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Modeling of Liquid-Liquid Extraction Process

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J. Chem. Chem. Eng. 8 (2014) 971-977
doi 10.17265/1934-7375/2014.10.006
D DAVID PUBLISHING

Modeling of Liquid-Liquid Extraction Process for

Glycerol Purification from Biodiesel Production

Ignacio Contreras-Andrade1, Maicol Martínez-González2, Luis Figueroa-Casallas2, Jonathan Parra-Santiago2 and

Carlos Alberto Guerrero-Fajardo3*
1. Universidad Autónoma de Sinaloa, Culiacán Rosales 80040, México
2. Universidad Nacional de Colombia, Bogotá 11001, Colombia
3. Universidad Nacional de Colombia, Bogotá 11001, Colombia

Abstract: This paper shows some generalities about the glycerin byproduct obtained from biodiesel production process, presents an
analysis of the ternary equilibrium between methanol, water and glycerol, and shows the influence that temperature has on the
balance. This phase diagram illustrates ternary equilibrium at 10, 20 and 50 oC, keeping the pressure constant at 1 atm (atmosphere)
to standardize the analysis. The purpose of it is to establish the best temperature for the purification of glycerol by liquid-liquid
extraction method under the “extraction in several stages cross flow” taking an initial mixture of glycerol with composition 15 wt.%
water, 25 wt.% methanol and 60 wt.% glycerol. Water was used as liquid-liquid extraction solvent in order to remove as much
methanol as possible from the initial solution due to the existence of a zone of insolubility between the glycerol and water in the
ternary equilibrium. By this reason, two solutions are obtained, one consisting of water and methanol containing a trace of glycerin
and the other consisting of water, glycerine and traces of methanol, which contain only 4.62% of the total methanol which enter in
the process of liquid-liquid extraction, with 60.62% of the total glycerol, which is sent to a fractional distillation process to purify
glycerin up to 98% by weight.

Key words: Ternary equilibrium, liquid-liquid extraction, glycerin, purification.

1. Introduction catalyzed by a base. These processes, showed in Fig. 1,

Glycerol is an important raw material for a wide
variety of industries such as pharmaceutical, cosmetic
and food industry, making it a valuable byproduct
obtained by biodiesel production. By this reason, it is
necessary to develop an economical process to obtain a
product of high quality and to make the biodiesel
production process more economically viable,
decreasing its price in the market at the same time [1].
There are two methods of glycerol production at the
industrial level. The first is the saponification reaction
used in the soap production by triglycerides, water and
a base such as NaOH or KOH, and the other option is
the transesterification reaction, in most of the cases
*Corresponding author: Carlos Alberto Guerrero-Fajardo,
Ph.D., Associated Professor, research fields: oils fuel,
renewable fuel and catalysis. E-mail:
caguerrerofa@unal.edu.co.
are used to obtain soap and biodiesel as the main
product, generating glycerol as a byproduct.
By any of these processes, a significant amount of
salts are produced and they are accumulated with
glycerol in the aqueous phase. Glycerol purification by
distillation is a hardness process because a
pretreatment is necessary to remove the produced salts
and a vacuum system must be used to reduce the
boiling point of glycerol due to other alternatives like
exchange resins are more expensive methods [2].
In many occasions to avoid this purification cost,
biodiesel producers prefer to sell it as an impure
product at low cost. But because the biodiesel
production rate is constantly increasing [3], it is
necessary to develop a process to decrease the amount
of salts and to obtain a pure glycerol to be marketed
with a competitive price.
972 Modeling of Liquid-Liquid Extraction Process for Glycerol Purification from Biodiesel Production
Fig. 1 Glycerol production by saponification
transesterification reaction.
In this way, liquid-liquid extraction is an adequate
alternative to decrease the energy used in the
purification system due to with an adequate selection of
extraction solvent is possible to carry out this process at
room temperature avoiding the high cost produced by
vacuum.
2. Glycerol from Biodiesel Production
Biodiesel is obtained by transesterification reaction
showed in Fig. 1, producing glycerol at the same time
by the reaction of a triglyceride molecule with three
molecules of alcohol. At the end of this process, two
phases are produced, an organic phase with a high
content of methyl esters and a liquid phase with
glycerol. These phases have a high insolubility and by
that reason a separation by decantation process is
sufficient to obtain each one of these phases [4].
Organic phase is washed with water to remove
residual alcohol and catalyst. The methyl esters are
purified by this way to obtain the final product
known as biodiesel and aqueous phase is subjected
to a purify treatment to obtain pure glycerol. Fig. 2
shows the process of biodiesel and glycerol production [5].
In most of the cases, the transesterification process
is carried out with methanol, obtaining diglycerides,
monoglycerides and glycerol subsequently by this
process as shown in Fig. 3. In each reaction, a mole of
methyl ester is produced, in this way 3 mol of
biodiesel (methyl esters) are obtained from 3 mol of
Fig. 2 Biodiesel production from vegetable oil.
and
Fig. 3 Reaction to obtain glycerol from triglycerides.
methanol and 1 mol of triglyceride [6]. Fig. 3 shows
these reactions to get glycerol.
Glycerol in aqueous phase contain most of the
methanol which did not react in the transesterification
process and some traces of fatty acids and salt
produced from neutralization of basic catalyst and a
few quantity of water from methanol used in
transesterification process. This composition depends
on raw material used in this process, alcohol (methanol,
ethanol), fatty material (animal fat, vegetable oil) and
catalyst (KOH, NaOH) [7].
This byproduct is commonly purified by a
sequence of operations, starting with a flash
distillation to remove the methanol content, and then it
is bleached, filtered and dried to obtain a final
concentration higher than 90% in glycerol. The high
cost of this operation to remove the final content of
methanol produces an overhead in this process and for
biodiesel producer, it is not economically viable, and
by this reason, glycerol is discarded as a waste of the
process [8].
 Modeling of Liquid-Liquid Extraction Process for Glycerol Purification from Biodiesel Production 973

3. Ternary Equilibrium
Methanol-Glycerol-Water
Ternary diagrams are used to represent the behavior
of a three components mix, and in the case of a
liquid-liquid extraction to represent a mixture of two
components and its interaction with extractive solvent.
These diagrams show different structures according to
the interaction between its comp ounds, by this reason
can exist diagrams with a total solubility or with some
insolubility regions [9], as shown in Fig. 4.
Systems with an insolubility zone are used in the
case of liquid-liquid extraction due to in that case is
Fig. 4 Ternary diagram for water/methanol/glycerol at 10 oC.
necessary to produce two phases in each extraction.
Then a phase has a high content of the compound of
interest and the other phase has impurities with a part
of extractive compound.
In the case of ternary equilibrium between water,
glycerol and methanol, an insolubility zone is
produced for water and glycerol, and this zone is used
to liquid-liquid extraction. Because solubility is a high
function of temperature with a low influence of
pressure, it is necessary to take into account the
behavior of insolubility zone for different
temperatures to analyze the best operation conditions
for the system [10]. By this reason, Figs. 4-6 show
ternary diagram for water/methanol/glycerol system at
Fig. 5 Ternary diagram for water/methanol/glycerol at 20 oC.
different temperatures.
A line from initial mix composition to extractive
solvent composition represents the equilibrium line of
this system in a process represented in a ternary
diagram, as shown in Fig. 6. By this reason, it is
necessary to know each one of these compositions,
especially for initial mix, because solvent purity is
selected according to it [11].
For this process, mix composition of aqueous phase
was taken as glycerol 60%, water 15% and methanol
25% [12], and pure water is used as extractive solvent
to obtain a high separation with a few amount of it. It
is necessary to produce a separation of phases that
operation line passes through the insolubility area. Fig. 6 Ternary diagram for water/methanol/glycerol at 50 oC.
974 Modeling of Liquid-Liquid Extraction Process for Glycerol Purification from Biodiesel Production
Taking into account these considerations and
according to ternary diagrams showed in Figs. 4-6,
operating temperature was selected. 50 oC is not an
optimum temperature to use pure water due to the
operative line pass outside of insolubility zone as
shown in Fig. 6. In the same way, 10 oC is a
temperature less than room temperature and it is hard
to obtain at industrial level. By this reason, 20 oC was
selected because it has an appropriate behavior of
solubility and insolubility zone, and it is near to room
temperature, decreasing energy cost in purification
process.
4. Analysis of Liquid-Liquid Extraction
Process
From methanol-glycerol-water ternary equilibrium
diagram at 20 oC and 1 atm, material balance was
carried out to determine the final composition of
glycerol without methanol after liquid-liquid
extraction process using pure water as solvent. Then it
is possible to know the number of ideal stages for this
process.
As previously mentioned, initial mix is composed
of glycerol 60% (A), water 15% (B) and methanol 25%
(C). To obtain its composition in moles, it is necessary
to take 100 g of initial mix as the base of calculation
and with molecular weight of each compound
(methanol = 32 g/mol, water = 18 g/mol, glycerol =
92 g/mol) is possible to calculate molar fraction of
each compound in initial mix. Table 1 shows mass
fraction and molar fraction of this mix.
Now it is possible to establish the amount of water
necessary to each one of the liquid-liquid extraction
units to obtain a product with a high content of
glycerol. In this way, 144 g of water (8 mol) for each
100 g of mix in a stage was established by some
assays.
Table 1 Mass and molar fraction of initial mix.
Compound Mass fraction Molar fraction
Glycerol 0.60 0.29
Water 0.15 0.37
Methanol 0.25 0.34
Fig. 7 Ternary diagram for water/methanol/glycerol at 20 oC
with equilibrium lines.
A methanol/glycerol/water ternary equilibrium
diagram at 20 oC and 1 atm and a distribution diagram
for methanol in water and glycerol was used to
determine the composition of each outlet process [12].
Fig. 7 shows the mass balance for each stage, F is the
composition of feed for extraction and S is the
composition of extractive solvent (it is pure, so its
composition is at the corner of the diagram).
On the other hand, two extraction processes were
proposed and these are represented by two solution
equilibria lines. In each one of these lines, M point is
the composition of mix between initial mixture and
extractive solvent and R and E are the compositions of
each one of the phases produced in liquid-liquid
extraction [13]. Because R has a high content of
glycerol, it is the mainstream in this case.
Then with compositions of R and E in each stream
is possible to stablish the quantity of glycerol and
methanol in the final process stream, it is the
composition of R2.
The quantity of each one of the compounds was
determined from weight of initial mix. Then taking
into account that our base of calculation is 100 g, each
weight percentage and molecular weight was used as
shown below:
100 × 0.60
𝑚𝑚𝑚𝑚𝑚𝑚𝐴𝐴 = = 0.65 mol
92
100 × 0.15
𝑚𝑚𝑚𝑚𝑚𝑚𝐵𝐵 = = 0.83 mol
18
100 × 0.25
𝑚𝑚𝑚𝑚𝑚𝑚𝐶𝐶 = = 0.78 mol
32
 Modeling of Liquid-Liquid Extraction Process for Glycerol Purification from Biodiesel Production 975

𝑚𝑚𝑚𝑚𝑚𝑚𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 = 0.65 + 0.83 + 0.78 = 2.26 mol

Then a total balance and a balance by compounds
were carried out. This balance was development in
function of methanol.
Total balance:
𝐹𝐹 + 𝐿𝐿 = 𝑀𝑀 = 𝐸𝐸 + 𝑅𝑅
Balance by compound:
𝐹𝐹 × 𝑋𝑋𝑀𝑀𝑀𝑀 = 𝑀𝑀 × 𝑋𝑋𝑀𝑀𝑀𝑀 = 𝐸𝐸 × 𝑋𝑋𝑀𝑀𝑀𝑀 + 𝑅𝑅 × 𝑋𝑋𝑀𝑀𝑀𝑀
The mean of each variable is:
F—moles of initial aqueous phase;
L—water moles; Fig. 8 Diagram of methanol distribution in glycerol and
M—moles of mix between initial aqueous phase water at 20 oC.

and water; The value of E1 is calculated:

E—moles of glycerol poor phase; 𝐸𝐸1 = 10.26 − 2.30 = 7.96 mol
R—moles of glycerol rich phase; Then, moles of A, B and C in R1 and E1 were
XMF—methanol molar fraction in F; determined with values of R1, E1, XMR1, XME1 and XAE1,
XMM—methanol molar fraction in P; XAR1, XBE1, XBR1 from ternary equilibrium:
XME—methanol molar fraction in E; 𝑋𝑋𝐴𝐴𝐴𝐴1 = 0.01
XMR—methanol molar fraction in R. 𝑋𝑋𝐴𝐴𝐴𝐴1 = 0.245
Now, it is possible to determine the composition of
𝐴𝐴 in 𝑅𝑅1 = 2.30 mol × 0.245 = 0.56 mol
mix M with F and L streams. Then XMM was
𝐴𝐴 in 𝐸𝐸1 = 7.96 mol × 0.01 = 0.079 mol
determined using the value of F and XMF.
𝐶𝐶 in 𝑅𝑅1 = 2.30 mol × 0.127 = 0.29 mol
2.26 mol + 8 mol = 10.26 mol
𝐶𝐶 in 𝐸𝐸1 = 7.96 mol × 0.060 = 0.48 mol
2.26 mol × 0.34 = 10.26 mol × 𝑋𝑋𝐶𝐶𝐶𝐶 𝐵𝐵 in 𝑅𝑅1 = 2.30 mol – 0.29 mol – 0.56 mol
2.26 mol × 0.34 = 1.45 mol
𝑋𝑋𝐶𝐶𝐶𝐶 = = 0.075
10.26 mol 𝐵𝐵 in 𝐸𝐸1 = 7.96 mol − 0.079 mol − 0.48 mol
The XCM composition was located in the ternary = 7.40 mol
equilibrium diagram as shown in Fig. 7 and XMR1 and Each one of these values was compiled in Table 2 for
XME1 values were calculated using Fig. 8 to establish each entering and outing streams and mixtures.
the value of R1 and E1. According to the molar ratio between the inflow
𝑋𝑋𝑀𝑀𝑀𝑀1 = 0.127
Table 2 Molar fraction and mole content of A, B, C in each
𝑋𝑋𝑀𝑀𝑀𝑀1 = 0.06 entering and outing steam for each phase in liquid-liquid
From mass balance: extraction process.
𝑀𝑀 = 𝐸𝐸 + 𝑅𝑅 ⇒ 𝐸𝐸 = 𝑀𝑀 − 𝑅𝑅 Steam XC XA
A B C Total
(mol) (mol) (mol) (mol)
And from the balance by compound:
F 0.34 0.29 650 830 780 2,260
𝑀𝑀1 × 𝑋𝑋𝑀𝑀𝑀𝑀1 − 𝐸𝐸1 × 𝑋𝑋𝑀𝑀𝑀𝑀1
𝑅𝑅1 = M1 0.075 0.06 650 8,830 780 10,260
X MR1 E1 0.06 0.01 790 7,400 480 7,960
𝑀𝑀1 × (𝑋𝑋𝐶𝐶𝐶𝐶1 − 𝑋𝑋𝐶𝐶𝐶𝐶1 ) R1 0.127 0.245 560 1,450 290 2,300
𝑅𝑅1 =
(𝑋𝑋𝐶𝐶𝐶𝐶1 − 𝑋𝑋𝐶𝐶𝐶𝐶1 ) M2 0.027 0.055 560 9,450 290 10,300
10.26 × (0.075 − 0.06) E2 0.025 0.005 48 9,390 240 9,680
𝑅𝑅1 = = 2.30 mol R2 0.058 0.636 394 190 36 620
(0.127 – 0.06)
976 Modeling of Liquid-Liquid Extraction Process for Glycerol Purification from Biodiesel Production
and outflow of glycerol, was established a yield. In
this case, the yield is expressed by:
Glycerol molar outflow
Yield = × 100
Glycerol molar inflow
394 mol
Yield = × 100 = 60.61%
650 mol
In the same way, methanol content in the final
glycerol solution in relation to methanol content in the
initial mix is quantified as shown in the next equation
to determine the percentage of remaining methanol.
Remaining methanol
Methanol molar outflow
= × 100
Methanol molar inflow
36 mol
Remaining methanol = × 100 = 4.62%
780 mol
According to it, yield of liquid-liquid extraction
process to recover glycerol of aqueous phase obtained
from biodiesel production process is 60.61% and the
percentage of methanol removed from it is 95.34%,
which is a high content taking into account that only
4.63% of initial methanol is remaining in the final
product of this process.
5. Conclusions
A yield higher than 60% in concentration of
glycerol was obtained from biodiesel production
process with a final content of 4.62% in methanol, the
equivalent to a yield of 95.34% in methanol removal.
The efficiency of glycerol content and methanol
removal was increased by the addition of a high
quantity of water in each stage of the process or
adding another stage, but it increases the equipment
and operational costs due to it is necessary a bigger
equipment and raw material (it is water as extractive
solvent).
The main advantages to use water as a solvents are
it has a low price, it is not toxic, easily recoverable
and reusable in other steps of biodiesel production
process. On the other hand, methanol is easily purified
from water due to a high difference in boiling point, in
this way, water with a content of energy is reusable in
preheated of raw material for biodiesel production
process.
Acknowledgments
Special gratitude to the research group: Energy
Recovery of Natural Resources—APRENA,
Department of Chemistry from National University of
Colombia for the contribution to this research.
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