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Removal of NaCl from glycerol by ion exchange

Article  in  Przemysl Chemiczny · January 2008

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Manuel Carmona Juan Francisco Rodríguez

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 Research Article
Received: 5 November 2008 Revised: 9 December 2008 Accepted: 13 January 2009 Published online in Wiley Interscience: 6 March 2009

(www.interscience.wiley.com) DOI 10.1002/jctb.2144

Purification of glycerol/water solutions from

biodiesel synthesis by ion exchange: sodium
and chloride removal. Part II†
Manuel Carmona, Anna Lech, Antonio de Lucas, Angel Pérez and
Juan F. Rodriguez∗

Abstract
BACKGROUND: Equilibrium studies were carried out with the aim of finding the basic design parameters for ion exchange
plants using a glycerol phase obtained from biodiesel production. The uptake of sodium and potassium ions on a strongly
acidic ion exchanger, Amberlite IR-120, in the proton form from glycerol/water mixtures has been studied. The effect on the
selectivity towards sodium of the percentage of water in glycerine/water mixtures on the macroporous resin Amberlite 252
has been analyzed. Finally, chloride removal by a strongly basic anionic-exchange resin Amberlite IRA-420 at three different
temperatures has been studied.

RESULTS: The strongly acidic ion exchanger Amberlite IR-120 exhibits higher selectivity for potassium versus sodium ions.
The ideal mass action law model was able to fit the experimental equilibrium data. The equilibrium data obtained at different
percentages of water in the glycerine/water mixture indicate that as the water content increased the resin selectivity for sodium
uptake is reduced. The selectivity of the anion exchange resin Amberlite IRA-420 for chloride ions decreases with temperature.
The ideal mass action law was accurate enough to fit the equilibrium data of the three systems and allowed the equilibrium
thermodynamic properties to be obtained.

CONCLUSIONS: These results confirm that macroporous resin Amberlite 252 could be a good choice to remove sodium ions
from glycerol/water solutions with a high salt concentration and also that a strongly basic anionic-exchange resin could be used
for chloride removal.

c 2009 Society of Chemical Industry

Keywords: glycerol; ion exchange; adsorption; biodiesel

INTRODUCTION conditions.6 Glycerol is obtained as a by-product with a production

In recent years the diminishing of fossil fuel supplies, the
increase of petroleum prices and the contribution of fossil fuel
combustion to global warming has created increasing interest in
the development of alternative fuels, mainly biodiesel or ethanol,
as renewable transportation fuels. Biodiesel reduces the net carbon
dioxide emissions, produces less smoke, diesel particulate matter,
carbon monoxide and hydrocarbon emissions. Additionally, it is
biodegradable, non-toxic, has a high octane number and provides
engine lubrication to low-sulfur diesel fuel.1,2 Recent government
measures like the EU Directive 2003/30/EC on the promotion of
the use of biofuels or other renewable fuels for transport and
the US Energy Policy Act (EPAct) passed in 1992 to accelerate
the use of alternative fuels in the transportation sector favour
biocomponents playing an increasing role in motor fuel.3,4
Biodiesel is made by the transesterification of vegetable oils and
animal fats with methanol or ethanol homogeneously catalyzed
by sulfuric or hydrochloric acid, sodium and potassium hydroxide,
or an enzyme such as lipase, or heterogeneously catalyzed by
cationic or anionic resins.5,6
Alkaline catalyts are the most widely used because they exhibit
1130
of close to 10 wt % with respect to the biodiesel.
The glycerol stream, 50 wt % glycerol, leaving the separator
contains methanol, catalyst and soap. Methanol is recovered by
vacuum distillation leaving the salt of the alkaline cation and
glycerol with a water content of about 85 wt %.7 – 10 Further
glycerol refining is required to obtain a product with a purity up
to 99.5–99.7% using ion exchange for salt removal followed by
vacuum distillation for water elimination.8
Although ion exchange seems to be one of the most suitable
methods for the removal of salts in the case of low salt
concentration in the glycerol solution or as a finishing step, there is
a lack of fundamental information about the influence of organic
∗ Correspondence to: Juan F. Rodriguez, Department of Chemical Engineering,
University of Castilla-La Mancha, Avda. de Camilo José Cela s/n, 13004 Ciudad
Real, Spain. E-mail: juan.rromero@uclm.es
† Part 1: J Chem Tech Biotechnol DOI 10.1002/jctb.2016.

Department of Chemical Engineering, University of Castilla-La Mancha, Avda.

a higher rate of transesterification under moderate reaction de Camilo José Cela s/n, 13004 Ciudad Real, Spain

J Chem Technol Biotechnol 2009; 84: 1130–1135 www.soci.org

c 2009 Society of Chemical Industry
Purification of glycerol/water solutions from biodiesel synthesis. Part II
solvents on the equilibrium and kinetics of this well known water
cation/anion/resin system.
Most of the work previously performed with ion exchangers
in non-aqueous media has been done with macroporous ion
exchangers.11 A practical example of this is the sorption of
nitrogenated compounds from gasoline onto Amberlite 15, which
requires in excess of 72 h to reach equilibrium.12 Also Amberlite
252, designated by the manufacturer as a macroporous strong
acid resin, has been used in previous studies of this group for the
removal of the alkaline catalyst after polyol production.13 – 16 In
almost all the applications of ion exchangers as catalyst in organic
synthesis a macroporous resin has been employed.17,18 Although
our research group has made efforts to study the behavior of a gel-
form resin in the removal of alkaline metal ions from non-aqueous
mixtures, experimental data on the performance of such resins in
non-aqueous media are scarce.19 – 21
If the studies and practical applications of ion exchange for the
purification of non-aqueous solution are scant, the knowledge of
the influence of the proportions of different solvents in a mixture
or the polarity of the solvents on the ion exchange equilibrium
or kinetic are almost non-existent.22,23 Equilibrium studies in non-
aqueous systems are limited and most cases do not progress
from the pure solvents.24,25 Some studies have shown that the
ratios between the solvents in a mixture can change the selectivity
towards the ions involved in a process dramatically.20 It would
therefore be of interest to know how the relative proportions of
glycerol and water affect the equilibrium uptake and selectivity of
the resin towards the ions involved in the process.
Studies have been made of a process in which the residual
alkaline hydroxide that remains in the glycerol phase after reaction
is neutralized with chloride, and obviously for glycerol purification
purposes, the chloride ion could also be removed afterwards
with an anion exchange resin. The information about anion
exchange in non-aqueous media is even more scarce than for
cation exchangers.26 – 28 Thus it is important to carry out a first
approximation of the possibility of using anion exchangers for this
purpose
The aim of this work is therefore to clarify the previously men-
tioned subjects. First, to understand the sodium and potassium
equilibrium data on the strongly acidic gell-form cation-exchange
resin Amberlite IR-120 at 318 K. Second, to compare the perfor-
mance of Amberlite IR-120 and 252 and to select the more selective
in glycerol-water media by studing the equilibrium of the binary
system H+ /Na+ on the selected resin in mixtures of glycerol/water
in different proportions. Third, to understand the equilibrium be-
haviour of chloride ions on the strongly basic anion-exchange resin
Amberlite IRA-420 in OH− -form at different temperatures. In the
three cases the basic equilibrium parameters of the H+ /Na+ and
OH− /Cl− systems was obtained by applying the mass action law.
Table 1. Properties of Amberlite IR-120 and Amberlite IRA-420
Active Particle size,
Resin group D (m)
Amberlite IR-120 Sulfonic 2.52 × 10−4
Amberlite 252 Sulfonic 4.94 × 10−4
Amberlite IRA-420 Quaternary Amine 4.90 × 10−4
J Chem Technol Biotechnol 2009; 84: 1130–1135

c 2009 Society of Chemical Industry
www.soci.org
EXPERIMENTAL SECTION
Chemicals
Glycerine (C3 H8 O3 ) with a water content of 2 wt % and purity
greater than 97% was supplied by Sigma-Aldrich (Madrid, Spain).
Sodium chloride, potassium chloride, hydrogen chloride (37 wt
%), sodium hydroxide and potassium hydroxide PA grade quality
were supplied by Panreac (Barcelona, Spain). Demineralised water
with conductivity lower than 5 µS was used to prepare the
synthetic glycerol solutions with 10 wt % of water simulating
the conventional solutions obtained from biodiesel production.
Ion exchange resin
Amberlite IR-120 (Rohm and Hass Co., Barcelona, Spain), is a gel-
form sulfonated polystyrene-divinylbenzene resin; Amberlite 252
(Rohm and Haas Co.), is a macroreticular sulfonated polystyrene-
divinylbenzene resin, and Amberlite IRA-420 (Rohm and Haas
Co.), is a gell-type strongly basic quaternaryamine cross-linked
styrene/divinylbenzene copolymer anion exchange resin. The
main physical properties of the three resins are given in Table 1.
The resins were pre-treated in a column by repeated treatment
with 1.0 mol L−1 NaOH and 1.0 mol L−1 HCl solutions in the proper
sequence to convert them to the H+ -form or OH− -form of
the cationic or the anionic resin, respectively. Finally they were
thoroughly rinsed with demineralised water.
Analytical methods
The sodium or potassium content of solutions was determined
by atomic absorption spectrophotometry with a Varian 220 AS
spectrophotometer (Madrid, Spain). The chloride content was
measured by ion chromatography (Metrohm 861 Advanced
Compact IC with sequential suppression, Madrid, Spain). The
standard uncertainty and reproducibility of measurements was
found to be ±0.1%.
Equilibrium experiments
The experimental set-up consisted of seven 250 mL Pyrex contain-
ers hermetically sealed and mechanically agitated, submerged
in a temperature-controlled thermostatic bath. The temperature
was kept constant with a maximum deviation of ±0.1 K. Different
known masses of resin, in the H+ -form or OH− -form, were placed
in contact with 100 mL of the synthetic mixture of glycerine/water
(90/10 by weight) containing a total concentration of 1 mol L−1 .
Synthetic mixtures were prepared by mixing different amounts of
a 1 mol L−1 solution of NaCl or KCl with solutions containing HCl
1 mol L−1 when the cationic resin was used, or NaOH 1 mol L−1
for the anionic resin. This dilution process was carried out with
the aim of decreasing the initial sodium, potassium or chloride
content and therefore, the amount of ion exchanger required for
the experiments. The accuracy of resin weighing was ±0.0001 g.
The suspension formed by the resin and solution was vigorously
agitated at 200 rpm with a multipoint magnetic stirrer. To ensure
Resin capacity for, sodium or Apparent density, ρR
chloride n∞ (mol kg−1 dry resin) (kg m−3 )
5.00 –
4.83 1.32
3.80 1.15
1131
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 www.soci.org M Carmona et al.

that equilibrium was reached, experiments were left stirring 1.0

overnight. At the end of this period, the mixtures were filtered to
remove the ion exchange resin. Then, the filtrate was analyzed for
sodium content as described above. The resin phase concentration
0.8
in equilibrium with the liquid phase was obtained by means of the
following mass balance equation:

(C0 − C ∗ ) · V 0.6
q∗ = · 103 (1)
W

yB+
where C0 and C ∗ are the initial and equilibrium concentrations
0.4 Experimental data
of sodium in the liquid phase (mol L−1 ), respectively; q∗ denotes
the resin phase equilibrium concentration of the entering ion in Sodium

mmol g−1 of dry resin, V and W are the initial volume of the Potassium
synthetic glycerine/water solutions in litres and the weight of dry 0.2 Theoretical curves
ion exchange resin in grams, respectively. Sodium
Potassium

0.0
RESULTS AND DISCUSSION 0.0 0.2 0.4 0.6 0.8 1.0
29
As shown in Part I of this paper, an accurate interpretation of the xB+
physical reality of the ion exchange process can be achieved using
a mathematical approximation based on the ideal mass action Figure 1. Ion exchange isotherms of sodium and potassium ions on
law. Briefly, the following ion exchange process occurs for a binary Amberlite IR-120 in mixtures of glycerine/water with 10% water at 318 K
and a total concentration of 1 mol L−1 .
system where the ion exchanger (r) is initially in the A-form and B
is the counterion in the solution:
concentration in a mixture with an organic solvent favours salt
β+ β+
r + αBs
βAα+ ⇔ βAα+
s + αBr (2) ionization and furthers the accessibility of the counter ions to the
resin active sites and thus, the capacity of the resin known to be
where α and β are the valences of the ionic species A and B, fully accessible in pure organic solvents is completely available
respectively. in glycerol–water mixtures.16 – 20 The equilibrium constants found
As the dimensionless form of ideal LAM equation will be used, for sodium and potassium are 1.939 and 3.603, respectively. These
the ionic fractions of the ions in both phases has to be defined: values indicate that this resin possesses higher selectivity for the
potassium than the sodium ions. This agrees with the higher affinity
CA∗ CB∗ that this resin exhibited for potassium in potassium–sodium
xA = ; xB = (3)
N N mixtures in aqueous media.20 This higher selectivity that the
∗
q q∗B Amberlite IR-120 exhibits for potassium with respect to sodium
yA = A ; yB = (4) ions can be attributed to the difference between the respective
q0 q0
hydrated ionic radii, 1.65 and 2.2 Å. Thus the lower the hydrated
Here yB and xB represent the ionic fraction of the ion B in the ionic radii the higher the selectivity of the ion-exchanger when
solid and liquid phases, respectively. N is the total concentration the exchangeable ions have the same charge.
of the co-ions in the solution phase (mol L−1 ); and q0 is the useful On the other hand, as shown in Table 1, both the cationic
capacity of the resin in the system studied (mmol g−1 of dry resin). resins Amberlite IR-120 and Amberlite 252 have the same kind
Considering ideal behaviour of both phases the equilibrium of ion exchange sites with high charge density (−SO− 3 ), which
constant equation is as follows: produce strong electrostatic fields without ion-pair formation.
Results reported in Part I for the macroporous resin Amberlite 252
yB (1 − xB ) at a water content of 10% indicate that its maximum capacity
KAB (T) = · (5) is a little lower than the value exhibited by Amberlite IR-120.
(1 − yB ) xB
Nevertheless, its equilibrium constant (6.802) is at least three
Ion exchange using the resin Amberlite IR-120 times higher than that found for Amberlite IR-120.29 This result
Figure 1 shows the equilibrium isotherms in dimensionless form for indicates that for sodium removal from glycerine–water mixtures
the system Na+ /H+ and K+ /H+ at 318 K in glycerol/water solutions the macroporous Amberlite 252 would be the best choice. Taking
on Amberlite IR-120. The experimental data were fitted perfectly into account the effect of the hydrated radii on ion exchange
by assuming ideal behaviour in both phases. This behaviour agrees process, it would be expected that this resin would also exhibit a
with that shown in Part I of this paper by the strongly acidic cation- higher preference for potassium than for sodium.
exchanger Amberlite 252.29 The fitting process gave the same
maximum ion-exchange capacity, q0 = 5.0 mmol protons g−1 dry Effect of water concentration on sodium removal using Amberlite 252
resin, found by Valverde et al.30 for the ions Cu2+ , Cd2+ and Zn2+ A glycerine–water mixture containing 10% water presents a
but a little lower than the values reported by Carmona et al.31 for problem of high viscosity when an ion-exchange process is
removal of the ions Pb2+ , Ni2+ and Cr3+ using this resin in aqueous employed. Two ways can be used to make this solution easier
media. to handle; increasing the temperature of the solution or increasing
As in Part I,29 it is important to point out that this result agrees its water content. The effect of temperature on sodium removal
1132

with previous work indicating that the presence of water at any was studied in Part I.

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c 2009 Society of Chemical Industry J Chem Technol Biotechnol 2009; 84: 1130–1135
Purification of glycerol/water solutions from biodiesel synthesis. Part II www.soci.org

1.0 8
Water content (%)
10
30

Equilibrium Constant (KAB)

6 50
0.8
100

4
0.6
Water content (%)
yNa+

Experimental data
10
2
0.4 30
50
100
Theoretical curves 0
0.2 10 40 50 60 70 80
30 Dielectic Constant
50
100 Figure 3. Relationship between dielectric constants and the equilibrium
constants for the binary system H+ /Na+ using the Amberlite 252 for
0.0 different glycerol/water mixtures at 318 K.
0.0 0.2 0.4 0.6 0.8 1.0
xNa+
exchange sites. As can be seen in Fig. 3, a linear relationship with
Figure 2. Ion exchange isotherms of sodium ions on Amberlite 252 in
a correlation factor R2 = 0.988 is obtained between the dielectric
glycerine/water mixtures with different water contents at 318 K and a total
concentration of 1 mol L−1 . constant and the equilibrium constant at different glycerol–water
mixtures (excluding pure water).32,33 These results indicate that
the glycerol effectively solvates the ions favouring its interaction
with the active sites of the resin and thus the resin selectivity for
Table 2. Equilibrium parameters of the system H+ /Na+ on Amberlite
sodium increases with glycerine content.
252 obtained by fitting the experimental data to the ideal mass action
law The increase in glycerine content produces an increase of the
selectivity of the resin for sodium. It seems clear that the greater
Water dielectric constant of glycerine makes it a good solvating agent.
T content q0
System (K) (%) (mmol g−1 ) KAB R2 Taking into account these results, ion exchange removal of
sodium using the macroporous resin Amberlite 252 should be
H+ /Na+ 318 10.0 4.34 6.80229 carried out at low water content and at the crude glycerol
30.0 3.848 0.988 production temperature (333 K).
50.0 4.34 2.085
100.0 1.560
Chloride removal by strongly basic anionic-exchanger Amberlite
IRA-420
Once the sodium ions have been eliminated using Amberlite 252,
Figure 2 shows the equilibrium isotherms in dimensionless form the chloride ions remain in an acidic mixture of glycerine/water
for the system H+ /Na+ at 318 K using four percentages of water and should be eliminated. To remove the chloride ions, an initial
in glycerine. The equilibrium data for a water content of 10% were solution with a concentration 1 mol L−1 NaCl was used because
reported in Part I.29 As expected, the experimental data for all four the use of an acidic solution containing 1 mol L−1 of HCl undergoes
different water contents were perfectly fitted by assuming ideal an irreversible process by neutralization of the protons with the
behaviour in both phases. hydroxyl ions forming water (Equation (6)). The use of an acidic
As can be seen in Table 2, the maximum ion-exchange capacity solution permits quantification of the maximum ion-exchange
is independent of the water content, confirming the above capacity. Thus, using NaCl as solute allows determination of the
comments in which the presence of any concentration of water maximum capacity and also study of the selectivity of the resin for
in a mixture with an organic solvent favours accessibility of the chloride versus hydroxide ions.
counter ions to the resin active sites and thus, the resin capacity
of the resin is fully accessible. On the other hand, the selectivity R OH− + H+ Cl− ⇔ RCl− + H2 O (6)
of the resin for the sodium ions decreases as the water content
increases. where R is an solid active centre.
In a previous paper20 it was stated that the presence of water Figure 4 shows the equilibrium isotherms in dimensionless form
in any concentration in the mixture exerts a stronger influence for the system OH− /Cl− at 303, 318, and 333 K in glycerol/water
than that of the organic solvent on the behaviour of the system, solutions on the strongly basic anionic-exchange resin Amberlite
because the isotherms were quite similar to the aqueous system IRA-420.
employing mixtures of methanol, ethanol and propanol with As can be seen, all the points are above the diagonal and
water. The dielectric constant of water, methanol, ethanol and the curve shape allows the assumption that the system OH− /Cl−
2-propanol at 25 ◦ C are 78.4, 32.6, 24.3 and 20.1, respectively. In exhibits ideal behavior, as was found for the cationic resins. Thus,
1133

this case water seems to be the main solvating agent of the ion the use of strongly acidic or basic resins for sodium chloride

J Chem Technol Biotechnol 2009; 84: 1130–1135

c 2009 Society of Chemical Industry www.interscience.wiley.com/jctb
 www.soci.org M Carmona et al.

1.0 of such large amounts of glycerine in solution. Thus, it is possible

to infer that the high dielectric constant of the glycerine/water
system makes the glycerine also a good solvating agent in this
case and that the slight shrinking of the anionic resin in the mixed
0.8 media does not produce any diminution of the resin capacity.
According to the equilibrium constants, the uptake of chloride
is favoured over hydroxyl ions, as in aqueous media at any
temperature studied. As can be seen, the equilibrium constant
0.6
is also affected by the presence of glycerine favouring the
uptake of chloride because its value in the glycerine–water
yCl–

mixture containing 10% water is almost ten-fold higher that

0.4 Experimental data
that exhibited in aqueous media.33 This result confirms that
T = 303 K the equilibrium constant is strongly affected by the presence
T = 333 K of glycerine, favouring chloride uptake. KAB values also indicate
T = 348 K that the selectivity of this resin for chloride ions decreases with
0.2 Theoretical curves temperature.
T = 303 K On the other hand, the negative value of G◦ indicates that the
T = 333 K ion exchange process is feasible and spontaneous; the negative
T = 348 K
value of H◦ confirms that the ion exchange processes are
0.0 exothermic, whereas the negative value of S◦ suggests that the
0.0 0.2 0.4 0.6 0.8 1.0
randomness decreases at the liquid/solid interface when hydroxyl
xCl–
ions are eluted from the solid by the chloride ions initially present
Figure 4. Ion exchange isotherms of chloride ions on Amberlite IRA-420 in in the liquid phase.
glycerine/water mixtures at 303, 318 and 333 K and a total concentration
of 1 mol L−1 .
CONCLUSIONS
removal from glycerine/water mixtures can be represented by the Equilibria for the sodium and potassium uptake from a solution
ideal mass action law model. of glycerine/water 90/10 w/w using Amberlite IR-120 in H+ -form
As was considered in Part I,29 the standard thermodynamic were favourable at 318 K and the equilibrium behaviour can be
properties of the binary system OH− /Cl− can be obtained by the considered as quasi-ideal. As expected, this resin presents higher
following thermodynamic relation: selectivity for potassium ions due to their lower hydrated ionic
radii.
1 The equilibrium data obtained at different water contents using
KAB (T) =
 ◦  (7) Amberlite 252 lead to the conclusion that the presence of glycerine
1 ·
H AB −S◦
AB in the glycerine/water mixture favours the selectivity of the resin
e R T
for sodium uptake and also that its maximum ion exchange
capacity is fully available. In addition, when glycerine is present
where R is the ideal gas constant, G◦ , H◦ and S◦ are changes
in the glycerine/water mixtures a linear relationship is obtained
in free energy, enthalpy and entropy, respectively.
between the equilibrium constant and the dielectric constant.
The equilibrium experimental data at the three temperatures
The equilibrium for chloride uptake from a 90/10 w/w mixture
studied were simultaneously fitted to the model comprised of
of glycerine/water using Amberlite IRA-420 in OH− -form was
Equations (5) and (7). Thus, the three unknown parameters of the
favourable over the temperature range 303–333 K and the ideal
model, i.e. the maximum capacity (q0 ) and the thermodynamic
mass action law model was able to fit the experimental equilibrium
properties H◦ and S◦ were calculated.
data.
Thermodynamical properties and equilibrium parameter for the
As expected, the maximum capacity of ion-exchange of the
system OH− /Cl− at each temperature obtained using the ideal
Amberlite IRA-420 was fully available for exchange in this non-
mass action law model are given in Table 3.
aqueous mixed media. The affinity of the resin for chloride ion
It is important to point out that the value of the available capacity
decreased with temperature, and the standard thermodynamic
of the resin obtained is the same as in pure water.34,35 Thus in
properties confirmed that this ion exchange process is exothermic,
this case the capacity of the resin is not affected by the presence
spontaneous and feasible.
These results indicate that the macroporous resin Amberlite 252
could be a good choice to remove sodium ions from glycerol/water
Table 3. Equilibrium and thermodynamic properties of the system solutions with a high salt concentration, and also that a strongly
OH− /Cl− on Amberlite IRA-420 obtained by fitting the experimental
data to the ideal mass action law
basic anionic-exchange resin could be used for chloride ion
removal.
q0 H0 S0 G0
T (mmol (kJ (J (kJ
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