Separation of Aromatic-Aliphatic using extracting agent by Gas

Chromatography
A
DISSERTATION
Submitted to

JHARKHAND UNIVERSITY OF
TECHNOLOGY, RANCHI

In Partial Fulfillment of the Requirement for the

Award of Degree of

MASTER OF TECHNOLOGY
IN
CHEMICAL ENGINEERING

With specialization in

PLANT DESIGN

Submitted by

SWATI
(20030720003)

Under the guidance of

Prof. Chelluboyana Vaishnava Raghunath & Amar Kumar

Assistant Professor, Department of Chemical Engineering
BIT, Sindri

CHEMICAL ENGINEERING
BIT SINDRI, DHANBAD-828123 (JHARKHAND)
DECEMBER, 2022
 BIT SINDRI, DHANBAD-828123
Department of Higher & Technical Education, Government of Jharkhand

CANDIDATE’S DECLARATION

I hereby certify that the dissertation entitled “Separation of Aromatic-Aliphatic

using extracting agent by Gas Chromatography ” which is being submitted in the

partial fulfilment of the requirement for the award of Master of Technology in Chemical
Engineering, with specialization in Plant Design, is a record of my own work carried out
under the supervision and guidance of Prof. Chelluboyana Vaishnava Raghunath & Amar
Kumar, Assistant Professor, Department of Chemical Engineering, BIT Sindri.

All information in this document has been obtained and presented per academic rules
and ethical conduct.
To the best of my knowledge, the contents presented in this dissertation have not been
submitted elsewhere for the award of any other degree/diploma.

Date: Signature
Place: B.I.T Sindri Swati
 BIT SINDRI, DHANBAD-828123
Department of Higher & Technical Education, Government of Jharkhand

CERTIFICATE OF DECLARATION FROM THE

SUPERVISOR

This is to certify that the work presented in the dissertation entitled “ Separation of

Aromatic-Aliphatic using extracting agent by Gas Chromatography ” in

partial fulfilment of the requirement for the award of Degree of Master of Technology in

Chemical Engineering with specialization in Plant Design at BIT Sindri is authentic work

carried out under my supervision and guidance.

To the best of my knowledge, the content of this dissertation does not form a basis for

the award of any previous Degree to anyone else.

Dr. Amar Kumar Dr. Chelluboyana Vaishnava Raghunath

(Guide) (Guide)
Assistant Professor Assistant Professor
Department of Chemical Engineering Department of Chemical Engineering
 BIT SINDRI, DHANBAD-828123 (JHARKHAND)
Department of Higher & Technical Education, Government of Jharkhand

CERTIFICATE OF APPROVAL FROM THE EXAMINERS

The foregoing dissertation entitled “Separation of Aromatic-Aliphatic using

extracting agent by Gas Chromatography” is hereby approved as a creditable study of

the research topic and has been presented satisfactorily to warrant its acceptance as a prerequisite

to the degree for Master of Technology in Chemical Engineering with specialization Plant

Design at BIT Sindri.

It is understood that by this approval, the undersigned do not necessarily endorse any

conclusion drawn or opinion expressed therein, but approve the dissertation for the purpose for

which it is submitted.

Internal Examiner External Examiner

Name: Name:
Designation Designation
Name of Department Name of Department
Name of the Institute Name of the Institute/Organization

Dr. Amit Kumar Gupta

Head, Department of Chemical Engineering
B.I.T SINDRI
 BIT SINDRI, DHANBAD-828123 (JHARKHAND)
Department of Higher & Technical Education, Government of Jharkhand

Plagiarism Evaluation Certificate

This is to certify that I, (Swati) of M. Tech (Plant Design) have checked my complete dissertation
entitled: (Separation of Aromatic-Aliphatic using extracting agent by Gas

Chromatography) for similarity/plagiarism using the “(Turnitin Official)”.

This is to certify that:
 The similarity in my dissertation is found to be (7%) {which is within the specified limit of
10% as per the JUT regulation}
 The similarity from a single source is (4%) maximum.
 Self-Plagiarism in my dissertation is found to be (%)
 The summary of the Plagiarism report is enclosed at last of the dissertation.

Swati Dr. Chelluboyana Vaishnava Raghunath & Amar

Kumar M. Tech (Plant Design)
Assistant
(20030720002) Chemical Engineering
Chemical Engineering BIT, Sindri
BIT, Sindri
 ACKNOWLEDGEMENT

I express my gratitude and sincere thanks to Prof. Amit Gupta and Prof.
Chelluboyana Vaishnava Raghunath for their guidance constant encouragement
and support during the course of our work. We truly appreciate and value their
esteemed guidance and encouragement from the beginning to the end of the thesis;
their knowledge and company at the time of crisis would be remembered lifelong.

I want to express my gratitude to Dr. Amit Kumar Gupta, Head of Department,

Chemical Engineering, BIT Sindri, Dhanbad, and special thanks to our respected PG
Coordinator’s Dr. Ashok Kumar Burnwal, and Dr. Ch. V. Raghunath Chemical
Engineering Department of BIT Sindri, Dhanbad, and all other faculty and staff
members of Department of Chemical Engineering, for their kind cooperation and
help.

Last but not the least, I would like to thank my parents and friends. We would like to
share this moment of happiness with them who rendered me enormous support of
love and care during the whole tenure of completion of this project.

Swati
 ABSTRACT

Chemical engineers faces a significant hurdle when attempting to separate aliphatic from aromatic
molecules. For mixtures containing less than 20 wt% aromatics, there is no effective separation
method. In this study, two distinct deep eutectic solvents (DESs) were investigated for their
viability as brand-new extracting agents for the separation of the mixture "hexane + benzene." A
set of DESs were tested for solubility at ambient temperature and atmospheric pressure in order to
choose the best solvent for this separation. The deep eutectic solvents used in this study were I
tetrahexylammonium bromide: ethylene glycol at a molar ratio of 1:2 (DES 1) and (ii)
tetrahexylammonium bromide: glycerol at a molar ratio of 1:2 (DES 2). At atmospheric pressure
and temperatures T = 293.2–343.2 K, measurements of density and viscosity were used to describe
the chosen DESs. Next, it was determined what the liquid-liquid equilibria (LLE) were for the
ternary systems (hexane + benzene + DES 1) and (hexane + benzene + DES 2) at T/K = 298.2 and
T/K = 308.2, respectively. Additionally, for the investigated ternary system with different solvents,
the solute distribution coefficient and selectivity values were determined and compared to LLE
data found in the literature. Finally, the nonrandom two-liquid (NRTL) model was used to correctly
correlate the experimental data. The results obtained indicate that DESs are promising extracting
agents for the industrial separation of naphtha streams with low aromatic concentrations.

Keywords-Benzene, Hexane, DES 1, DES 2, Aromatic, Aliphatic.

INTRODUCTION

In the petrochemical sector, distinguishing aromatic from aliphatic chemicals is not only
crucial but also incredibly difficult. Aromatics recovery from naphtha cracking streams is
critical because of two main reasons: (1) new requirements on the petroleum products which
demand a reduction of the level of sulfur and aromatic compounds to minimize their
environmental impact and (2) the economic value of the aromatic components as raw
material. This mixture contains azeotropes and components with close boiling points, making
separation problematic. 1,2 Sulfolane is used in industry to carry out this separation.
Sulfolane is used as the extracting agent in this method, which involves liquid-to-liquid
extraction. Extractive distillation is then used to recover the solvent. For combinations with
an aromatic content lower than 20%, this is not an effective separation technique due to the
significant energy investment required for the sulfolane recovery. Due to the higher aromatic
concentration at this point in the naphtha cracking process, the separation of aromatics from
aliphatic compounds is carried out. However, if the solvent recovery issue could be solved,
the separation could be carried out before naphtha cracking. As a result, the energy needs for
the entire cracking process would be decreased because there would be fewer flows that
needed to be heated in the columns. Several solvents have been researched recently as
sulfolane substitutes. Ionic liquids (ILs) have been suggested as extracting agents for this
separation. Some ILs have selectivity and solute dispersion coefficients that are comparable
to those of sulfolane. Furthermore, the solvent recovery issue mentioned above is solved by
ILs' minimal vapour pressure. For instance, flash distillation could make it simple to recover
ILs following the extraction. However, the greatest drawback for large-scale applications is
the high cost of the ILs as a result of their difficult synthesis. A novel class of solvents known
as deep eutectic solvents (DESs) was originally identified about ten years ago. When
combined in the right molar ratio, one or more hydrogen bond acceptors (HBAs) and one or
more hydrogen bond donors (HBDs) form DESs, which have a markedly lower melting point
than the original compounds. Many characteristics between DESs and ILs are similar,
including low vapour pressure, a broad range of liquid compatibility, and nonflammability.
In light of the previously noted solvent recovery issue, all of these characteristics are
intriguing. Additionally, when compared to ILs, DESs are simpler and less expensive to make
simply combining the various parts and heating them. The solvent recovery issue with the
traditional sulfolane technique and the high synthesis cost of the ILs would therefore be
solved if any DES exhibited distribution coefficient and selectivity values comparable to
those of sulfolane. The purpose of this work is to assess the efficacy of two various DESs as
extracting agents for the liquid–liquid extraction-based separation of aliphatic and aromatic
hydrocarbons. The mixture of benzene and hexane was chosen since ILs have been
extensively used in studies on its separation, whereas DES investigations have been quite rare
(so far). First, the solubility of benzene in several DESs was measured at T/K = 298.2 and
atmospheric pressure in order to choose an appropriate DES for this separation. After that, the
hexane solubility of those DESs with the highest benzene solubility was also determined. The
chosen DESs were I tetrahexylammonium bromide: glycerol with a molar ratio of 1:2 and (ii)
tetrahexylammonium bromide: ethylene glycol with a molar ratio of 1:2 based on the
solubility difference (DES 2). Second, the density and viscosity at T/K = 293.2-343.2 and air
pressure were measured to describe the chosen solvents. Third, at T/K = 298.2 and T/K =
308,2 and atmospheric pressure, the liquid-liquid equilibrium (LLE) data of the ternary
systems "hexane + benzene + DES 1" and "hexane + benzene + DES 2" were determined.
This was done to investigate the effects of temperature as well as the role of the deep eutectic
solvent's hydrogen bond donor (HBD) on the extraction of benzene from hexane. The solute
distribution coefficient and the selectivity were also computed from the experimental LLE
data and compared to the literature to assess the suitability of the tested DESs for separation.
Finally, the nonrandom two-liquid (NRTL) thermodynamic model was used to corroborate
the experimental LLE data. The DESs were handled as a single compound for the duration of
this article.
2. LITERATURE REVIEW

In 2020, Claudia Ricardo et.al. The need for precise amount enantiomers is currently
critical in a variety of fields, including pharmaceutical, agrochemical, forensic toxicology,
food, and environmental studies, among others. This article combines analytical techniques
for enantio seperation by gas chromatography, including direct and indirect techniques, and
discusses how they might be used in forensic toxicology, food, and environmental
investigation.

In 2019, Georg Dierkes et.al. Pressurized liquid extraction (PLE) and pyrolysis GC-MS
have been combined in an analytical technique to enable low quantification limits. A pre-
extraction step using methanol is followed by a PLE using tetrahydrofuran in the automated
extraction process. Limits of quantification for the most widely used synthetic polymers,
polyethylene (PE), polypropylene (PP), and polystyrene (PS), were attained down to 0.007
mg/g. For solid matrices like soil and sediment, recovery rates of more than 80% have been
attained. The created method was used to measure MP in environmental samples like
sediment, suspended matter, soil, and sewage sludge. From 0.03 to 3.3 mg/g in each of these
matrices. All three polymers were present in sewage sludge samples at concentrations
between 0.08 and 0.02 mg/g (PP) and 0.3.

In 2016, Sheng Ming Xie and Li Ming Yuan examined since 2010 the development of
chiral stationary phases for GC-based enantiomer separation. In the past six years, chiral
porous materials (MOSs, POFs, POCs, and inorganic mesoporous materials) have been
developed as well as cyclofructan derivatives, and their enantiomeric separation
characteristics and chiral recognition mechanisms have been described. Among the various
types of novel chiral stationary phases, some chiral stationary phases, like POCs-based
stationary phases, demonstrated excellent chiral recognition ability towards a variety of
racemic compounds. These phases were discovered to have the potential for widespread
applications in a number of fields as well as future commercialization.

In 2016, Jamie Schenk.et.al. To investigate the systematic deconvolution of mixtures of

coeluting isomers of dimethylnaphthalenes, a vacuum ultraviolet spectroscopic detector and
gas chromatography were used. To test the detector's proper accuracy, precision, and
sensitivity for differentiating overlapping isomers that had distinct but strikingly similar
absorption spectra, a variety of ratio combinations of 75:25, 50:50, 25:75, 20:80, 10:90, 5:95,
and 1:99 were prepared. It was discovered that all of the pairwise overlapping isomers tested
could be deconvoluted up to nearly two orders of magnitude (up to 99:1) in relative
abundance under reasonable injection conditions.

In 2016, Anumola P D.et.al. Benzyl alcohol is used in foods and pharmaceutical products,
so researchers looked into the straightforward and speedy gas chromatographic method for
identification of residual solvents present in benzyl alcohol. In the production of benzyl
alcohol, organic solvents like benzene, chlorobenzene, and toluene are frequently used.
Despite such manufacturing processes, a few solvents are still present in trace amounts. For
benzene, chlorobenzene, and toluene, respectively, the retention times were determined to be
8.824, 13.467, and 11.461 min when taken individually and in spiked standard solutions.

In 2016, Mir Ali Farajzadesh.et.al Six organophosphorous pesticide residues (malathion,

phosalone, dichlororvor, diazinon, profenofos, and chlorpyrifos) were determined, pre-
concentrated, and extracted in fruit juice and aqueous samples using elevated temperature,
dispersive, liquid-liquid microextraction/gas chromatography—flame ionisation detection.
Dimethyl sulfoxide, the disperser solvent, and 1,2-dibromoethae, the extraction solvent, were
swiftly injected into the sample that had been heated to a high temperature. Limits of
detection (0.82-2.72mg ml-1), linearity (r>0.994), enrichment factors (1600-2075), and
quantification (2.60-7.36 mg ml-1) are among the analytical parameters.

In 2015, Sergey P. Verevkin.et.al Deep eutectic solvents (DESs), which have been studied,
are thought to be a promising, environmentally friendly, and cost-effective replacement for
traditional volatile organic solvents. A helpful tool for making the best selection of the
selective solvent is the limiting activity coefficient. The activity coefficient at infinite dilution
of 23 solutes in DESs has been measured for the first time (aliphatic and aromatic
hydrocarbons, alcohols, ketones, ethers, and esters). Choline chloride and glycerol were
combined to form the DESs in molar ratios of 1:1 and 1:2. The measurements were
performed using gas-liquid chromatography in the 2978–358K temperature range. The
perturbed-chain statistical associating fluid theory was used to confirm the separation
effectiveness of DESs (PC-SAFT).

In 2015, Nerea R.Rodriguez.et.al Deep eutectic solvents (DESs) were investigated as a

novel extracting agent for the separation of a mixture of (hexane + benzene) in order to study
the separation of aliphatic and aromatic components. A solubility test of a group of DESs was
performed at ambient temperature and atmospheric pressure in order to choose the best
solvent for this separation. Tetrahexylammonium bromide: ethylene glycol with a molar ratio
of 1:2 (DES1) and tetrahexylammonium bromide: glycerol with a molar ratio of 1:2 were
chosen as the deep eutectic solvents for this investigation (DES2). At air pressure and
temperature T=293.2-343.2K, the density and viscosity of the chosen DESs were measured in
order to describe them. At air pressure and temperature T=293.2-343.2K, the density and
viscosity of the chosen DESs were measured in order to describe them. The results obtained
indicate that DESs are promising extraction agents for the commercial separation of neptha
streams with low aromatic concentrations.

In 2015, Ling Bai.et.al. Gas chromatography detectors based on vacuum ultraviolet (VUV)
spectroscopy (GC-VUV), which simultaneously collect full scan (115-240nm) VUV and UV
absorption of eluting analytes, were applied to analyse mixtures of permanent gases. These
complex mixtures of permanent gases included low molecular weight hydrocarbons, inert
gases, and toxic species. In order to separate gases, a porous layer open tubular column was
used. Natural gas and the headspace of water samples contaminated by natural gas were
separated and components like C1 and C5 linear and branched hydrocarbons, water, oxygen,
and nitrogen were found. The detection of flammable and toxic gases, including methane,
ethylene, chloromethane, dimethyl ether, 1-3-butadiene, CS2, and methylproprionate, among
others, was required for the transport of lithium batteries.

In 2015, Tiantian Jiao.et.al The phenol and cresols from low-temperature coal tar (model
oil) were successfully separated through complexing using the newly discovered reaction
agent (urea). Investigations were done into how contact time, reaction temperature, and initial
concentration affected the results. The chemical bond of the complex of urea and m-cresol
was examined using a Fourier transform infrared spectrometer to determine the upper layer's
phenol content. Finally, urea can be recovered via a reaction with diethyl ether, and after
three cycles, the phenols removal efficiencies can stay constant.

In 2015, Mohammed yahya Hadi.et.al. Phytochemicals under investigation are frequently

referred to as secondary metabolites. There were found to be 28 bioactive phytochemicals. in
the Nigella sativa methanolic extract. Molecular formulae, peak area, retention time, and
molecular weight are used to identify phytochemical compounds. The components -pinene,
D-glucose, 6-O—Dgalactopyranosyl, O-Cymene, DL-Arbinose, glucopyranosyl-
(1,fwdarw,3)—D-fruc, and O-Cymene were identified by (GC-MS) analysis of Nigella
sativa. Thymoquinone, Phenol, 4-methoxy-2, 3,6-trimethyl,pyrolidin-2-one-3 (Prapanoic
acid, methyl ester), 5-methylene-4, isopropylidene-5-methylex-4-enal, limonen-6-ol, pivalate,
longifolene, 2-(4-Nitrobutyryl) cyclooctane, and bisabolene.

In 2015, Marzieh Kaman Kesh.et.al. A simple and quick analytical method for the
simultaneous determination of 16 polycyclic aromatic hydrocarbons (PAHs) in grilled meat
was developed using microwave-assisted extraction and dispersive liquid-liquid
microextraction (MAE-DLLME), then the results were analysed using gas chromatography-
mass spectrometry (GC-MS). The efficient DLLME process parameters were optimised.
With a correlation coefficient (R2) greater than 0.98, there are good linear relationships mg g-
1. The upper and lower limits of quantification were 0.47 mg g-1 and 0.15 to 0.13 mg g-1,
respectively. Seven analyses had relative standard deviations (RSD%) that were lower than
9%. The percentages of those compounds recovered from grilled meat ranged from 85% to
104%.
In 2014, Yaowapa Lorjaroenphon and Keith R.Cadwallader Gas chromatography-
olfactometry and gas chromatography-mass spectrometry were used to characterise the
aroma-active compounds in common cola-flavored carbonated beverages. Eugenol, which
has a spicy, clove-like, and sweet aroma, and coumarin, which has a sweet, herbaceous
aroma, predominated in all coals. According to analysis of the enantiomeric compositions, (S)
- (+)-enantiomer (65.66%) was less potent as an odorant than (®-(-) linaloal (34.5%). The
three coals' aroma profiles matched those of the strong odorants that AEDA had identified.

In 2014, Alen Albreht et.al. Investigated the creation of a new derivation process and chiral
GC method for the quick screening of L-enantiomeric Carnitine's purity in different sample
matrices. The GC analysis of acrylcarnitines should also benefit from the derivatization
process. L-carnitine is widely used in functional foods and dietary supplements, so it is
crucial to maintain its enantiomeric purity. Maximum conversion of carnitine to -acetoxy-
butyrolactone was achieved (98% of the desired lactone and 2% of the side product -
crotonolactone) through optimization of the process.

In 2013, Luisa Schipillili.et.al. The citrus liquers under investigation are alcoholic drinks
made through maceration. Producers frequently add natural and or synthetic flavours to the
alcoholic syrup for technological and economic reasons to create artificial spirit drinks. The
purpose of this study is to compare the carbon isotope ratios of Italian liqueurs made from
lemon, bergamot, and mandarin to those found in real cold-pressed oils in order to determine
the authenticity of the products. These liqueurs are locally referred to as "limoncello,"
"bargamino," and "mandarinetto." To ascertain the enantiomeric distribution of particular
chiral volatile GC-MS for the qualitative analysis, additional analyses using direct
enantioselective gas chromatography were carried out.

In 2012, Masoom Raza Siddiqi For the simultaneous determination of heptane acetone,
tetrahydrofuran, ethyl acetate, methanol, 2-propanol, dichloromethane, toluene, and pyridine
in docetaxel, a straightforward and sensitive gas chromatographic method has been developed
and is volatile. The DB-WAXETR polyethylene glycol column, which has a length of 60
metres, a diameter of 0.0250 millimetres, and a film thickness of 0.25 minutes, was used to
separate the mixture. A systematic peak shape, good resolution, and reasonable retention time
are all features of the newly developed gas chromatographic method for all solvents.
Methanol, acetone, isopropanol, ethyl acetate, toluene, dichloromethane, tetrahydrofuran,
pyridine, and heptane were found to have respective limits of detection of 0.027, 0.50, 0.12,
0.070.0.180, 0.040, 0.170, and 0.040.

In 2010, Oznur Yasa Sahin.et.al. A new chiral liquid crystal, (s) -5-(10-undecenyloxy) -2-4-
(2-methyl butoxy) phenyliminomethyl phenol (UMBPIMP), was studied for its synthesis,
characterization, and mesomorphic properties. By using inverse gas chromatography,
differential scanning calorimetry, and optical polarising microscopy, the phase transition
temperatures of this mesogenic compound have been studied. In order to comprehend
UMBPIMP's selectivity as a stationary phase in gas chromatographic probes, the
thermodynamics of the compound were looked into. Inverse gas chromatography was used to
plot the retention diagrams of the isomers between 30 and 110 degrees Celsius.

In 2003, Marta Dregus.et.al. Enantio differentiation was accomplished using

multidimensional gas chromatography and heptakis (2,3,6-tri-o-ethyl) —cyclol-extrin as a
chiral stationary phase. The enantiomeric composition of 2-methylbutanol (1), 4-
methylhexanol (2), 2-methyl-butanoic acid (3), and 4-methylhexanoic acid (4) present in
rhubarb stalks were investigated. The enantiomeric ratios for all compounds were in favour of
the ® - enantiomers. The ratios of the alcohols (1 and 2) varied slightly from batch to batch,
but generally showed high excess of the ® - enantiomers. For the acid (3), a relatively small
range with an average of 65%(R):35%(S): was noted.

In 1997, J.F.Van Bosclaer.et.al. We recently reported finding phenylethylamine in a number

of samples we had taken from the illegal drug trade. Powders that typically contained
amphetamine and caffeine were initially found to contain -Phenylethylamine. Then, a couple
that had a history of drug use was discovered dead in their apartment. Large amounts of
amphetamine and phenylethylamine were found in the urine samples from both victims. To
ascertain the chirality of the detected drug, gas chromatography was used to reexamine all of
the positive samples. These findings further support the synthetic origin of -
phenylethylamine, attributing both victims' urine for its presence to either intentional or
unintentional ingestion. The urine samples' disproportionate isomeric composition supports
earlier claims of a stereoselective metabolism.
 3. MATERIALS AND METHOD
Materials.

Table 1 lists the substances used to determine the LLE data, along with their purity and
source. The substances employed for the solubility test, as well

Table 1. Chemicals Used in This Work

Chemical Purity Source

Acetone ≥99 VWR
benzene ≥99.9 VWR
 ethylene glycol ≥99 Merck
Hexane ≥99 Sigma-Aldrich
Pentane ≥99 Reidel-de Haen
glycerol ≥99 Merck
tetrahexylammonium ≥99 Across Organics
bromide

are displayed in the supporting information, Table 1, along with purity and source. None of
the compounds were further purified before usage.

DES Preparation

A Mettler AX205 balance was used to prepare the DESs, with a measurement uncertainty of
0.2 104 g. In a flask, the HBA and HBD were combined and heated while being stirred until a
clear liquid was produced. A thermostatic bath with temperature controller (IKA ETS-D5)
was used to regulate the temperature, and the measurement error was 0.1 K. T/K = 333.2 was
used to create DES 1 and DES 2. Table 2 displays the molecular structures of DES 1 and
DES 2.

DES Characterization.

Density and viscosity were measured using an Anton Paar SVM 3000/G2 Stabinger
densimeter and viscosimeter respectively with a high-precision thermostat with a stability of
0.005K at T/K= 293.2-343.2 and atmospheric pressure.

Table 2. DESs Selected for This Work; HBA, HBD, and Molar Ratios between Them

Abbreviatio HBD Molar Ratio HBA

n
DES 1 Ethylene glycol 1:2 Tetrahexylammonium bromide
DES 2 Glycerol 1:2 Tetrahexylammonium bromide

The density (with viscosity correction) and viscosity measurements have uncertainties of
±0.0005 gcm3 and ±0.35%, respectively.

Solubility Test.
The cloud point approach was used to calculate the solubilities of benzene and hexane in the
investigated DESs at T/K= 298.2 and atmospheric pressure. Hexane or benzene was added
dropwise to a vial containing around 4 g of DES until a minor turbidity in the samples was
noticed. The samples' components were then ascertained through weighing. A thermostatic
bath with temperature controller (IKA ETS-D5) was used to regulate the temperature with a
±0.1 K accuracy.

LLE Determination.

Atmosphere-pressure conditions and T/K values of 298.2 and 308 were used to calculate the
experimental LLE data. Weighed mixes of the investigated components within the
immiscible area were created for the experimental determination of the tie lines. The mixes
were put into 15 mL rubber-sealed vials to prevent losses from evaporation or moisture
absorption. The two phases were then vigorously agitated for at least three hours to allow for
close contact. They were then allowed to settle in a thermostatic bath overnight to ensure that
the balance was attained. Following phase separation, both phases were sampled with a
needled syringe, and gas chromatography was used to determine their contents (GC). Since
DESs have a very low vapour pressure, GC cannot be used to analyse them. As a result, only
hexane and benzene were examined in each phase, and a mass balance calculation was used
to determine the concentration of DES in each phase. The gas chromatograph used was a GC
Optima 3007 with FID (MDL< 1.8 Pg C/ s), capillary column, nitrogen as carrier gas with a
flow rate of 2.5 ml mn-1 and sample is injected using syringe having capacity of
10µl.equipped with a flame ionization detector. The following were the analysis's parameters:
DB-FFAP (30m × 0.538mm, 1µ) capillary column, 313.2 K column oven temperature for 2
minutes; 373.2 K temperature ramp (rate = 40 K/min) for 2.75 minutes; nitrogen as the
carrier gas; 2 mL/min flow rate; 548.2 K injector temperature; and 473.2 K detector
temperature. The split ratio used for the injection was 250, and the injection volume was 1μL.
The DES was collected in an empty injector liner, which was washed with water and acetone
before being used, to prevent column contamination. After measuring each sample at least
three times, it was discovered that the relative standard deviation was less than 1%.
RESULTS AND DISCUSSIONS

SOLUBILITY TEST.

The following criteria must be met by an ideal DES to effectively separate aromatic from
aliphatic hydrocarbons: (I)high solubility of aromatic hydrocarbons in the DES; (ii) no or low
solubility of aliphatic hydrocarbons in the DES; (iii) high selectivity and high solute
distribution coefficient; and (iv) simple recovery of the extracting agent. In addition,
additional factors should be taken into account for simpler handling and utilisation (e.g.,
DESs liquid at room temperature, low viscosity). A solubility test was carried out to verify
the first two requirements. 60 distinct DESs were created for this test (a list of the prepared
DESs can be found in the Supporting Information, Table 2). The list displayed in Table 2 was
condensed to 34 different DESs since only those DESs that stayed liquid at room temperature
and demonstrated acceptable viscosity were taken into consideration for additional research.
Using the cloud point method as stated in section 2.4, the solubility of benzene in the 34
different DESs that were chosen was experimentally calculated at T/K = 298.2 and
atmospheric pressure. The solubility of hexane in those DESs with the highest benzene
solubility was then measured in the same manner. The most encouraging results are displayed
in Table 3. The experimental solubility of benzene in all the examined DESs may also be
found in Table 3 (in the supporting information).

Table 3. Solubility of Hexane and Benzene in the Most Promising DESs

DES X benzene X hexane

Tetraethylammonium chloride: ethylene glycol (1:2) 0.003 0.193
Tetrahexylammonium bromide: ethylene glycol (1:2) 0.205 Fully soluble
Tetrahexylammonium bromide: glycerol (1:2) 0.157 0.844
Methyltriphenylphosphonium bromide: ethylene glycol (1:4) 0.005 0.135

Atmospheric pressure and T/K = 298.3 were used to measure the solubility (expressed as a
mole fraction).

It is clear from Table 3 that all DESs are more soluble in benzene than hexane. The existence
of -electrons around benzene (resulting from the molecule's aromatic character), which results
in a larger electrostatic field around the aromatic molecule, can be used to explain this
behaviour. Higher solubilities are implied by interactions between the -electron cloud and the
solvents. Hexane-DES interactions are weaker than benzene-DES interactions because there
is no -electron cloud surrounding the hexane molecule.  All of the DESs listed in Table 3
meet the first two requirements for choosing the best extracting agent previously mentioned.
However, because the high solubility in aromatic compounds is the most crucial condition,
the following DESs were chosen for further study: I tetrahexylammonium bromide: ethylene
glycol 1:2 (DES 1); and (ii) tetrahexylammonium bromide: glycerol 1:2. (DES 2). The LLE
data of the ternary systems must be experimentally measured in order to calculate the solute
distribution coefficient and the selectivity, even though the difference in solubilities is a sign
that the separation will work. The viability of the separation will be determined by these two
common criteria (see section 3.3)

Characterization.

Some physicochemical parameters, such as density and viscosity, should be examined in

order to utilise a solvent as an extracting agent for liquid–liquid extraction. Table 4 displays
the experimentally determined densities and viscosities of the two chosen solvents at
atmospheric pressure and at T/K = 293.15343.15 respectively.

Table4. Experimental Density and Viscosity of the Examined DESs at the Various
Atmospheric Pressure and Temperature

DES 1
DES 2

T ¿) ⍴(g/cm3) η( mPa . s) T ¿) ⍴(g/cm3) η(mPa . s)

293.15 1.005 229.4 293.15 1.045 1198
5
298.15 1.004 172.3 298.15 1.043 810
2 0
303.15 1.001 132.0 303.15 1.039 560
3 0
308.15 0.998 102.5 308.15 1.035 403
5 5
313.15 0.994 81.0 313.15 1.032 295
9 9
318.15 0.991 64.5 318.15 1.029 216.
5 0 4
323.15 0.988 51.9 323.15 1.026 162.
1 1 4
328.15 0.985 42.3 328.15 1.022 123.
0 9 1
333.15 0.982 35.2 333.15 1.020 97.4
2 0
338.15 0.978 29.5 338.15 1.016 77.9
5 0
343.15 0.975 24.50 343.15 1.013 63.5
0 0

A linear equation that describes the relationship between density and temperature exists:
⍴
( )
g
cm
3
=a+bT ¿ )

where a and b are movable parameters that are described in the supporting information, and is
the density in g/cm3, T is the temperature in K. (Table 4). The experimental density data's
standard relative deviation, from its fitting values was computed as

ndat 1 /2
z−z cal
σ ={∑ (( ) ¿ ¿ 2/ n dat )} ¿
i z cal

Where n dat is the quantity of experimental data points and z and z cal are the values of the
physical qualities that have been measured experimentally and calculatedly, respectively.
The values are also displayed in Table S4 of the supporting data. With the help of the
correlation shown in eq 1, the relationship between temperature and density. Both the
Vogel-Fulcher-Tammann (VFT) and the Arhenius-like equations were used to fit the viscosity
values, η. The Arrhenius-like law is the equation that is most frequently employed to relate
viscosity variation to temperature:

−B
η=A exp ⁡( )
RT

where A (mPa.s), the viscosity at infinite temperature; B (kJ.mol -1); and R (8.314 Jmol-1. K-1),
the gas constant, are the fitting parameters. The relationship between viscosity and
temperature was also fit using the Vogel-Fulcher-Tammann (VFT) equation using the
following expression:

B
η=A exp( )
T −T ˳

The supporting information, presents the fitting parameters for both viscosity correlations
together with the standard relative deviations, (derived using eq 2). This table makes it
feasible to see that the VFT equation provides the best fit for viscosity because its relative
standard deviation is lower. But it should also be remembered that the Arrhenius equation
only has two fitting parameters, but the VFT equation has three. As a result, a better match
using the VFT equation should be anticipated. displays the experimental viscosity against
temperature along with the VFT equation's fitting. Studying the effects of temperature and
the HBD on the physical characteristics of the two examined DESs is possible. When would
be expected, as the temperature rises, the density reduces linearly while the viscosity
quickly decreases. Additionally, the glycerol-based DES exhibits higher densities and
viscosities throughout the whole temperature range under study. Given that both DESs are
made at the same molar ratio with the same HBA and that glycerol has higher densities and
viscosities than ethylene glycol, this result was expected. The DES 1 (ethylene glycol-based
DES) would be the best option for acting as the extracting agent in this separation, despite
the fact that the LLE data are required for the evaluation of the selected solvents in the
extraction. Furthermore, when compared to ethylene glycol and glycerol, respectively, DES
1 and DES 2 would be preferable. The explanation is that low viscosity solvents can alleviate
both mass transfer restrictions and operating expenses related to problems like liquid
pumping. Experimental LLE Data, section 3.3. {Hexane (1) + benzene (2) + DES 1 (3)} and
{Hexane (1) + benzene (2) + DES 2 (3)} experimental LLE data were measured at T/K = 298.2
and T/K = 308.2, respectively, and atmospheric pressure. The solubility values of the
investigated DESs at T/K = 298.2 and 302.5. The experimental results for the ternary systems
including DES 1 and DES 2, respectively. The experimental data as a triangular diagram. The
solute distribution coefficient (β) and the selectivity (S) are two measures that can be used
to assess the separation's effectiveness. These expressions can be used to calculate these
parameters:

x 2, E
β=
x 2 ,R

S=
( )
x2
x1 E

( )
x2
x1 R

where "E" and "R" stand for the extract (DES-rich phase) and raffinate (aliphatic-rich phase),
respectively, and "x1" and "x2" stand for the mole fractions of aliphatic and aromatic
compounds, respectively. For systems containing DES 1 and DES 2, the solute distribution
coefficient and selectivity values are displayed in. illustrate the solute distribution coefficients
and selectivities for the systems "{hexane (1) + benzene (2) + DES 1 (3)}" at T/K = 298.2
and T/K = 308.2 and "{hexane (1) + benzene (2) + DES 2 (3)}" at T/K = 298.2 and T/K =
308.2, respectively, as a function of the aromatic concentration in the aliphatic-rich phase.
Table 5 shows that an increase in temperature causes the solubility of hexane and benzene in
the investigated DESs to slightly increase. Additionally, it should be noted that both
hydrocarbons are more soluble in the DES (DES1) that is based on ethylene glycol than in the
DES that is based on glycerol (DES 2). Last but not least, the total miscibility of benzene in
the DES 1 is interesting since it deviates from benzene's typical behaviour in earlier
extraction investigations that used both ILs and DESs.

The solubility information in Table can be compared to that in Supporting Information which
lists the solubilities of benzene and hexane in pure glycerol and ethylene glycol. It is clear
that the DES has substantially higher solubilities for both hydrocarbons than pure glycerol or
ethylene glycol. The rise in solubility, particularly for benzene, is striking. For instance, while
benzene is completely soluble in the ethylene glycol-based DES, it is only partially soluble in
pure ethylene glycol (Xbenzene = 0.023). (DES 1). The solubility of benzene in pure glycerol
is Xbenzene = 0.007, but in the glycerol-based DES, it is Xbenzene = 0.844. (DES 2). When
a DES is formed, the connections between the molecules of glycerol or ethylene glycol are
broken, resulting in intramolecular hydrogen

bond interactions that increase the solubility of the DES. Figure 3 shows that the ternary
systems containing ethylene glycol-based DESs fall into the type 1 category, where two pairs
of compounds exhibit complete miscibility (hexane + benzene and benzene + DES 1) and one
pair exhibits partial miscibility (hexane + DES 1), in accordance with the classification
proposed by Srensen et al.29. Additionally, the ternary systems containing glycerol-based
DESs fall into the type 2 category because only one pair of compounds{hexane + benzene}is
miscible across the whole range of compositions, while two pairs {hexane + DES 2} and
{benzene + DES 2} show partial miscibility. The impact of temperature on separation can be
examined. The effect of temperature may be seen to be rather minimal in both systems.
However, for T/K = 298.2 compared to T/K = 308, both the solute distribution coefficients
and the selectivity values are marginally greater. In other words, cold temperatures encourage
the separation. Therefore, it is recommended to extract at T/K = 298.2 in order to reduce the
energy requirement. As seen in Figure 4, the solute distribution coefficient values of DES 1
and DES 2 drop as the concentration of aromatic in the aliphatic-rich phase rises, reaching an
aromatic mole fraction in the aliphatic-rich phase of around Xbenzene = 0.5 in all the systems
under study. The solute distribution coefficient rises with the concentration of aromatic
compounds in the aliphatic-rich phase, starting from the concentration specified, when it
finds its minimal value. The extraction of aromatic components is therefore more
advantageous at low aromatic concentrations or at high aromatic concentrations, but less
advantageous in the area from 0.35 to Xbenzene to 0.6 in the aliphatic-rich phase. Sulfolane
exhibits a similar pattern of solute distribution coefficient behaviour. It is clear that when the
concentration of aromatic component in the aliphatic-rich phase increases, the selectivity
values of DES 1 and DES 2 drop. Additionally, it was discovered that the selectivity values in
every system under study were higher than unity, suggesting that the separation utilising
these DESs would be possible. Additionally, the behaviours of DES 1 and DES 2 as
extracting agents for the separation of "hexane + benzene" can be compared. In terms of
solute distribution coefficient, DES 1 displays greater values than DES 2, while in terms of
selectivity, DES 2 displays higher values over the entire range of concentrations. The
electrostatic potential of the HBD could be used to explain this behaviour. The HBD-HBA
interactions of the glycerol-based DES (DES 2) are stronger than those of the ethylene
glycol-based DES because glycerol exhibits a larger electrostatic potential than ethylene
glycol (DES 1). The interactions with benzene and hexane are reduced as a result of the
greater contacts in DES 2 producing a more delocalized charge. This explains why DES 1 has
larger distribution coefficient values due to the increased solubility of benzene and hexane.
After analysing the data, it is feasible to draw the conclusion that using DES 1 rather than
DES 2 would be preferable for separating benzene from "hexane + benzene." Higher solute
distribution coefficients are more profitable overall because they suggest lower solvent-to-
feed ratios, which translate into less volumes of solvent that need to be recovered and thus
reduced energy demands. On the other hand, high selectivity values (DES 2) primarily
influence the size of the equipment, resulting in an initial expenditure with a less significant
economic impact on the effectiveness of the separation. Additionally, DES 1 displays lower
density and significantly lower viscosity values than DES 2, which is also advantageous for
the process' economy.

3.4. Literature Comparison

A literature comparison was done to assess the performances of DES 1 and DES 2. We
contrasted our solvents' solute distribution coefficient and selectivity values with those of
previously investigated solvents (sulfolane/ILs) in the literature. The selectivity values and
the solute dispersion coefficients are compared. Sulfolane and the ILs have very different
molar masses, hence the comparison was done using mass fractions rather than moles in
order to provide more accurate estimates of how well the solvents applied. When DES 1 and
DES 2 are contrasted with sulfolane, it is evident that the performance of the latter is
comparable to that of the former for low aromatic concentrations in the aliphatic rich phase.
However, starting from a concentration of around Wbenzene = 0.15 in the aliphatic-rich
phase, the solute distribution coefficient values of sulfolane are higher than those of DES 1
and DES 2. Only ILs based on bis(trifluoromethylsulfonyl)imides, such as 1-decyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide (C10MimNTF2) and 1-dodecyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imid (C12MimNTF2), which contain
relatively long alkyl chain length. DES 1, DES 2, C10MimNTF2, and C12MimNTF2 exhibit
lower selectivity values than sulfolane. In terms of industrial application, we will, however,
choose larger distribution coefficient values above higher selectivity values. This is due to the
fact that high distribution coefficient values indicate a reduced requirement for solvent during
the extraction process, which means a reduction in operational costs related to energy
(solvent recovery) and chemicals (solvent makeup stream). High selectivity values, on the
other hand, imply lesser equipment requirements; nonetheless, equipment scaling is often
advantageous and only requires an initial capital cost expenditure. Furthermore, they appear
to be an intriguing commercial option when taking into account the distribution coefficient
values of the DESs at low aromatic concentrations. Due to their insignificant vapour
pressures, the investigated DESs and the aforementioned ILs provide a simpler and less
expensive solvent recovery compared to volatile solvents (such as sulfolane). The
fundamental drawback of the sulfolane process—the substantial energy requirements for the
solvent recovery—is overcome by the straightforward solvent recovery. Therefore, using
DES 1 and DES 2 as extracting agents for the "hexane + benzene" separation seems more
promising and economically viable than using ILs.

Correlation.

The NRTL thermodynamic model,30 which treats the DESs as a single component, was used
to correlate the experimental LLE data. By minimising the subsequent objective function, the
model was put into practise. where n is the number of ingredients in the mixture, m denotes
the number of tie lines, and (1/β) exp
and (1/β) cal
denote the inverse experimental and
calculated values of the solute distribution ratio, respectively. The following formula has
been used to get the composition's root-mean-square deviation, x:
 ( ( ) ( )
)
cal exp 2
1 1
−
m n
β ij βij
OF =∑ ∑
(β )
exp
i=1 j=1 1
ij

where m is the number of tie lines, n is the total number of mixture's components, and
(1/β) exp and (1/β) cal. are, respectively, the inverse experimental and calculated values
of the solute distribution ratio. The following formula has been used to get the
composition's root-mean-square deviation, σ x:

σ x=100.

( )
m n−1 1

∑ ∑ ( x ijI , exp−x ijI , cal ) −( xijII ,exp−x ijII ,cal )

2 2 2

i j
2 mn

The mole fractions of the components for each tie line are compared between
experimental and computed values in this deviation. The fitting parameters and the
composition's root-mean-square deviation. The no randomness parameter was varied
between 0.05 and 0.30 during the fitting. The values for aij shown in Table 8 produced the
best results. A suitable model for fitting LLE data containing ILs is NRTL.
CONCLUSION

The use of a novel class of solvents, known as DESs, as extracting agents for the separation
of the benzene + hexane combination has been investigated in this work. To select DESs that
meet the solubility requirements for this separation, a solubility test was conducted first. The
DESs with the highest benzene solubility have been chosen for more study. The solvents in
question were I tetrahexylammonium bromide: ethylene glycol with a molar ratio of 1:2
(DES 1) and (ii) tetrahexylammonium bromide: glycerol with a molar ratio of 1:2. (DES 2).
Second, the chosen solvents have been characterised; experimental measurements of density
and viscosity as a function of temperature have been made. Second, the solvents were
characterised by taking experimental measurements of density and viscosity as a function of
temperature. It was discovered that as temperature rises, both density and viscosity decrease.
It was also discovered that the glycerol-based DES has higher density and viscosity values
across the entire temperature range studied. Following that, the LLE data of the systems
hexane (1) + benzene (2) + DES (3) were measured at T/K = 298.2 and T/K = 308.2, as well
as atmospheric pressure. The solute distribution coefficient and selectivity values were
calculated and compared to previously investigated solvents. The temperature effect on
separation has also been investigated, with low temperatures promoting separation and
lowering energy requirements. Given the solute distribution coefficient and selectivity values,
DES 1 would be preferred for this separation over DES 2. The lower density and viscosity
values of DES 1 compared to DES 2 also indicate that DES 1 will be the best option among
the DESs studied. Finally, by treating the DESs as a single component, the NRTL model was
successfully applied to the experimental data. The solute distribution coefficients of the
investigated DESs were found to be lower than that of sulfolane. Only DES 2 has a higher
solute distribution coefficient than sulfolane and the previously studied ILs at low aromatic
concentrations in the aliphatic-rich phase. It was also discovered that the selectivity values for
sulfolane are higher than those for any of the other DESs studied. However, if the negligible
volatility of the DESs is taken into account, the main disadvantage of the sulfolane process,
the amount of energy required for solvent recovery, may be overcome. It was also discovered
that the performance of the DESs under consideration is comparable to that of the ILs.
Because DESs are two times cheaper, they can overcome ILs' main disadvantage, which is
their high price. As a result, preliminary results indicate that this new generation of solvents
can be used as effective extracting agents for the separation of the hexane + benzene mixture.
The use of a novel class of solvents, known as DESs, as extracting agents for the separation of the
benzene + hexane combination has been investigated in this work. To select DESs that meet the
solubility requirements for this separation, a solubility test was conducted first. The DESs with
the highest benzene solubility have been chosen for more study. The solvents in question were I
tetrahexylammonium bromide: ethylene glycol with a molar ratio of 1:2 (DES 1) and (ii)
tetrahexylammonium bromide: glycerol with a molar ratio of 1:2. (DES 2). Second, the chosen
solvents have been characterised; experimental measurements of density and viscosity as a
function of temperature have been made. Second, the solvents were characterised by taking
experimental measurements of density and viscosity as a function of temperature. It was
discovered that as temperature rises, both density and viscosity decrease. It was also discovered
that the glycerol-based DES has higher density and viscosity values across the entire temperature
range studied. Following that, the LLE data of the systems hexane (1) + benzene (2) + DES (3)
were measured at T/K = 298.2 and T/K = 308.2, as well as atmospheric pressure. The solute
distribution coefficient and selectivity values were calculated and compared to previously
investigated solvents. The temperature effect on separation has also been investigated, with low
temperatures promoting separation and lowering energy requirements. Given the solute
distribution coefficient and selectivity values, DES 1 would be preferred for this separation over
DES 2. The lower density and viscosity values of DES 1 compared to DES 2 also indicate that
DES 1 will be the best option among the DESs studied. Finally, by treating the DESs as a single
component, the NRTL model was successfully applied to the experimental data. The solute
distribution coefficients of the investigated DESs were found to be lower than that of sulfolane.
Only DES 2 has a higher solute distribution coefficient than sulfolane and the previously studied
ILs at low aromatic concentrations in the aliphatic-rich phase. It was also discovered that the
selectivity values for sulfolane are higher than those for any of the other DESs studied. However,
if the negligible volatility of the DESs is taken into account, the main disadvantage of the
sulfolane process, the amount of energy required for solvent recovery, may be overcome. It was
also discovered that the performance of the DESs under consideration is comparable to that of the
ILs. Because DESs are two times cheaper, they can overcome ILs' main disadvantage, which is
their high price. As a result, preliminary results indicate that this new generation of solvents can
be used as effective extracting agents for the separation of the hexane + benzene mixture.
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