found using Eq. 8.

1 1 1
= + [8]

Thus, through this experiment, we aim to study the hydrodynamic characteristics of liquid-liquid spray column and find
dispersed phase, continuous phase and overall mass transfer coefficient. This data, if collected accurately and analyzed
properly, can be beneficial in designing of actual industrial spray columns or can be used for further studies in liquid-liquid
extractions and spray columns.

3. Materials and Methods

The spray column of diameter 15 cm used constructed from glass, has arrangement of funnel at top to fill it with
continuous phase and cork to hold nozzle of diameter 2.8 cm for dispersed phase was acquired from Omega Glass Works.
Bottom collector is connected to a liquid seal. The binary system used in the experiment is that of pure methyl isobutyl
ketone (MIBK) and water. Water (density =996 kg/m3; viscosity, 9.5x104Pas) and MIBK (density = 802 kg/m3; purity >99%;

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viscosity, 5.8x 104Pas; product of Thomas Baker Chemicals Pvt. Ltd.) are used as the dispersed phase and the continuous
phase, respectively. There is a distributor present at the top of the spray column to create the dispersed phase droplets. A
rotameter at the inlet shows the corresponding flow rate of water entering the column having a least count (LC) of 0.1 cm.

Rotameter has been calibrated and found that 1 rotameter scale unit =1.3909 ml/min. The liquid heights/level in either
case is measured using a ruler scale of least count (LC) of 0.001m. To obtain 5ml of the sample from the column was taken
out using pipette of least count (LC) of 0.2ml. For the analysis of MIBK in extract aqueous phase titration was done using
burette of least count (LC) of 0.1 ml which hold 0.5N NaOH.

The Figure 2 is a schematic of the experimental setup used for carrying out the experiment. The liquid distributor
is connected with pipes to a liquid rotameter to measure flow rate of dispersed liquid. The flow of dispersed phase from an
overhead tank is maintained by use of a valve as shown. A liquid seal is used to maintain liquid level in the column. The
experiment is repeated at various flow rates of the dispersed phase keeping the continuous phase constant.

Figure 2 - Schematic of the experimental setup. The diagram shows a spray column with MIBK, there is rotameter for aqueous
phase, the feed streams are circulated via pumps and stored in the overhead tank as shown. There is a view glass at the top
and bottom of the column to look for the interface formation during the experiment.
The column is filled with MIBK to such a height that the tip of the dispersed phase (water) nozzle dips into the continuous
MIBK phase. Constant water flow rate is maintained and the outlet of the column is so maintained that the interface of
the two phases formed in the column remains at a constant level which is noted. Giving ten minutes to reach steady state,
about 30 of the outlet sample is collected. The inlet and the outlet of the column are then closed simultaneously and the

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rise in the level of the interface is noted which is used to calculate the holdup. The same procedure is then followed for
different values of flow rates.
For analysis, 5 mL of the sample solution of MIBK in water is mixed with 25 ml standard hydroxylamine hydrochloride
solution which reacts with ketone as follows:

The free HCl can be used for RR'CO determination. The mixture is refluxed for about thirty minutes on a steam bath with
intermittent shaking. The refluxed liquid is titrated against standard NaOH using Bromophenol blue as an indicator. End
point is yellow to green to a final blue. A blank titration of standard hydroxylamine solution is also done. The difference in
readings gives the MIBK concentration in the sample taken. The flow rates are measured and the corresponding titrated
reading can be tabulated.

Figure 3: Actual Experimental Setup available in the laboratory. It shows the extraction column along with the water
rotameter and a sample collection facility as schematically illustrated in

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4. Observations

Least Counts:

Burette mL
Pipette mL
Measuring Cylinder mL
Rotameter reading
Vernier Calliper cm

Standardization of NaOH:

N1: Normality of oxalic acid N

V1: Volume of oxalic acid mL
N2: Normality of NaOH N
V2: Volume of NaOH mL

Rotameter Calibration:

Rotameter reading Flow rate (ml/s)

Observation Table:
Volume of sample dispersed phase taken for analysis: -

Rotameter reading h1 h2 Titration reading h2 h1

(cm) (cm) (mL) (cm)

Diameter of column: -

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5. Checklist

Determine the least counts of all the apparatus to be used.

Standardize the given sodium hydroxide solution.
Calibrate water rotameter.
Make sure that methyl isobutyl ketone (MIBK) is filled in the column upto the distributor.
Ensure that the interface in the column remains at a constant level for every reading.
Allow 10 minutes for steady state to be reached.
Close inlet and outlet of column and note the height of the interface.
After drawing sample from outlet, add hydroxylamine hydrochloride solution.
Reflux the liquid for 30 minutes on a steam bath and then titrate against NaOH.
End point for the above titrations is yellow to green to blue. Note it.
Also, carry out a blank titration of standard hydroxylamine solution.
Take readings for 3-4 flow rates.
Measure diameter of spray column using Vernier calliper.
If time permits, determine whether the concentration of oxalic acid is accurate using a conductometer.

References

[1] Hayworth, C. B., & Treybal, R. E. (1950). Drop formation in two-liquid-phase systems. Industrial & Engineering
Chemistry, 42(6), 1174-1181.
[2] Ruby, C. L. and Elgin, J. C. (1955). Mass transfer between liquid drops and a continuous phase in a countercurrent
fluidized system: liquid liquid extraction in a spray tower, Chem Eng Prog Symp Ser, 51(16): 17 29.
[3] Handlos, A. E., & Baron, T. (1957). Mass and heat transfer from drops in liquidliquid extraction. AIChE Journal, 3(1),
127-136.

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