REMOVAL OF LEAD FROM WATER USING LIQUID-LIQUID

EXTRACTION PROCESS
A transfer of mass occurs between the two phases in the process of liquid-liquid
extraction (LLE) as described by Koncsag and Barbulescu (2011). This transfer
takes place due to the varying solubility or distribution coefficients of the
immiscible solvents, resulting in the movement of a constituent from one solvent to
another through the extraction process (Wadegaonkar, n.d.). The LLE process is
visually represented in Figure.

Figure: The LLE process conducted in a separation funnel

There is one liquid phase of the feed that contains both solute and solvent while the
other extracting solvent is present in the other phase (Koncsag and Barbulescu,
2011). During the extraction, the solute that is soluble in both phases is extracted
and transferred from the feed to the solvent. The extracting solvent will be stirred
with the feed during extraction to promote the transfer of solute and the extracting
solvent will form a separate layer when stirring is stopped (Wadegaonkar, n.d.).
After that, the feed becomes a raffinate due to the absence of a solute from the feed
and the solvent transforms into an extract at the end of the extraction process.[1]
Extraction of lead with cyanex 302

In the present work, a new method for the solvent extraction separation of lead (II)
with cyanex 302 into toluene has been developed and the lead thus, separated was
stripped into HNO3 for its spectrophotometric determination by PAR from binary
mixtures, alloys and environmental samples.

Reagents
Stock solution of lead (II) was prepared by dissolving 2.0 g of lead nitrate in 250
ml of distilled water containing 0.5 ml of concentrated nitric acid. The solution was
standardized complex metrically using EDTA and working solutions of lower
concentration were prepared by suitable dilutions.

A 0.1 mol dm−3 stock solution of cyanex 302.

Extraction as a function of pH
Lead (II) was extracted in the pH range of 1.0–10.0 with 5×10 −3 mol dm−3 cyanex 302 in
toluene. [2]

Extraction of lead (II) from succinate media with n-octylaniline in

toluene

Experimental procedure.
The lead (II) stock solution was created by dissolving 1.598 g of lead nitrate
(which had been dried at 110 °C) in double distilled water with the addition of 1 ml
of concentrated nitric acid. To ensure accuracy, the lead(II) stock solution was
standardized using complex metric analysis . The diluted lead (II) solution was
then prepared by appropriate dilution.

Extraction in PH.
Lead (II) can be extracted within a pH range of 1–10 when weak organic acids like
sodium succinate (0.005 M), sodium malonate (0.01 M), and sodium salicylate
(0.05 M) are present. The extraction of lead (II) is quantitatively observed in the
pH range of 8.0–8.3 using 0.005 M sodium succinate solution. However, at higher
pH levels, there is a possibility of hydrolysis occurring. This hydrolysis indirectly
promotes competing equilibrium, leading to the formation of ion-pair complexes.
As a result, the extraction efficiency decreases with an increase in pH.

Separation and determination of lead (II) from binary

mixture
The investigation revealed that Tl(I), Tl(III), Cu(II), Th(IV), Sn(VI), Sb(III), and
Ca(II) were not extracted when subjected to basic conditions with lead(II) using a
solution of 0.005 M sodium succinate and 10 ml of 5% (v/v) n-octylaniline in
toluene. The organic phase containing the desired compounds was then treated
with water (2×25 ml) and analyzed using complex metric methods.

Conclusion:
1. It allows for the selective separation of lead (II) from other metals that are
commonly found together with it.
2. It is not affected by numerous foreign ions that are typically found alongside
lead (II) in its natural state.
3. Only a small amount of reagent is needed to fully recover lead(II)
quantitatively.
4. The equilibration process is completed within a very short time span of just 30
seconds
5. Lead (II) is extracted by n-octylaniline in toluene from sodium succinate media.
[3]
Lead (II) extraction from aqueous solutions by pyridine Extractants

The goal of this work was to study the extraction of lead(II) from chloride and
chloride/nitrate solutions by 1-(3-pyridyl)undecan-1-one oxime and its quaternary
salts:3--1-propylpyridinium chloride and 3- -1-propylpyridinium bromide.

Reagents:
All chemicals utilized in this investigation were of reagent grade. Toluene
(⩾99.5%, POCH, Poland) and decan-1-ol (⩾98%, Merck, Germany) were
employed as constituents of the organic phase. Lead (II) nitrate (ACS reagent,
Fluka, Germany), sodium chloride, sodium nitrate (p.a., POCH, Poland), lithium
nitrate and hydrochloric acid (37%) (p.a., POCH, Poland), and nitric acid (65%)
were utilized to form the aqueous phase.

The Impact of Shaking Time

The impact of shaking time on the extraction of 0.005 mol/L Pb(II) from an
aqueous solution containing 3.5 mol/L NaCl and 0.5 mol/L HNO3 using the
investigated extractants dissolved in toluene with a 10% (v/v) addition of decan-1-
ol was examined within the time range of 5-60 minutes. It was observed that the
separation of phases occurred rapidly, completing within 1 minute, and no
formation of emulsion was detected. When utilizing 1-(3-pyridyl) undecan-1-one
oxime, the extraction of lead (II) from chloride/nitrate solution was successful.

Conclusions:

The extraction of lead (II) from chloride/nitrate solution was observed for all the
extractants studied, namely 1-(3-pyridyl)undecan-1-one oxime, 3-[1-
(hydroxyimine)undecyl]-1-propylpyridinium bromide, and 3-[1-
(hydroxyimine)undecyl]-1-propylpyridinium chloride. The efficiency of the
extraction process strongly relied on the concentration of chloride ions in the
aqueous phase (HCl or NaCl concentration) and the concentration of the extractant
in the organic phase. It is worth noting that the extraction from HCl solutions
exhibited higher efficiency compared to other solutions of the extractant.[4]

Mercury extraction mechanism in ionic liquids

The rate of the process is highly influenced by experimental conditions such as

temperature, the anionic component of the 1mL of ionic liquid of 1 mL of a
5 × 10−3 M HgX2 solution in 0.5M sodium acetate buffer solution, and the PH
4.68 was added. The addition of inorganic salts like NaCl or NaBr to the aqueous
phase enhances the extraction rate of metal ions. Within 30 minutes, over 90% of
the metal ions are transferred into the organic phase, and complete ion removal is
achieved within four hours. The salt effects can even overcome the high viscosity
of the ionic liquid, making it a simple method for large-scale Hg (II) extraction.
The transfer process of mercuric ions from the aqueous phase to hydrophobic ionic
liquids without the use of chelating agents. Various experimental factors were
altered, including the anionic component of the 1-octyl-3-methylimidazolium salt,
the anion of the metal salt, and the composition of the aqueous phase used to
dissolve the mercuric salt. Although the complete removal of Hg(II) ions was
consistently achieved, the duration required to fully extract the metal ions from the
aqueous phase varied.[5]

Removal of Mercury ions from aqueous solution

The poly (allylamine-co-methacrylamide-co-dimethylurea chelating polymer

containing amino group and thiourea evaluated for its ability to eliminate mercury
ions (Hg2+) from water-based solutions. The impact of various factors such as pH,
contact time, and initial Hg concentration on the removal of Hg (II) was
investigated. The maximum adsorption of Hg (II) occurred within 1 hour of
reaching equilibrium. The adsorption of Hg ions took place over a period of 4
hours at pH 7. The highest adsorption of Hg (II) was achieved at pH 7 and a
concentration of 400 mg L−1.

Afterwards, the p (AA-co-MA) was functionalized with sulfur (S)-containing

thiourea using methyl isothiocyanate, resulting in the formation of p(AA-co-MA-
co-DMTU). Subsequently, extensive testing was conducted on the p(AA-co-MA-
co-DMTU) to evaluate its capacity for removing Hg(II) from aqueous solution
under different condition .
The synthesis of p(AA-co-MA-co-DMTU) was conducted with the aim of
eliminating Hg from an aqueous solution. The successful functionalization of the
polymer with thiourea was confirmed through FTIR analysis. The efficiency of Hg
adsorption was found to be highest at pH 7, as observed in experiments conducted
at different initial pH values.
[6]
Mercury (II) ion in water by solvent extraction followed by
reversed‐phase HPLC
This method has been evolved for the selective determination of mercury (II) ions
in water using reversed-segment high performance liquid chromatography
(HPLC). in this method, a 5 mL water pattern changed into positioned in a ten-mL
centrifuge tube ready with a stopper. in the end, 1 mL of a 2-mol/L (M) acetate
buffer solution with a pH of five.5 became brought to the centrifuge tube. After
thorough mixing, 1 mL of a zero.five M tetrabutylammonium bromide (TBA-
Br) solution and zero.3 mL of one-octanol had been introduced. with the aid
of shaking the contents for 10 mins, the mercury ions have been extracted into
an natural layer. The reproducible (RSD) of height areas for Hg ions at
concentrations of five-, zero.5-, and 0.05-ppm have been observed to be
1.8%, 0.6%, and 0.6%, respectively (N = 5). moreover,
the affect of diverse overseas ions on the approach became investigated the use
of a zero.2-ppm Hg trendy and 55 unique metallic ions.

with a purpose to determine the composition of the extracted Hg

compound, various starting substances which includes HgSO4, HgI2, Hg
(CH3COO)2, and HgBr2 had been examined. on the grounds that HgSO4 and
HgI2 confirmed moderate solubility in water, solvent extractions have
been performed the usage of aqueous answers (a thousand ppm Hg) of (1) HgCl2,
(2) HgBr2, and (three) Hg(CH3COO)2. The resulting top area ratio for
the 3 answers become about 10:10:6.
Our findings continually reveal that the extracted Hg compound became [(TBA+)
2HgBr4 2−]. To begin with, the Hg ion (which includes HgCl4 2−) underwent
conversion to HgBr4 2− in the presence of TBA‐Br during the
extraction technique. Ultimately, it was extracted as an ion pair of TBA2HgBr4.

The approach supplied for mercury evaluation necessitates

a conventional HPLC equipment that is equipped with a photometric
detector. Unlike different techniques, this technique does no longer contain the
usage of chlorinated solvents or acetonitrile for extraction or HPLC separation.
It exhibits a high degree of selectivity for Hg ions,
as maximum different metal ions do no longer produce any chromatographic top.
The extraction procedure is simple and does no longer require
any unique knowledge. This approach has been established to have linear
calibration curves over an extensive variety of concentrations (10 ppb–10 ppm),
with reproducible within various less than 2% as RSD. [7]

Mercury elimination from synthetic petroleum produced water

using green solvent via liquid-liquid extraction

The primary objective of this research is to examine the utilization of alternative

vegetable oils, namely corn, linseed, and canola oil, as environmentally friendly
extractants in the liquid-liquid extraction (LLE) process for mercury.

The extraction parameters encompass the choice of vegetable oil, pH of the feed
solution, time, and O/A ratio. By utilizing response surface methodology (RSM),
the optimization of three parameters in the stripping process is achieved. The
mutual solubility of corn oil is examined using models NRTL, UNIQUAC, and
Van't Hoff, while different temperatures are explored for the various strippants
(NaOH, HCl, and thiourea). The results obtained under optimal conditions reveal
extraction and stripping percentages of mercury reaching 99.4% and 95.4%
respectively. Corn oil has been found to be the optimal solvent for extracting
mercury within the pH range of 2-8. The evaluation of extraction reaction
mechanisms is conducted using density functional theory (DFT), Fourier-transform
infrared spectroscopy (FTIR), and ultraviolet-visible spectroscopy (UV-vis). The
kinetics of extraction and stripping processes are determined to follow first-order
(k = 0.182 min^-1) and second-order (k = 0.9244 L∙mg^-1min^-) kinetics,
respectively.
The aqueous solution used in this study was prepared by dissolving standard
solutions (1000 ppm) of mercury (II), arsenic (III), iron (III), magnesium (II),
calcium (II), and NaCl in distilled water. This solution, known as produced water,
was utilized for the experiment.
The order of extraction efficiency, from highest to lowest, was as follows: corn oil
(99.4%), canola oil (82.0%), and linseed oil (72.4%). Therefore, it can be
concluded that corn oil demonstrated the highest extraction capability and served
as the primary extractant.
The extraction percentages achieved a peak of 99.4%. Corn oil demonstrated
superior extraction capability for HgCl2 at pH 3, O/A ratio of 1, equilibrium time
of 20 minutes, and a temperature of 303.15 K under optimal conditions. In terms of
the stripping process, the ideal conditions were found to be 2 M HCl and a stirring
speed of 420 rpm.[8]

Separation of mercury from its aqueous solution through supported

liquid membrane using environmentally benign diluent

This paper provides an experimental observe on the facilitated transport of

mercury via a flat sheet supported liquid membrane (SLM)
that carries trioctylamine (TOA) as a carrier and coconut oil as a diluent, that is an
environmentally pleasant solvent. The co-transport mode of
mercury switch was investigated using an aqueous solution of NaOH as
the strip segment. Distinct polymeric helps had
been tested to decide the foremost SLM configuration. The mixture of "PVDF-
TOA-coconut oil" because the SLM confirmed promising consequences and
remained strong for a length of ninety eight hours. The extraction system relies
upon on various essential parameters, which include the pH changed
into 1.5 and concentration of the feed phase, the concentration of the strip phase,
and the service concentration. It become located that the
extraction efficiency turned into highest at a feed segment pH of one. interestingly,
the carrier awareness had a minimal effect at the extraction method,
as approximately ninety one% of mercury separation turned into carried
out even with none service in the SLM.
Even under the maximum favorable running conditions (zero.3 M NaOH, four%
TOA, and pH 1), the the extraction efficiency reached up to ninety five
%. Moreover, coconut oil exhibited superior overall performance inside
the separation of mercury in comparison to other natural solvents such
as dichloroethane and heptane.
in this observe, coconut oil and TOA have been used as diluents and extractants
to break up mercury from aqueous solutions thru SLM. A take a look at have
become achieved to evaluate the effectiveness of coconut oil as a diluent within
the mercury elimination approach. Polyethylene (PE), polytetrafluoroethylene
(PTFE), polyvinylidene fluoride (PVDF), nylon 6, 6 and so forth. Special kinds
of polymer materials, which consist
of polymer substances, were tested to decide the most appropriate for SLM and
its effect at the feeding of the ribbon. SLM is mercury. SLM is
mercury. Additionally, the steadiness of the SLM was assessed, and the overall
performance of coconut oil changed into as compared to that
of other organic solvents, particularly dichloroethane and heptane.
The investigation specializes in studying the important
thing elements that affect the transportation of mercury in SLM so as
to decide the highest quality operating conditions for attaining the very
best viable separation of mercury from its aqueous answer. The
various numerous SLM combos tested, the combination of "PVDF–TOA–coconut
oil" demonstrates the most favorable outcome in terms of separation efficiency. [9]

Solvent extraction of cadmium (II) from chloride solutions by

pyridyl ketoximes

The solvent extraction of cadmium(II) from chloride solutions using 1-(2-

pyridyl)-tridecane-1-one (2PC12), 1-(2-pyridyl)-pentadecane-1-one (2PC14), 1-
(four-pyridyl)-tridecane-1-one (4PC12) and 1-(four-pyridyl)-pentadecane-1-one
(4PC14) oximes has been studied. The influence of extractant concentration,
metallic attention, chloride ion concentrations and of diverse polar and non-
polar diluents was studied. Cadmium (II) become effectively extracted using a
chloroform and hydrocarbons mixed with decan-1-ol as diluents and stripped
from the loaded organic segment with water and ammonia aqueous solutions.
Hydrophobic 2- and 4-alkyl pyridyl ketoximes as character model extractants
had been used. In toluene, 2-pyridyl ketoximes have appropriate solubility,
however four-pyridyl ketoximes display restricted solubility. The extraction
residences of pyridyl ketoximes depend upon the placement of the oxime group
in the pyridine ring, the aqueous chloride ion concentration and the solvating
houses of the diluent. The extraction of cadmium (II) changed into maximum
the use of chloroform as diluent and did not rely upon the chloride ion
awareness. but cadmium(II) extraction the usage of toluene with 10% (v/v)
addition.[10]

Removal capacity of Cd(II) from aqueous solution using emulsion

liquid membrane (ELM)
The emulsion liquid membrane (ELM) become utilized to eliminate Cd(II) from
aqueous answer. The liquid membrane was composed of trioctylamine (TOA) as
a provider, kerosene as an organic diluent, ammonia as a stripping solution, and
Span 80 as an emulsifying agent. The emulsion changed
into prepared using ultrasonic generation. Several critical parameters have
been investigated to decide their effect on the emulsion diameter and
the elimination capacity of Cd(II). Those parameters protected emulsification time,
surfactant concentration, service awareness, and volume ratio of membrane
to internal section. Additionally, the effect of emulsion diameter on
the permeation procedure changed into also studied. The outcomes discovered that
the emulsion diameter ranged from 0.878 to 246 μm. The best removal capacity of
Cd (II) changed into carried out at 0.493 mg Cd/ml emulsion, while the
lowest membrane breakage became determined at zero.117%. Its
miles worth mentioning that everyone aqueous solutions had been prepared the
usage of deionized water. The trioctylamine (TOA) used as an extractant did now
not undergo in addition purification. Span 80 turned into employed because
the surfactant. Hydrochloric acid (HCl) and sodium hydroxide (NaOH) had
been applied to alter the pH of the feed phase. to research the effect of
emulsification time at the emulsion diameter,
emulsions were prepared at numerous time durations ranging from 5 to 30 minutes.
It was observed that longer emulsification time resulted in smaller emulsion
diameter and a more solid emulsion. The emulsion turned into organized with a
Span 80 attention of 4 wt.% and a TOA concentration of four wt.%.[11]

Elimination of cadmium from wet process phosphoric acid with

Alamine 336

The extraction of Cd from WPA was achieved through solvent extraction,

specifically using amine extractants such as "Alamine 336" as a tertiary amine
extractant. In batch tests conducted under optimal conditions, the extraction of Cd
from WPA was determined to be 74 ± 2.54% (95% confidence limit).

Based on the results, it can be concluded that the organic phase, consisting of 1%
(vol) Alamine 336 + 1.5% (vol) iso-dodecanol in B-65 kerosene, exhibits good
stability and high efficiency in removing Cd from WPA. The average Cd
extraction, after 20 recyclings of the organic phase in the solvent extraction circuit,
was calculated to be 68.57%.

This study primarily focuses on the separation of Cd from WPA using solvent
extraction and amine extractants, particularly "Alamine 336" as the tertiary amine
extractant. Various parameters affecting Cd extraction were investigated and
optimized in the laboratory.

For the experiments, Alamine 336 (a mixture of tri-n-octylamine and tri-n-

decylamine from Henkel Ind.), TBP, D2EHPA, and TOPO (from Fluka Ind.) were
used without any additional purification.

The results of Cd extraction from WPA indicate that a mixture of 1% (vol)

Alamine 336 and 1.5% (vol) iso-dodecanol in B-65 kerosene, as the organic phase,
along with WPAAC 51% P2O5 as the aqueous phase and 5 minutes of mixing at
ambient temperature, provide the optimum conditions.

Under these optimum conditions, the average Cd extraction from WPAAC (with a
95% confidence limit) was determined to be 74 ± 2.54%.

B-65 kerosene was chosen as the diluent due to its cost-effectiveness, safety, and
higher process efficiency..[12]

Solvent extraction of cadmium (II) from sulphate solutions using

TOPS 99, PC 88A, Cyanex 272

In this paper, we report the solvent extraction studies of cadmium from sulphate
solutions using the commercial extractants, TOPS 99, PC 88A and Cyanex 272 and
their mixtures. Various parameters studied include equilibrium pH, extractant and
metal concentration, synergism, different salts, loading capacity, stripping of
cadmium from loaded organic, extraction from Ni–Cd mixtures and preparation of
cadmium–TOPS 99 solid complex. Characterization of the solid complex of
cadmium with TOPS 99 by FTIR, 31P NMR supported metal complex formation
with the phosphorus-hydroxyl (P-OH) group.

Commercial extractant TOPS 99, (an equivalent of di-(2-ethylhexyl) phosphoric

acid, Heavy Water Plant,PC 88A (2-ethylhexyl phosphonic acid mono 2-ethyl
hexyl ester, and Cyanex 272 (bis (2,4,4-trimethyl pentyl) phosphinic acid,
Cytec ,were used as received. Distilled kerosene (bp: 165–200 °C) was used as the
diluent. The sodium salts of the extractants (60% neutralized) were prepared by
adding stoichiometric amounts of concentrated NaOH solutionThis paper presents
a study on the extraction of cadmium from sulphate solutions using different
commercial extractants, namely TOPS 99, PC 88A, and Cyanex 272, as well as
their mixtures. The study investigates various parameters such as equilibrium pH,
extractant and metal concentration, synergism, different salts, loading capacity,
stripping of cadmium from loaded organic, extraction from Ni-Cd mixtures, and
the preparation of cadmium-TOPS 99 solid complex. The solid complex of
cadmium with TOPS 99 is characterized using FTIR and 31P NMR, which
confirms the formation of a metal complex with the phosphorus-hydroxyl (P-OH)
group. The commercial extractants TOPS 99, PC 88A, and Cyanex 272, along with
distilled kerosene as the diluent, were used as received. The sodium salts of the
extractants were prepared by neutralizing them with concentrated NaOH solution.
The extraction of Cd (II) from aqueous sulphate solutions turned into studied
within the pH variety of three.6-7.6 using the sodium form of TOPS ninety nine, pc
88A, and Cyanex 272 at different concentrations in kerosene. the share extraction
of Cd (II) increased with an growth within the equilibrium pH of the aqueous
segment.. The mechanism of metal transfer involves the formation of a 1:3 metal to
extractant complex. The addition of salts had a variable effect on the percentage
extraction of Cd (II), and mixtures of extractants showed TOPS 99 as the best
synergist. [13]

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