Chapter 1

INTRODUCTION

1.1 Overview of liquid-liquid extraction

Liquidliquid systems are used in different processes such as extraction, emulsion
polymerization, phase transfer catalysis, homogenous catalyst screening, precipitation,
crystallization and cell separation. The separation process in which a component of a liquid
solution is separated when in contact with another insoluble liquid is named as Liquid-liquid
extraction. Typically, the separation occurs due to difference in the solubility of the
components in the incompletely miscible or immiscible liquids. In such sort of operations,
the solution which is to be extracted is called the feed, and the liquid with which the feed is
contacted is called solvent. The solvent rich phase after extraction is known as the extract or
concentrate, and the remaining liquid from which solute has been transferred is called
raffinate (Treybal, 1981). Solvent extraction principally relies on the favorable distribution
of the solute between the solvent and feed. The distribution coefficient and the selectivity are
the two parameters which fix the number of extraction stages and solvent usage.

1.2 Sources for production of aromatics

The major sources to produce aromatics are fuel oil, hydrocarbons, naphtha, pyrolysis
gasoline. The aromatics can be produced by the various industrial processes. In the coal
carbonization process, light oil acquired contains about 2 to 8 kg of BTX aromatics per ton
of coal. The steam cracking of hydrocarbons and naphtha like ethane and propane produced
pyrolysis gasoline contains around 65% of aromatics content. In the process of catalytic
reforming, aromatics rich in BTX are produced by involving the major reactions such as de-
hydrogenation of naphthenes and dehydrocyclization of paraffins. The UOP cyclar process
used propane and butane as raw materials to produce BTX aromatics by the de-aromatization
reaction. In the isomerization process, the C8 stream conversion produces the O-xylene and
P- xylene as products. Some other processes, which produces the aromatics are de-
aromatization of naphtha, KTI pyro forming (Gary and Handwerk, 2001).

1
1.3 Uses of aromatics
An aromatic complex is a blend of process units that converts petroleum naphtha and
pyrolysis gasoline feed-stocks into the basic petro-chemical intermediates such as Benzene,
Toluene, and Xylene (BTX). Aromatics are used to make fibers and utilized as a part of
easy-care clothing and furnishing fabrics. In addition, aromatics are used to contribute their
part in the areas of computer casings, touch-sensitive panels on telephones, compact discs.
(I. D. Mall, 2007).
Benzene is used to decrease the knocking in engines and to make dyes, detergents, drugs,
rubbers and plastic items. It is generally used to produce the derivatives such as ethyl
benzene, cumene, cyclohexane, toluene. Toluene can be used as solvent in paints, paint
thinners, silicon sealants and used in gasoline fuels for internal combustion engines.
Furthermore, it is used as a part of the generation of toluene diisocynate, gasoline
components. Xylene is used as a solvent for the removal of synthetic immersion oil from
microscopic object in light microscopy. It is used as clearing agent and to make baths with
dry ice at the laboratory scale. Xylene is used in the production of terephthalic acid, phthalic
anhydride and derivatives of the ester fibers (Gary and Handwerk, 2001).
1.4 Need for aromatic separation
The necessity of the removal of aromatics in the industries is to produce the desired product,
to enhance yields and to diminish coke lay down in cracking units and to reduce the smoke
liberation, which enhances the smoke point. In the cracking process, the feed contains 25-
30% of aromatic content, which involves huge capacity in the reactor section. The removal
of aromatics is the major challenging process, since they have very close range of boiling
points and there by chance of forming azeotrophic blends. The separation of aromatics
promotes the purity of products and make high quality fuels (Kareem et al., 2012)
The commercial methods suitable for the removal of aromatics are liquid-liquid
extraction which removes 20-65% of aromatic amount, extractive distillation appropriate for
65-90% separation of aromatics, azeotrophic distillation suitable for higher aromatic
separation around 90% and above.

1.5 Solvent selection

The quantities such as high selectivity, high distribution coefficient, insolubility of solvent,
high interfacial tension, low chemical reactivity, high freezing point, non- flammability, low
cost plays a vital role in the selection of good solvent and elevates to choose the solvent.

2
 Conventional solvents such as sulfolane used in the hydrocarbon extraction process,
diethylene glycol used in Universal Oil Product dow extraction process, tri ethylene glycol
used in tetra process, methyl-2- pyrolidone used in extraction process, n- formyl morphaline
used in morphylane extraction process, dimethyl foramide used in REDEX process are used
as a solvent for the separation of aromatics.
1.6 Deep Eutectic Solvents
A eutectic system is a mixture of chemical elements that exhibits a single chemical
composition that solidifies at a lower temperature than any other composition. Eutectic
systems with a very large depression of the melting point are known to be deep eutectic
solvents (DESs).
In general, there are three kinds of DESs
Kind 1: Metal salt + organic salt
Kind 2: Metal salt hydrate + organic salt
Kind 3: Hydrogen Bond Donor + organic salt
The commonly utilized organic salts are choline chloride, methyl tri phenyl phosphonium
bromide due to their biocompatible nature. The HBDs are cheap and environmental benign
like urea, ethylene glycol, glycerol. By mixing and heating at the desired temperature and
rotational speed, we can produce the DES with high purity (Zhang et al., 2012). Reported
DESs in the literatures are Choline chloride + Urea, Choline Chloride + Triethylene glycol,
methyl triphenyl phosphonium bromide + ethylene glycol/ glycerol, tetra methyl ammonium
chloride + glycerol/ ethylene glycol, Choline chloride + glycerol.

1.7 Synthesis of Deep Eutectic Solvents

The deep eutectic solvents are synthesised by mixing properly quarternary ammonium salt
with different hydrogen bond donor in screw-capped bottle in the molar ratio of desired
organic salt to hydrogen bond donor. Then the bottle was stirred at a desired temperature and
maintained at respective rotational speed, until the clear homogenous form is formed (Zhang
et al., 2012).
1.8 Advantages of DES over Ionic liquids
Ionic liquids are solvents that have been utilized as a part of the past time. They are
environmental friendly compared to the organic solvents used in the operations of liquid
liquid extraction and separation processes. The issue with ionic liquids in large scale

3
applications is their complex reaction mechanism, synthetic processes and the raw material
chemicals are too expensive.
An alternative had been recognised to ionic liquids, named Deep Eutectic Solvents(DES),
due to its features such as cost effective, non-toxic, non-volatility, non-flammability,
availability, recyclability, non-reactive with water, bio-degradable and moreover
environmental friendly. Above all, DES can be prepared easily in high purity at low cost,
and the purity of the mixture depends upon the purity of the individual components (Leron et
al., 2012). Contrasting with Ionic liquids which comprises of a cation and a complex anion,
DESs consists of a cation, an anion and a complexing agent. By using DES as a solvent, the
reactions can be performed at low temperature with decreased reaction time and increased
eco-friendliness (Emma L. smith et al., 2014).

1.9 Microfluidics: Origin, Applications and Advantages

Microfluidics is the science and technology of systems that processes small amounts of
fluids, utilising channels with dimensions of 10-102 micrometres. The field of microfluidics
has a vital role in regions of information technology, biological analysis and chemical
synthesis. But, the field is in developing stage due to smaller dimensions of microchannel
reactors and the surface area to volume ratio is high. Consequently, it provides many
advantages for microchannel reactor over conventional reactors. The field of microfluidics
has arrived from areas such as molecular biology, bio-defence, molecular analysis and
micro-electronics. Microfluidics offer numerous approaches to overcome many problems in
molecular biology like requirement of higher sensitivity and throughput. The microfluidics
are used in the areas of solvent extraction, two phase chemical reactions, gas absorption,
biomedical engineering, pharmaceutical industries, Electrochemistry, Micro-fuel cells (G.
M. White sides, 2006). To fabricate the micro channels, the materials significantly utilized
are metals, glass, polymers and ceramics. The techniques that are executed for the process of
fabrication are etching, lithography, electroplating, molding, polymer microinjection
molding, and engraving.

The microchannel reactors are playing their part in the chemical and pharmaceuticals
industries by replacing the conventional methods of technologies. The application part of
micro reactors has spread in the various areas of solvent extraction, organic synthesis, Nano
particle crystallization, protein folding, bio process optimization, biological screening. With

4
the introduction of micro channels, a drastic change of improvement has been observed in
the chemical engineering sector. The micro-structured reactor offers very high mass transfer
and heat transfer when compared to other conventional reactors/contactors like static mixer,
plate heat exchanger, stirred tank reactor etc. Some of the advantages of micro channel over
conventional equipment are high surface to volume ratio, effective mixing at laminar flow
condition, enhanced heat and mass transfer rates, less amount of power is required for
operation, only small volume of fluid is required, an increase in the rate of reaction can be
achieved, precise mixing/dosage and heating can be attained.

1.10 Flow patterns inside a microchannel

Different kinds of flow patterns that can be observed in the micro-channel are

1.10.1 Droplet Flow

The droplet flow is considered, when the bubble with diameter less than or equal to the
microchannel diameter. In a micro channel, this flow is formed at relatively high continuous
phase flow rates and low dispersed phase flow rates, that is the flow of dispersed phase is
much lower than the fluid that completely wets the wall of the reactor.

1.10.2 Slug flow

Slug flow is formed when the flow rate of dispersed phase and continuous phase are equal
and low. In this flow, the interfacial tension plays a main role than the viscous and inertial
forces. Both fluids pass through the channel as an elongated bubble with hydraulic diameter
larger than the channel diameter. In this regime, one liquid flows as a continuous phase
while the other flows in the form of dispersed slugs with diameter longer than diameter of
the microchannel.

1.10.3 Stratified Flow

It is also known as parallel flow. In this type of flow, one of the fluid flow above the other
one and the inertial force prominent over the surface tension force. This flow provides easy
phase separation of product mixture at exit compared to another flow pattern.

1.10.4 Annular flow

Annular flow is formed, when the flow rate of dispersed phase is lower than the continuous
phase. In this flow, the inertial force prominent over the interfacial tension and viscous force
because of increase in superficial velocity (T. Jing et al., 2013).

5
1.10.5 Churn flow
This flow pattern is formed when the liquid flow rate is very high and it is very unusual to
form this flow in micro-channel.

1.11 Objectives of the thesis

The objectives of the thesis are
1. To synthesize the deep eutectic solvents for the extraction studies.
2. To measure the physical properties of deep eutectic solvents suitable for the
extraction process.
3. To perform the extraction of aromatics from aliphatic/aromatic mixture by using
deep eutectic solvent in micro-channels with various geometries and flow rates.
4. To generate the bubble and slug flow inside the micro-channels.
5. Power requirement to transport deep eutectic solvent through micro-channels

1.12 Organization of Thesis

A brief description of thesis is described here

Chapter 1 Introduction
This chapter contain an overview of solvent extraction, need for aromatic extraction, uses of
aromatics, selection of solvents, deep eutectic solvents, synthesis of deep eutectic solvents,
Advantages of DES over ionic liquids, flow pattern inside microchannel, advantages of
micro-channels, objectives of the thesis, organization of the thesis.
Chapter 2 Literature review
This chapter presents the literature review on experimental studies in microchannel.
Chapter 3 Experimental method
The experimental setup, experimental procedure, details of chemicals used and their
properties are described in this chapter.
Chapter 4 Results and discussions
In this chapter, the obtained experimental results are discussed
Chapter 5 Conclusion
This chapter summarizes the thesis.
Appendix
The snapshots of slugs and bubbles formed in microchannel are presented in Appendix.

6
 Chapter 2
Literature review
This chapter presents the review on experimental studies of liquid-liquid extraction
conducted in micro channels. There are few publications on my topic of research study and
limited results of experimental studies on extraction in micro channels by using deep eutectic
solvent as solvent. In the various journals the performance of extraction in micro-channel
reactor can be characterized by varying and checking with the different dimensions and flow
conditions.
M. A. Kareem et al (2010) measured the physical properties such as melting temperature,
density, viscosity, pH as a function of temperature of the selected phosphonium-based DESs
such as methyl triphenyl phosphonium bromide + glycerine (molar-ratio of 1:1.75), methyl
triphenyl phosphonium bromide + ethylene glycol (1:4),methyl triphenyl phosphonium
bromide + 2,2,2-triflouracetamide (1:8), benzyl triphenyl phosphonium chloride + glycerine
(1:5), benzyl triphenyl phosphonium chloride + ethylene glycol (1:3), benzyl triphenyl
phosphonium chloride + 2,2,2-triflouracetamide (1:3). They synthesized these novel class of
DESs by stirring up with mechanical stirrer. They observed the formation of homogeneous
colourless liquid by keeping the temperature at 70 C and mixing time for 3 h respectively.
They found that the type of the salt and hydrogen bond donor and the mole ratio of both
compounds have a paramount effect on the studied properties.
M. A. Kareem et al (2012) studied the extraction of aromatics hydrocarbons from
aromatic/aliphatic mixtures by the application of phosphonium based deep eutectic solvent.
They obtained the data for liquid-liquid equilibria for various mixtures of benzene + hexane
+ DES system at the different temperatures of 27, 35, 450C respectively. They observed that
the ethylene glycol used in preparation of deep eutectic solvent (Methyl triphenyl
phosphonium bromide + ethylene glycol) was not present in the raffinate layer using gas
chromatographic analysis, which eliminates the step of further separation of solvent. They
had studied by varying the molar ratio of DES in the ratio of 1:4 (hydrogen bond acceptor:
hydrogen bond donor) and achieved selectivity greater than 93 and showed high extraction
efficiency at the lower aromatic concentration at the conditions of feed to DES of 1:1 mass
ratio and temperature of 450C.
M. A. Kareem et al (2013) conducted the experiments for the separation of aromatic
hydrocarbons from aromatic/aliphatic mixtures by using phosphonium-based DESs. They

7
investigated the application of the DESs formed by mixing ethyl triphenyl phosphonium
iodide as a salt with ethylene glycol as a HBD. They measured the LLE data at different
temperatures and concentrations of toluene in the toluene/heptane mixtures. They analysed
the presence of hydrogen bond donor in the raffinate phase by using the gas chromatogram
and found that there was no presence of ethylene glycol in raffinate layer. They found that
the high selectivity of 65.83 was obtained for the DES (ethyl triphenyl phosphonium iodide+
ethylene glycol in the molar ratio of 1:10) at low aromatic concentration and temperature of
500C.
Y. Hou et al (2015) performed experiments to separate toluene from the mixture of toluene
and n-hexane using tetra butyl phosphonium bromide + levulinic acid in the molar ratio of
1:6. They studied the effect of temperature, mole fraction of toluene, mole ratio of DES to
toluene, hydrogen bond donor and hydrogen bond acceptor on extraction efficiency and
selectivity such that as temperature increases the efficiency remains in range of 51.4 and
54.4% and as mole fraction of toluene increases from 0.1 to 0.6 the extraction efficiency
increases from 45.6 % to 87.1% and selectivity decreases from 122.3 to 69.3, as mole ratio
of DES to toluene increases from 3 to 13 the extraction efficiency increases and selectivity
increases from 2 to 6 mole ratio and then it decreases with further increasing of mole ratio.
N. R. Rodriguez et al (2015) studied the separation of benzene from hexane/ benzene
mixture by using DES as extracting agent. They used tetrahexylammonium bromide:
ethylene glycol with molar ratio = (1:2) (DES 1) and tetrahexylammonium bromide: glycerol
with molar ratio = (1:2) (DES 2). They determined the properties such as density and
viscosity and found that both are decreasing with increase in temperature. They found that
the solute distribution coefficient and selectivity values, DES 1 would be preferred over DES
2 for this separation and the lower values of density and viscosity of DES 1 compared to
DES 2 also suggest that DES 1 will be the best option from the studied DESs.
M. K. Alomar et al (2016) synthesized the six DESs, which are based on glycerol as a HBD
and six different salts such as methyl triphenyl phosphonium bromide (MTPB); benzyl
triphenyl phosphonium chloride (BTPB); allyl triphenyl phosphonium bromide (ATPB);
choline chloride (ChCl); N, N diethyl ethanol ammonium chloride (DAC); and tetra-n-
butylammonium bromide (TBAB). The mixture of the salt and HBD were mixed at 400 rpm
and 353 K with the mixing time of 3hours. They have investigated the physical properties of
the prepared DESs such as density, viscosity, conductivity, and surface tension as functions
of temperature.

8
P. K. Naik et al (2016) performed liquid- liquid equilibrium experiments for the ternary
systems: heptane+ toluene+ (methyl tri phenyl phosphonium bromide + ethylene Glycol
(1:4)) DES1, heptane+ toluene+ (methyl tri phenyl phosphonium bromide + glycerol (1:4))
DES2, heptane+ quinoline+DES1, heptane+ quinoline+ DES2 for the removal of toluene
and quinoline respectively. They analysed the concentration of DES in raffinate layer by
NMR spectrometer. DES1 is preferable over DES2 due to the system with DES1 have high
distribution ratio of 35.27 and selectivity of 3344.2. They found that the selectivity and
distribution ratio is highest for quinoline over toluene and found higher values at low
concentration of aromatic feed. So, they preferred DES1 as a solvent over DES2 for toluene
extraction.
K. A. Kurnia et al. (2016) determined the experimental liquid-liquid equilibrium information
for three novel ternary systems {hexane + (pyridine, or benzene, or toluene) + DES}at
temperature 298.15 K and at atmospheric pressure. The considered DES was composed by
Choline Chloride and D-glucose and it is prepared by mixing 1:1 ratio of [Ch]Cl to glucose,
then the mixture was stirred under constant speed at 500 rpm and at 353.15 K until
homogenous transparent colourless liquid was formed. They resulted that the DES formed
had the ability on extracting aromatic compound from aliphatic hydrocarbon. They
investigated the impact of aromatic compounds, namely benzene, toluene, and pyridine
chemical structures on the liquid-liquid extraction. They have calculated the selectivity and
solute distribution ratio and concluded that the selectivity values are greater than unity for all
the studied ternary systems. They confirmed that the studied DES could be used as solvent
for the extraction of aromatics from aliphatic hydrocarbons. They reported that the large
amounts of DES were required due to very low distribution ratios. The highest value of
selectivity obtained for the (hexane + toluene + DES) system which hold the value of
177.16. They compared the calculated solute distribution ratio and selectivity of the three-
novel ternary system with the ternary system of hexane + benzene+ sulfolane and found that
the selectivity was resulted to be higher by using DES over to sulfolane.
N. R. Rodriguez et al (2016) studied the performance of different DESs for the separation of
aromatics from the aromatics and aliphatic mixture and effect of the alkyl chain length of
cation. They found that solubility of the aromatic component is higher than that of the
aliphatic component of the selected DESs. They measured the composition of the system of
benzene, hexane, DES by using the gas chromatography equipped with a flame ionization
detector. They showed that the increase of the alkyl chain lengths of the cations leads to
increase of distribution ratio of benzene and which decreases the selectivity.
9
2.1 Research Gap
In most of the literatures, they used the conventional solvents such as sulfolane,
furfural, ethylene glycol, diethylene glycol, triethylene glycol, tetra ethylene glycol, N-
Methyl-2-pyrrolidone, N-Formyl morpholine for the process of extraction of aromatics from
the feed mixture, yet the selectivity achieved for the considered conventional solvents was
found to be low compared to deep eutectic solvents. No work was done on experimental
study of liquid- liquid extraction of aromatics using deep eutectic solvents as a solvent in
micro-channels, for which study on the liquid-liquid equilibria is required, because no
particular papers are there on liquid-liquid extraction.
Hence, the aim of the present work is to perform the experimental studies on liquid-
liquid extraction of aromatics using deep eutectic solvent in micro-channels, there by
performing the operations and evaluating the results.

10
 2.2 Summary of Literature Review

Table 2.2.1 Overview of Literature Review

DES synthesis Solute distribution ratio and
Author Year System Extraction Efficiency
conditions Selectivity
Kareem et al 2010 phosphonium-based DESs Mixing time- 3 hrs
Temperature- 700C
Kareem et al 2012 Hexane-Benzene- Mixing time- 3 hrs Highest value of distribution ratio Observed high efficiency at the
Phosphonium based DES Temperature- 600C obtained is 93 for the DES (molar ratio of lower aromatic concentration at
(Methyl tri-phenyl Rotational speed-200 1:4) the conditions of feed to DES of
phosphonium bromide + rpm 1:1 mass ratio and temperature
ethylene glycol) of 450C.
Kareem et al 2013 Heptane- Toluene- Mixing time- 3 hrs High distribution ratio was obtained at Highest extraction efficiency is
phosphonium-based DESs Temperature- 800C 400C for the DES (1:6) of 0.6110 obtained at 600C for the DES
(Ethyl tri-phenyl Rotational speed-600 Highest selectivity value of 65.83 was (1:10)
phosphonium iodide + rpm obtained for DES (1:10) at low aromatic
ethylene glycol) concentration and at 500C
DES synthesis Solute distribution ratio and
Author Year System Extraction Efficiency
conditions Selectivity

12
Hou et al 2015 Hexane- Toluene- (tetra-butyl Mixing time- 1 hrs Effect of hydrogen bond donor gives the Effect of hydrogen bond donor
phosphonium bromide + Temperature- 800C highest selectivity of 100 gives extraction rate of 54.4%.
levulinic acid Rotational speed-40 Effect of mole ratio of DES to toluene Effect of mole ratio of DES to
(1:6)) rpm obtained, the highest peak of selectivity toluene gives extraction rate of
and extraction rate of 110 and 64%. 64%.

Rodriguez et al 2015 1. Hexane- benzene-DES1 Mixing time- 3 hrs Highest distribution value was obtained High efficiency was obtained,
(tetra hexyl ammonium Temperature- 600C for the DES1, which is of 1.41 for the DES1 system over DES2
bromide + ethylene glycol Highest selectivity of 8.58 was obtained system
(1:2)) for DES at low aromatic concentration
2. Hexane- benzene-DES2
(tetra hexyl ammonium
bromide + glycerol (1:2))

Alomar et al 2016 Glycerol based DESs Mixing time- 3 hrs

Temperature- 800C
Rotational speed-400
rpm
DES synthesis Solute distribution ratio and
Author Year System Extraction Efficiency
conditions Selectivity
P. K. Naik et al 2016 1.Heptane- Toluene/ Mixing time- 24 hrs Highest distribution ratio value of 35.27

11
 Quinoline - (Methyl tri phenyl Temperature- 600C was obtained for the (heptane+ quinoline
phosphonium bromide + Rotational speed-800 + DES1) system.
Ethylene Glycol (1:4) DES1) rpm Highest selectivity value of 3344.2 was
2. Heptane- Toluene/ obtained for 30% concentration of
Quinoline - (Methyl tri phenyl quinoline for the (heptane+ quinoline +
phosphonium bromide + DES1) system.
Glycerol (1:4) DES2)
Kurnia et al 2016 hexane + pyridine, or benzene Mixing time- 2 hrs Highest distribution ratio value of 0.66
or toluene + DES (Choline Temperature- 800C was obtained for the (hexane + pyridine +
chloride + Glucose (1:1)) Rotational speed-400 DES) system.
rpm Highest selectivity value of 177.16 was
obtained for the (hexane + pyridine +
DES) system.
DES synthesis Solute distribution ratio and
Author Year System Extraction Efficiency
conditions Selectivity
Rodriguez et al 2016 1. Hexane- Benzene- Glycerol Mixing time- 2 hrs Distribution ratio increases with increase
0
based DES Temperature- 25 C of the alkyl chain lengths of the cations
2. Hexane- Benzene- Ethylene Rotational speed-500 and the highest distribution ratio value is
Glycol based DES rpm obtained of 0.86 for the DES
(Tetrahexylammonium chloride +
Ethylene glycol (1:2)).

12
 Selectivity decreases with increase of the
alkyl chain lengths of the cations and the
highest selectivity value of 171.43 is
obtained for the DES
(Tetraethylammonium chloride +
Ethylene glycol (1:2)).

13
 Chapter 3
EXPERIMENTAL SETUP

In this chapter, description of the chemicals used, physical properties of the

chemicals, experimental methods, experimental setup and procedure are reported.

3.1 Chemicals used

The chemicals used in the experimental work were deep eutectic solvent (Methyl
triphenyl phosphonium bromide/choline chloride + ethylene glycol/glycerol). Methyl
tri phenyl phosphonium bromide, choline chloride, glycerol and ethylene glycol are
used in the experiment with a purity of 98 %, 99 %, 99 %, and 99 % respectively.
These chemicals are used without further purification. The experiments were
conducted at room temperature. The chemicals used in experiment are listed in Table
3.1.1.

Table 3.1.1 Chemicals used in present work

S. No. Name Supplied By
Methyl triphenyl phosphonium
1. Loba Chemie Pvt. Ltd
bromide
2. Choline Chloride Loba Chemie Pvt. Ltd
3. Ethylene glycol Loba Chemie Pvt. Ltd
Thermo Fischer Scientific India Pvt.
4. Glycerol
Ltd
5. Toluene Spectro chem Pvt. Ltd
6. n-Heptane Spectro chem Pvt. Ltd

3.2 Physical Properties of Chemicals

3.2.1 n-Heptane
n-Heptane is an alkane of seven carbon atoms with the chemical formula C7H16. It is
colorless liquid at room temperature with boiling point of 98.830C. It is widely applied
in the laboratories as a non-polar solvent. Table 3.2.1.1 and Figure 3.2.1.1 shows the
physical properties and structure of n-Heptane.

14
Table 3.2.1.1 Physical properties of n-Heptane
Molecular formula C7H16
Molar mass 100.21 gmol1
Appearance Colourless liquid
Density 0.6795 g/cm3 at 20C
Odor Petrolic
Viscosity 0.386 mPa*s at 20C
Melting Point -90.549C
Boiling Point 98.380C

Figure 3.2.A.1 Structure of n-Heptane

3.2.2 Toluene
Toluene is an important organic compound with the chemical formula C7H8 and
because it contains carbon and hydrogen atoms, toluene comes under the hydrocarbon
class. It is a colorless and highly flammable liquid with a sweet smell. It is widely used
as an industrial feedstock and a solvent. Table 3.2.2.1 and Figure 3.2.2.1 shows the
physical properties and structure of toluene.

Molecular formula C7H8

Molar mass 92.14 g.mol-1
Appearance Colorless-liquid
Odor Sweet, pungent
Density 0.87 g/mL (200C)
Melting point -95 0C
Boiling point 111 0C
Viscosity 0.590 cP (200C)

15
Table 3.2.2.1 Physical Properties of Toluene

Figure 3.2.2.1 Structure of toluene

3.2.3 Deep Eutectic solvents

Based on the literature, four DESs such as
DES1: 1 mol Methyl triphenyl phosphonium bromide + 4 mol ethylene glycol,
DES2: 1 mol Methyl triphenyl phosphonium bromide + 3 mol glycerol,
DES3: 1 mol Choline chloride + 2 mol ethylene glycol,
DES4: 1 mol Choline chloride + 2 mol glycerol were considered as a solvent for the
extraction process.
Each DES was synthesised by mixing in the molar proportion, then the mixture was
mixed under specified conditions of mixing time, temperature and rotational speed,
until the homogeneous transparent colourless liquid form was obtained. The prepared
deep eutectic solvents were stored in the sealed laboratory vials and extreme
precautionary measures were taken for holding it air moisture tight. The temperature
and rotational speed maintained for the proper mixing of the DESs are tabulated in
Table 3.2.3.1.

Table 3.2.3.1 Temperature and Rotational speed maintained for proper mixing of
DESs
S. No DES Mixing time Temperature Rotational
(0C) speed(rpm)

1 DES1 3 hrs 60 200

2 DES2 3 hrs 80 400
3 DES3 3 hrs 70 300
4 DES4 30 mins 80 400

16
The measured physical properties of the synthesized DESs were refractive index,
density, pH, surface tension and contact angle as a function of temperature and
compared with the literatures values and observed that the not much variation in the
measured values with the literature values.

3.2.3.1 Refractive Index

Refractive indices of the synthesized DESs were measured by varying the

temperatures from 20 to 50 0C utilizing ATAGO RX-7000i Automatic Digital
Refractometer, shown in the Figure 3.2.3.1.1. This meter has a built-in method for
calibration using deionized water. The calibration was done automatically before each
test. We can observe the stage of calibration on the display as zero set end. The desired
sample chosen should be placed over the surface of prism, and the readings can be
noted down once the set temperature was reached.

Table 3.2.3.1.1 Comparison of Experimental and Literature values of refractive

indices of the synthesized DESs as a function of Temperature

Temp
(C) DES1 DES2
Exp. Value Lit. Value (Error) Exp. Value Lit.Value (Error)
20 1.56343 1.56000 0.00343 1.57462 - -
25 1.56176 1.55836 0.00340 1.57301 1.5715 0.00151
30 1.56005 1.55660 0.00345 1.57138 - -
35 1.55835 1.55490 0.00345 1.56974 - -
40 1.55661 1.55318 0.00343 1.56803 - -
45 1.55494 1.55140 0.00354 1.56628 - -
50 1.55318 1.54972 0.00346 1.56408 - -

Temp
(C) DES3 DES4
Exp. Value Lit. Value (Error) Exp. Value Lit.Value (Error)
20 1.46931 - - 1.48525 - -
25 1.46844 1.46823 0.00021 1.48419 1.48675 -0.00256
30 1.46740 1.46699 0.00041 1.48309 1.48558 -0.00249
35 1.46635 1.46575 0.00060 1.48193 1.48433 -0.0024
40 1.46532 1.46445 0.00087 1.48077 1.48326 -0.00249

17
 45 1.46406 1.4632 0.00086 1.47962 1.48211 -0.00249
50 1.46286 1.46197 0.00089 1.47847 1.48093 -0.00246

Figure 3.2.3.1.1 ATAGO RX-7000i Automatic Digital Refractometer

Table 3.2.3.1.1 provides the comparison of experimental and literature values of

refractive indices of the synthesized DESs as a function of temperature, which
demonstrates the Refractive index is a function of temperature. Figure 3.2.3.1.2
provides the plot to give relation such an extent that refractive index decreases with
increase in the temperature. In general, refractive indices of materials decrease with
increasing temperature due to the reduction in density. The highest refractive index
value of 1.57462 was recorded for DES2 at the temperature of 20 C. DES3 at a mole
ratio of 1:2 salt to hydrogen bond donor displayed the lowest value of 1.46286 at 50

C. The refractive indices for the measured DES1 are observed to be greater than those
reported literature values (Kareem et al., 2010). This is expected because of the high
content of ethylene glycol which has a high refractive index value due to its high
density.

18
 DES1 DES2 DES3 DES4
1.6

1.58

1.56
REFRACTIVE INDEX

1.54

1.52

1.5

1.48

1.46

1.44
0 10 20 30 40 50 60
TEMPERATURE (C)

Figure 3.2.3.1.2 Variations of Experimental values of refractive index with

temperature

3.2.3.2 Density
Kruss DS7800 Density Meter was used for measuring the density of the
synthesized DESs at various temperatures, which was shown in Figure 3.2.3.2.1. The
temperature range for the density meter was 10 to 50 C. The device is very compact,
precise and suitable for all liquids, emulsions and pastes. The low sample volume that
can be injected for the required reading was around 0.9ml. In this work, the density of
the synthesized DESs were measured in temperature range of 10-450C. Table 3.2.3.2.1
provides the experimental density values for the synthesized DESs and compared
with the literature values and the error obtained is found to be in the trace value, which
shows the density is a function of temperature. Figure 3.2.3.2.2 provides the plot to
give relation such an extent that density decreases with increase in the temperature.

19
 Figure 3.2.3.2.1 Kruss DS7800 Density Meter
Table 3.2.3.2.1 Comparison of Experimental and Literature values of densities of
the synthesized DESs as a function of Temperature

Temp
(C) DES1 DES2

Exp. Value Lit.Value (Error) Exp. Value Lit.Value (Error)

10 1.2483 - - 1.4963 - -
15 1.2446 - - 1.4927 - -
20 1.2408 - - 1.4892 - -
25 1.2371 1.2325 0.0046 1.4823 1.4875 -0.0052
30 1.2335 1.2290 0.0045 1.4810 1.4840 -0.0030
35 1.2300 1.2255 0.0045 1.4775 1.4805 -0.0030
40 1.2265 1.2220 0.0045 1.4725 1.4770 -0.0045
45 1.2229 1.2185 0.0044 1.4695 1.4735 -0.0040

20
Temp
(C) DES3 DES4

Exp. Value Lit. Value (Error) Exp. Value Lit. Value (Error)
10 1.1272 - - 1.2025 1.2001 0.0024
15 1.1249 - - 1.1996 1.1973 0.0023
20 1.1214 1.11704 0.00436 1.1967 1.1943 0.0024
25 1.1187 1.11416 0.00454 1.1938 1.1912 0.0026
30 1.1158 1.11129 0.00451 1.1910 1.1885 0.0025
35 1.1131 1.10842 0.00468 1.1882 1.1857 0.0025
40 1.1105 1.10557 0.00493 1.1854 1.1823 0.0031
45 1.1077 1.10271 0.00499 1.1827 1.1802 0.0025

The results showed that highest density value of 1.4963 was recorded for DES2 at the
temperature of 200C and the lowest value of 1.1077 was displayed at 450C. At 450C,
the densities of DES1, DES2, DES3, DES4 were 1.2229, 1.4695, 1.1077, 1.1910
g.cm3 respectively. In general, density decreases as temperature increases. This is due
to the increase in activity and molecular mobility, which increase the molar volume of
the solution, which thereby reduces the density.

DES1 DES2 DES3 DES4

1.6000

1.5000

1.4000
DENSITY (g/ml)

1.3000

1.2000

1.1000

1.0000

0.9000

0.8000
0 10 20 30 40 50
TEMPERATURE (C)

Figure 3.2.3.2.2 Variation of Experimental values of Densities with temperature

21
The results of the work were compared to results that has been reported in literature. A
slight error of 0.0024 was observed between DES1 measured value, which was 1.2371
g cm3 and MTPB:EG reported by (Kareem et al., 2010) which was 1.2325 g cm3 at
250C, even though the molar ratio used in that study was 1:4. Furthermore, the density
of DES2, DES3 and DES4 was found to be agreed with reported values but shows
difference in the traces (Leron et al., 2012).

3.2.3.3 pH

The pH of the synthesized DESs was measured at different temperatures using Auto
Digital pH meter. The readings were taken as a function of temperature ranging from
20 to 60 0C. The Auto Digital pH meter was calibrated by standard pH buffer
solutions.
Table 3.2.3.3.1 pH of the synthesized DESs as a function of Temperature

Property pH
Temp (C) DES1 DES2 DES3 DES4
20 6.46 6.8 5.5 6.8
30 6.31 6.72 5.42 6.64
40 6.21 6.57 5.37 6.41
50 6.14 6.46 5.34 6.11
60 6.05 6.4 5.32 5.89

In this work, the pH values of glycerol-based DES as function of temperature varied in

the range of 5.89 6.8. The room temperature measurement of pH for phosphonium
based-DESs was around 6.8, indicating approximate neutral behaviour. Table 3.2.3.3.1
shows the parameters of the pH values of the synthesized DESs with respect to
temperature. As shown in Figure 3.2.3.3.1, the pH of DES1 and DES3 does not change
significantly within the range of the temperatures 20 to 60 0C. The studied DES
formed between methyl triphenyl phosphonium bromide and glycerol in the ratio of
1:4 and the DES formed between choline chloride and glycerol in the ratio of 1:2
resulted in obtaining the similar pH values. It is clear that the pH of Phosphonium
based DESs and Choline chloride based DESs has low sensitivity to temperature.
From Fig. 3.2.3.3.1, we can conclude that the temperature pH relationship was
displayed linearly.

22
 DES1 DES2 DES3 DES4
7

6.5

6
pH

5.5

4.5

4
0 10 20 30 40 50 60 70
Temperature (C)

Figure 3.2.3.3.1 Variations of pH with Temperature

3.2.3.4 Surface tension and Contact angle

The surface tension and contact angle of the synthesized DESs were measured at the
room temperature using Kruss DSA25 Drop Shape Analyzer shown in Figure
3.2.3.4.1. The surface tension readings were taken by selecting the pendant drop mode
with the needle size of 1.835mm and the camera position of full tilted (00).
Surface tension is an important property which is measured as the energy required to
increase the surface area of a liquid by a unit of area. It is used in many areas
especially in emulsions and surfactants applications. In this work, the surface tension
of the selected four DESs was measured at room temperature of 250C. The values of
surface tension at room temperature for DES1, DES2, DES3 and DES4 were 51.53,
60.29, 50.61 and 61.68 mN m1 respectively. Table 3.2.3.4.1 shows the surface tension
readings with respect to room temperature for the selected DESs. The results showed
that the highest surface tension was recorded for DES4 at room temperature, and this
agreed with the result reported (zhang et al., 2012).

23
 Figure 3.2.3.4.1 Kruss DSA25 Drop Shape Analyzer
Table 3.2.3.4.1 Comparison of Experimental and Literature values of surface
tension of the synthesized DESs at room temperature (250C)
S. No DES Measured Surface tension Surface tension Lit.
(mN/m) values (mN/m)

1 DES1 51.53 51.29

2 DES2 60.29 58.94
3 DES3 50.61 49
4 DES4 61.68 58.79

The contact angle was measured by considering the sessile drop mode with the
needle requirement size of 0.5mm and the camera reading of vertical position (20).
Table 3.2.3.4.2 shows the contact angle readings with respect to room temperature for
the selected DESs. The receding and advancing angles for each DES were denoted by
CA(R) and CA(L) respectively. The mean of the both angles was denoted by CA(M).
The contact angle of the four selected DESs was measured at room temperature
of 25 0C. The contact angle values at room temperature for DES1, DES2, DES3 and
DES4 were 31.12, 41.95, 49.99 and 67.26 mN m1 respectively.

24
Table 3.2.3.4.1 Experimental values of Contact angle of the synthesized DESs at
room temperature (250C)

Property DES1 DES2 DES3 DES4

CA(R) 30.89 42.24 50.4 66.74

CA(M) 31.12 41.95 49.99 67.26
CA(L) 31.35 41.67 49.58 67.78

3.3 Analysis method

The refractive index method is used for analyzing the concentration of samples in the
either of the phases. The instrument used for the study of the calibration process was
the ATAGO RX-7000i Automatic Digital Refractometer with the feature of
temperature range of 10 to 50 0C.

3.3.1 Calibration plot

The analysis part was done by considering the sample mixtures of ternary system, until
the phases reaches the equilibrium state. For this, the samples were taken in the vials
by adding at different proportions of components on the weight basis. The BSA224S-
CW electronic weighing balance was used for the weighing the samples. Then the
samples were subjected for mixing on magnetic stirrer at the temperature of 35 0C and
rotational speed of 300 rpm respectively for one hour and then kept for settling at the
constant temperature of 35 0C in the incubator for 5 hours, until it forms homogenous
clear liquid.
The samples were then tested by measuring the refractive index by placing two to
three drops of sample on sensor, which reads the RI value. Likewise, for each sample
prepared, the RI values were taken three to four times for accurate values and thereby
reducing the error in calibration graph. Then after, the graph plotted between mole
fraction of component and refractive index for the calibration, which was shown by
model plot in Figure 3.3.1.1. The plot leads to the straight line and the refractive index
values noted for the unknown concentration of the samples were obtained by plotting
corresponding mole fraction of component for the obtained measured RI value.

25
 1.559

1.558

1.557
Refracctive Index

1.556

1.555

1.554

1.553

1.552
0.6500 0.7000 0.7500 0.8000 0.8500 0.9000 0.9500 1.0000
Mole fraction of component

Figure 3.3.1.1 calibration plot model

3.4 Experimental Setup
Figure 3.4.1 demonstrates the experimental setup which constitutes of glass syringes,
syringe pumps, micro-channel fabricated on acrylic sheet, PVC tubes, camera operated
with computer, light source.
The syringe pumps were supplied by Yashtech India Pvt. Ltd., Nasik, India. The
sample fluids were introduced to micro-channel using syringe pumps. The volumetric
flow rate of the pumps is in the range of 0.01- 9.99 mL/min. The glass syringes with 5
mL and 10 mL capacities were supplied by Top Syringe Mfg Co Pvt Ltd. The PVC
tube was used for connecting the syringes to microchannel. The liquids were filled in
two glass syringes separately which were then loaded on the syringe pumps.
The syringes with 5 mL volume were used when the flow rate was less than 1
mL/min and 10 mL volume syringes were used for flow rate above 1 mL/min. The
micro-channels of three different widths, namely 0.75 mm, 1.0 mm with T-shaped
cross-section and 0.6 mm with perpendicular T- shaped cross-section were utilized for
the experiments.
The camera used was high speed camera which can focus on the flow in the
microchannel and observe the regime and thereby justify the pattern of flow with the
help of the light source. Figure 3.4.2 shows the schematic diagram of the setup used.

26
 Figure 3.4.1 Experimental setup

computer

camera
syringe

microchannel

Syringe pump

Light Sample
collection
source
Syringe pump

Figure 3.4.2 Schematic diagram of experimental setup

27
3.5 Microchannel Engraving
Acrylic sheet was utilized for fabricating the microchannel. The plexi glass used was
chemically resistant towards the liquids used for the experiment, and was supplied by
Bombay hydraulics and pneumatics, Jaipur. The channeling was done by using laser
engraving technique and operated by laser engraving cutter (MK Advertising, Jaipur).
The channel design was done using Auto-CAD package and imported the file to Corel
draw 7 which further refines the minor mistakes like joining at the edges.
Two acrylic plate with same dimensions 80 mm x 290 mm was used for fabricating
microchannel reactor. Two micro-channels used were engraved with dimensions of
0.75, 1.0 width and length 240 mm respectively shaped T-junction in one of the plate
and other microchannel used was with dimensions of 0.6 width and length 240mm
shaped perpendicular T-junction in one of the plate. The remained plate without
etching was applied vacuum grease to make air sealed and placed over the channeled
plate and tightened with allen nuts-bolts. The inlets and outlet of the micro-channel
was fitted with brass connectors of inch through which the liquids were introduced
into the channel using PVC tube which were connected from syringes to inlets of
microchannel.

28
 Figure 3.5.1 Laser Engraving machine

Figure 3.5.2 Image of a 0.6 mm x 0.5 mm x 240 mm microchannel reactor

29
Figure 3.5.3 Image of a 0.75 mm x 0.5 mm x 240 mm microchannel reactor

30
 Figure 3.5.4 Image of a 1.0 mm x 0.5 mm x 240 mm microchannel reactor

3.6 Experimental procedure

The experiments were carried out in three different channels of widths 0.6 mm, 0.75
mm and 1.0 mm respectively. 1 mol of methyl triphenyl phosphonium bromide+ 4 mol
of ethylene glycol (Deep eutectic solvent) which was a novel solvent was used as
solvent, while mixture of toluene and n-heptane was used as feed. Deep eutectic
solvent and mixture of toluene and n-heptane were filled in glass syringe individually.
The glass syringes were settled on the syringe pumps such that no bubbles were
observed inside the syringes. Filled liquids inside the syringes were subjected to enter
the microchannel at respective flow rates.

31
The flow rates were adjusted to the requirement for the experiment to be performed
and normally to the extent of work, the flow rates were in the scope of 0.01 mL/min to
0.5 mL/min for solvent filled syringe pump and 0.01 mL/min to 5 mL/min for feed
mixture filled syringe pump. The slug and bubble flow was observed in the main
channel due to the acting shearing forces and formed like dispersed phase taken after
by continuous phase in microchannel. The dispersed layer formed was observed to be
deep eutectic solvent (methyl tri phenyl phosphonium bromide+ ethylene glycol), that
does not wet the surface of the channel due to its polar in nature. On the other side, the
followed layer, so called continuous layer formed was observed to be mixture of
toluene and n-heptane because it is non-polar in nature and wet the surface of the
channel. The samples obtained from the outlet were subjected to refractive index
analysis. The experiments were conducted at the different flow rates for various
geometries and studied the impacts of slug length, total velocity, flow rate, flow ratio
(ratio of flow rate of solvent to feed) on slug volume, extraction efficiency and
volumetric mass transfer coefficient. The experiments were repeated for two to three
times and the obtained average value was reported.
For the experimental study, the images were captured and analyzed using imageJ
software for calculating slug length. A 10mm dimension scale was marked above or
below the main channel, such that used dimension (pixel) in imageJ programming can
be converted into mm. From the calculated slug length, the variation in the slug
volume and interfacial area were calculated.
The concentration of toluene in the extract phase was analyzed by using
refractive index method. With the help of experimental liquid-liquid equilibria data
values, the equilibrium mole fraction of toluene in the extract phase is 0.343. The
refractive index value reading is taken for two to three times for each sample to obtain
the accurate reading. The obtained refractive index values were plotted in calibration
plot between mole fraction of toluene and refractive index and obtain the mole fraction
of toluene in the extract phase. The refractive index values were measured for the
experiments conducted in three different micro-channels of width 0.6, 0.75, 1.0 mm
with various flow rates.

32