Fluid Phase Equilibria 497 (2019) 55e63

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Sodium salts solubility in ternary glycerolþwaterþalcohol mixtures

present in purification process of crude glycerol from the biodiesel
industry
Alexis R. Velez a, b, J. Romina Mufari a, Laura J. Rovetto a, b, *
a rdoba, Argentina
Instituto de Ciencia y Tecnología de los Alimentos ICTA, Facultad de Ciencias Exactas Físicas y Naturales, Universidad Nacional de Co
b n en Ingeniería de Procesos y Química Aplicada IPQA (UNC - CONICET), Facultad de Ciencias Exactas Físicas y Naturales,
Instituto de Investigacio
Universidad Nacional de Co rdoba, Argentina

a r t i c l e i n f o a b s t r a c t

Article history: In this work sodium salts solubility data were obtained for relevant systems involved in crude glycerol
Received 21 December 2018 purification processes. Several binary and ternary mixtures of glycerol þ water and
Received in revised form glycerol þ water þ alcohol were saturated with sodium chloride (NaCl), sodium sulfate (Na2SO4) and
24 May 2019
sodium phosphate (Na3PO4) under different conditions and their respective solubility values were
Accepted 27 May 2019
Available online 31 May 2019
determined. The studied variables were the glycerol:water mass ratio (2:1, 4:1, 9:1), temperature
(T ¼ 293, 303 and 313 K) and type and alcohol concentration added to the mixture as anti-solvent at
p ¼ 0.1 MPa; ethanol, methanol and isopropyl alcohol were added as anti-solvents from 0 to 70 wt% for
Keywords:
Crude glycerol purification
NaCl, and up to 40 wt% for Na2SO4 and Na3PO4 (in salt-free base glycerol þ water þ alcohol mixtures).
Anti-solvent effect Solubility, measured as the total content of anhydrous inorganic salt dissolved in the mixtures, was
Sodium salts determined gravimetrically and using UV spectroscopy. The obtained results show the best anti-solvent
Solubility effect by isopropyl alcohol followed by ethanol, with major efficiencies observed at higher alcohol
concentrations. The water content in the mixture increased sodium salts solubility. Na3PO4 exhibit the
lowest solubility values in the studied systems. Temperature effect was almost negligible in the studied
range.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction % of its initial mass is transformed into glycerol; considered a

Research on renewable energy has been growing over last de-
cades, due to modern lifestyle and the consequent intensive use
and depletion of fossil fuels. Among many different energy sources,
biodiesel, as a biomass derivative fuel, plays an important role into
the energy matrix [1].
The most used and general process to obtain biodiesel is by
transesterification of triglycerides with methanol. This reaction is
usually carried out at atmospheric pressure, temperatures close to
333 K with the use of a base catalyst, such as sodium hydroxide
(NaOH) or sodium methoxide (CH3NaO) [2]. The reaction products
are a mixture of fatty acid methyl esters (i.e. biodiesel) and glycerol.
When conversion of triglycerides is complete, approximately 10 wt
* Corresponding author. Instituto de Investigacio  n en Ingeniería de Procesos y
Química Aplicada IPQA (UNC - CONICET), Facultad de Ciencias Exactas Físicas y
rdoba, Argentina
Naturales, Universidad Nacional de Co
E-mail address: laura.rovetto@unc.edu.ar (L.J. Rovetto).
byproduct of the biodiesel production process [3]. Glycerol is a
versatile molecule consumed as raw material for different type of
industries, such as cosmetic, food and pharmaceutical [4].
Crude glycerol obtained from biodiesel production process is
composed by 20e60 wt% of glycerol [5e9]. Depending on process
conditions, the impurities present in crude glycerol can be meth-
anol, water, methyl esters, free and saponified fatty acids, rests of
catalyst and inorganic salts [8,9]. Several enrichment procedures,
with the aim of increase the glycerol concentration in the mixture,
are described in the open literature. Usually, different chemical and
physical treatments are involved, generally including an evapora-
tion step to eliminate the excess of alcohol and water, and the
subsequent acidification of crude glycerol, which in some cases is
followed by a neutralization step [6e11]. Such acidification step
refers to the addition of an inorganic acid such as sulfuric (H2SO4)
[6,10,11], phosphoric (H3PO4) [7,12,13], hydrochloric (HCl) [8,14,15],
acetic (CH3COOH) [9,13] or perchloric (HClO4) [16]; this step is
needed to induce phase segregation, in order to separate matter

https://doi.org/10.1016/j.fluid.2019.05.023
0378-3812/© 2019 Elsevier B.V. All rights reserved.
56 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63
organic non glycerol (MONG) mainly composed by free and
saponified fatty acids and methyl esters. During this procedure,
salts are formed due to the presence of sodium or potassium base
catalyst. In order to promote the precipitation of formed inorganic
salts dissolved in the glycerol rich phase, the acidification process
must be carried out in the presence of alcohol, which acts as an
anti-solvent [6e8,11]. The decrease in solubility, known as the anti-
solvent effect, has been reported for different systems when
ethanol is added to the mixtures [17,18].
The glycerol rich phase is physically separated from the MONG,
and after this procedure, two main paths in the purification process
can be followed: a) neutralization of the remaining glycerol rich
phase with sodium or potassium hydroxide, with further genera-
tion of inorganic salts which can either, precipitate or, depending
on the system conditions, remain solubilized in the glycerol rich
phase; b) no neutralization, in which case the present salts are the
result of the initial acidification step.
Salt formation and precipitation is function of the process
temperature, the type of alcohol present in the mixture, the inor-
ganic salt formed due to the acidification and/or the neutralization
step, and the amount of water present in the system.
Kongjao et al. [6] used concentrated H2SO4 for acidic treatment
to separate MONG and NaOH in the latter neutralization step and
ethanol to achieve the precipitation of the sodium sulfate (NaSO4).
Javani et al. [7] reports a three steps acidification process with
phosphoric acid (H3PO4) and addition of isopropyl alcohol to pre-
cipitate potassium phosphate (K3PO4) from crude glycerol. Man-
osak et al. [13] compare the effect of the addition of: methanol,
absolute ethanol or propanol, for phosphate salts precipitation
present in the glycerol rich phase, and claim that in all cases,
propanol exhibit the best anti-solvent effect followed by ethanol.
Hidawati and Sakinah [11] used H2SO4 during the acidification step;
the glycerol rich phase was extracted with diethyl ether for com-
plete MONG removal, and afterwards treated with chilled methanol
to precipitate NaSO4. Ha jek and Skopal [9] added methanol previ-
ous to the acidification step and studied different inorganic acids
(H2SO4, H3PO4 and HCl) effect; and report that precipitation yield of
inorganic salt, is enhanced by increasing the volume of added
methanol.
The subsequent stages of the glycerol purification process after
separation of the MONG phase and salt precipitation, depending on
the author, may include many different operations, such as: filtra-
tion, ion exchange adsorption, vacuum distillation, discoloration,
etc. [19].
Data related to inorganic salts solubility in glycerol þ
water þ alcohol mixtures, is of substantial importance for purifi-
cation process of crude glycerol obtained from biodiesel industry,
and to the best of our knowledge not available in the open litera-
ture. Therefore, the aim of the present work is to investigate the
effect of temperature, water content, and amount and type of
alcohol, on solubility of sodium chloride (NaCl), sodium sulfate
(Na2SO4) and sodium phosphate (Na3PO4) in ternary mixtures of
the components present in the glycerol purification process.
2. Experimental section
2.1. Materials
The inorganic salts sodium chloride anhydrous (NaCl,
Mw ¼ 58.44 g/mol), sodium phosphate anhydrous (Na3PO4,
Mw ¼ 163.94 g/mol) and sodium sulfate anhydrous (Na2SO4,
Mw ¼ 142.04 g/mol), were purchased from Anedra (Buenos Aires,
Argentina). Glycerol, methanol, isopropyl alcohol and absolute
ethanol used in this work were supplied by Cicarelli Laboratorios
(Santa Fe, Argentina). The purities of the compounds, together with
Table 1
Suppliers and purity of the compounds used in the experiments.
Chemical name Supplier Purity
Sodium chloride anhydrous Anedra 99%
Sodium phosphate anhydrous Anedra 99%
sodium sulfate anhydrous Anedra 99%
Glycerol Cicarelli 99.5%
Methanol Cicarelli ACS reagent
Isopropyl alcohol Cicarelli ACS reagent
Absolute ethanol Cicarelli 99.5%
the names of suppliers, are presented in Table 1. All products were
used as received without further purification. All solutions were
prepared with distilled water.
2.2. Saturation of mixtures procedure
The experimental apparatus used in this work consist of a 50 mL
jacketed glass vessel equipped with a magnetic stirrer for agitation
of the liquid mixture. Silicone oil was used as a thermostatic fluid to
keep constant the system temperature. A Pt100 sensor ( ±0.1 K) was
immersed in the mixture for temperature monitoring. To start an
experiment 30 g of the liquid solution was placed into the vessel
and kept at the set temperature under agitation. The mother binary
solution used for the solubility experiments was prepared with a
mixture composed by a fixed mass ratio of glycerol:water 2:1, 4:1
and 9:1, to simulate in some extent the range of water and glycerol
content in crude glycerol mixtures.
To evaluate the anti-solvent effect of alcohols, the system be-
comes a ternary mixture by adding to the mother binary system, a
certain amount of ethanol, methanol or isopropyl alcohol according
to the experiment to be carried out (alcohol concentration
expressed in salt-free base). As a result, homogeneous ternary
systems with a specific glycerol:water ratio and different type and
concentration of alcohol were obtained.
The binary (glycerol þ water) or ternary
(glycerol þ water þ alcohol) mixtures were kept at the set tem-
perature under agitation, then 8e10 g of the inorganic sodium
anhydrous salt were added to the mixture assure oversaturated
conditions. The necessary amount of salt added to achieve the
oversaturation of the mixture was estimated in previously explor-
atory experiments not reported. The saturation was reached when
the concentration of the dissolved salt in the mixture was
measured constant over a period of at least 2 h under intense
agitation conditions. Usually took between 4 and 5 hours to reach
equilibrium, at this point the agitation stopped and the system was
kept in a resting state (1e2 h) to allow the complete segregation of
the solid phase. The saturated liquid phase was sampled using a
preheated glass syringe to quantify the dissolved salt.
For each equilibrium point, two experiments were carried out,
and from each experiment two samples were measured; thus, the
reported solubility data corresponds to the average of four values.
Standard deviation and uncertainties for all the measurements
are reported in Tables 2e4 for NaCl, Na2SO4, and Na3PO4
respectively.
2.3. Quantification of dissolved salt
Solubility of NaCl and Na2SO4 was measured by a gravimetric
procedure. A certain amount of saturated solution was weighted in
a ceramic crucible and introduced in a muffle were water and
alcohol present were evaporated and the glycerol content ther-
mally degraded to volatile compounds. The temperature program
was a modification of the total ashes technique [20], initially the
 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63 57

Table 2
Solubility of NaCl at different experimental conditions determined by gravimetric method at p ¼ 0.1 MPa.
1 a
Type of alcohol Temperature (T/K) Mass ratio Glycerol:Water Alcohol content (wt% salt-free base) Solubility (s/g salt$100 g of mixture )
Methanol 303 2:1 0 12.728 ± 0.023
20 9.636 ± 0.063
40 6.769 ± 0.104
70 3.328 ± 0.048
4:1 0 10.298 ± 0.024
20 8.081 ± 0.064
40 6.029 ± 0.080
70 3.433 ± 0.047
9:1 0 8.473 ± 0.083
20 7.009 ± 0.041
40 5.533 ± 0.018
70 3.267 ± 0.019
Ethanol 293 4:1 0 9.894 ± 0.049
20 7.016 ± 0.028
40 4.480 ± 0.014
70 1.450 ± 0.021
303 2:1 0 12.728 ± 0.023
20 8.798 ± 0.043
40 5.365 ± 0.019
70 1.704 ± 0.007
4:1 0 10.298 ± 0.024
20 7.126 ± 0.049
40 4.613 ± 0.012
70 1.565 ± 0.006
9:1 0 8.473 ± 0.083
20 6.137 ± 0.039
40 4.065 ± 0.038
70 1.412 ± 0.023
313 4:1 0 11.382 ± 0.014
20 7.260 ± 0.004
40 4.642 ± 0.009
70 1.615 ± 0.005
Isopropyl alcohol 293 4:1 0 9.894 ± 0.049
20 6.801 ± 0.007
40 4.133 ± 0.031
70 1.145 ± 0.030
303 2:1 0 12.728 ± 0.023
20 8.467 ± 0.192
40 5.359 ± 0.055
70 1.350 ± 0.009
4:1 0 10.298 ± 0.024
20 6.674 ± 0.246
40 4.096 ± 0.093
70 1.115 ± 0.003

The standard uncertainties u are u(s) ¼ 0.0002s (g salt/100 g of mixture), u(T) ¼ 0.1(K).
a
The results are expressed in g salt/100 g of mixture, mean with standard deviation are reported (n ¼ 4).

temperature was increased up to the boiling point of the alcohol
(rate ¼ 10 K/min) and maintained for 1 h for complete alcohol
evaporation. Afterwards, the temperature was raised up to 378 K
(rate ¼ 10 K/min) and kept constant for 1 h to evaporate the water
content completely. Finally, the temperature was increased up to
873 K (rate ¼ 20 K/min) and maintained for 6 h to degrade glycerol
and all organic matter that could be present in the sample. When
the thermal treatment was finished, crucibles were cooled in an
anhydrous environment and weighted to gravimetrically deter-
mine the total content of the inorganic salt, both of them, in
anhydrous form.
To measure the solubility of Na3PO4 the gravimetric technique
was not applicable, because at the required temperatures to elim-
inate the glycerol content from the sample, the phosphate de-
composes. Therefore the solubility of Na3PO4 was determined by a
spectrometric technique. Total phosphate content was determined
by the colorimetric method for inorganic phosphorus determina-
tion in the presence of molybdic acid [21]. For the analysis, 1 mL of
the test solution was combined with 1 mL of ammonium molybdate
(2.5% m/v in 3 N sulfuric acid), 3.6 mL of double-distilled water and
0.4 mL of reductive solution (0.25% m/v of amino naphthol sulfonic
acid in 15% m/v sodium bisulfite solution). The sample was agitated
continuously for 1 min to guarantee the complete mixing of the
liquids, and left to stand for 5 min for color development. The
absorbance was measured at 600 nm using a UVevisible spectro-
photometer (PerkinElmer Lambda 25, Shelton, CT, USA). Method
calibration was carried out with standard solutions of Na3PO4 in
glycerol:water 4:1 mass ratio mixture, in a concentration range
between 0 and 0.004 mg of phosphorus/g of solution. Method
LQ ¼ 0.049 g Na3PO4/100 g mixture.
3. Results
3.1. Solubilities of sodium salts with ethanol as anti-solvent
Solubilities of NaCl, Na2SO4 and Na3PO4 on glycerol:water (4:1
mass ratio) þ ethanol mixtures were compared as shown in Fig. 1.
In all cases the alcohol acts as anti-solvent, decreasing the solubility
of the salt in the ternary mixture. The same trend is observed at all
the measured temperatures (293, 303 and 313 K).
NaCl exhibited the highest solubility in the studied binary and
ternary mixtures, which remained significantly higher than Na2SO4
58 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63

Table 3
Solubility of Na2SO4 at different experimental conditions, determined by gravimetric method at p ¼ 0.1 MPa.
1 a
Type of alcohol Temperature (T/K) Mass ratio Glycerol:Water Alcohol content (wt% salt-free base) Solubility (s/g salt$100 g of mixture )
Methanol 303 2:1 0 5.215 ± 0.033
10 2.717 ± 0.039
20 1.480 ± 0.031
40 0.409 ± 0.012
4:1 0 2.958 ± 0.053
10 1.642 ± 0.012
20 0.931 ± 0.010
40 0.312 ± 0.002
Ethanol 293 4:1 0 3.037 ± 0.008
10 1.512 ± 0.020
20 0.859 ± 0.006
40 0.194 ± 0.003
303 2:1 0 5.215 ± 0.033
10 2.504 ± 0.011
20 1.235 ± 0.023
40 0.314 ± 0.008
4:1 0 2.958 ± 0.053
10 1.382 ± 0.013
20 0.759 ± 0.025
40 0.227 ± 0.017
313 4:1 0 2.793 ± 0.002
10 1.359 ± 0.039
20 0.793 ± 0.002
40 0.135 ± 0.003
Isopropyl alcohol 293 4:1 0 3.037 ± 0.008
10 1.536 ± 0.024
20 0.823 ± 0.011
40 0.230 ± 0.003
303 2:1 0 5.215 ± 0.033
10 2.532 ± 0.022
20 1.382 ± 0.008
40 0.388 ± 0.004
4:1 0 2.958 ± 0.053
10 1.385 ± 0.072
20 0.805 ± 0.055
40 0.250 ± 0.018

The standard uncertainties u are u(s) ¼ 0.0002s (g salt/100 g of mixture), u(T) ¼ 0.1(K).
a
The results are expressed in g salt/100 g of mixture, mean with standard deviation are reported (n ¼ 4).

Table 4
Solubility of Na3PO4 at different experimental conditions determined by spectrophotometric method at p ¼ 0.1 MPa.

Type of alcohol Temperature (T/K) Mass ratio Glycerol:Water Alcohol content (wt% salt-free base) Solubility (s/g salt$100 g of mixture 1)a
Ethanol 293 4:1 0 1.184 ± 0.012
10 0.771 ± 0.005
20 0.658 ± 0.015
40 0.180 ± 0.006
303 4:1 0 1.059 ± 0.015
10 0.711 ± 0.007
20 0.611 ± 0.005
40 0.183 ± 0.003
313 4:1 0 1.051 ± 0.014
10 0.673 ± 0.006
20 0.584 ± 0.020
40 0.174 ± 0.005

The standard uncertainties u are u(s) ¼ 0.049 (g salt/100 g of mixture), u(T) ¼ 0.1(K).
a
The results are expressed in g salt/100 g of mixture, mean with standard deviation are reported (n ¼ 4).

and Na3PO4 in the complete range of ethanol concentration studied
(0e70 wt% in salt-free base). NaCl solubility is at least 3-fold higher
than the sulfate salt. Na3PO4 is the less soluble salt over the
experimental range analyzed and about 7 times less soluble than
NaCl. The potential precipitation of hydrated salts in the case of
Na2SO4 and Na3PO4 will certainly decrease the availability of water
in the system, and consequently decrease the solubility (i.e. lower
amount of dissolved species); nevertheless, regardless of the
characteristics of the solid phase formed, the dissolved species are
reported as anhydrous salts (according to the described experi-
mental procedure).
For the system with NaCl, a linear dependence of the salt
solubility with the ethanol concentration is observed in the
0e70 wt% (salt-free base) range of alcohol. Using a linear
regression method at the lowest temperature (293 K), a coeffi-
cient of determination R2 equals to 0.99 was obtained. At this
temperature a maximum solubility of 9.894 ± 0.049 (g/100 g so-
lution) was measured in absence of ethanol; at 70 wt% of ethanol,
the dissolved concentration NaCl measured reaches 1.450 ± 0.049
(g/100 g solution) at the same temperature. The calculated co-
efficient of determination R2 for linear regression at 303 and
313 K are equal to 0.99 and 0.97 respectively. As the temperature
 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63
Fig. 1. Solubility behavior of: a) NaCl, b) Na2SO4 and c) Na3PO4 with temperature in
glycerol:water 4:1 mass ratio mixtures, at increasing concentration of ethanol (in salt-
free base).
59
Table 5
pH values of glycerol þ water þ ethanol ternary mixtures saturated with Na3PO4.
Glycerol:water 4:1 mass ratio at p ¼ 0.1 MPa.
Ethanol content (wt% salt-free base) Temperature (T/K)
293 303 313
0 10.90 ± 0.03 11.07 ± 0.02 11.54 ± 0.04
10 11.04 ± 0.02 11.21 ± 0.03 11.57 ± 0.04
20 11.36 ± 0.02 11.42 ± 0.02 11.68 ± 0.03
40 11.44 ± 0.04 11.64 ± 0.04 11.95 ± 0.04
The standard uncertainty u is u(pH) ¼ 0.01.
*Mean with standard deviation are reported (n ¼ 3).
increase, the behavior slightly deviates from the linear
dependence.
In Fig. 1c, the solubility of the phosphate sodium salt shows an
apparent discontinuity when 20 wt% of ethanol was added to the
mixture; this could be due to the co-existence of different phos-
phate spices. Although the main objective of this study is to mea-
sure the concentration of dissolved species (which are quantified
and reported as total phosphate, as explained in the experimental
section) when the alcohol concentration increases in the mixture, it
is important to consider the occurrence of the acid species of the
inorganic phosphate salts which are pH dependent, and which
existence may cause this kind of behavior. The measured pH of the
ternary glycerol þ water þ ethanol mixtures in absence of salts was
pH ¼ 5,86 ± 0,05 regardless of the ethanol content (with constant
glycerol þ water mass ratio 4:1). Table 5 shows the measured pH
values for the glycerol þ water þ ethanol mixtures when saturated
with Na3PO4 at increasing ethanol concentrations. The pH values
for these mixtures saturated with phosphate salt oscillate from
10.90 ± 0,03 and 11.95 ± 0,04 showing higher values at each tem-
perature as the ethanol concentration increases. It is
known that the different phosphate species have different solubi-
lity in aqueous solution; at pH values between 11 and 12, the
predominant form of dissociated phosphate salts in water are
HPO2 3 1
4 > PO4 >H2PO4 [22]. The variation in the concentration of
the phosphate ionic species present in the aqueous medium ac-
cording to the pH values could also occur in the measured ternary
glycerol þ water þ ethanol system. The occurrence of different
types of dissolved sodium phosphate salts, could originate the
apparent discontinuity in the solubility curve of Fig. 1c. Neverthe-
less, this assumption and the actual concentration of each of the
species involved should be corroborated using the appropriate
analytical methods to characterize the species, which is beyond the
scope of this study, where the amount of dissolved phosphate salt
in solution is reported as total phosphate.
While solubility of Na2SO4 is almost 3 times higher than Na3PO4
in the binary glycerol þ water mixture (in absence of alcohol),
when  20 wt% (salt-free base) of ethanol is added to the mixture
their solubilities are almost the same, reaching similar values
regardless of the identity of the salt.
NaCl shows lower sensitivity against alcohol concentration in
this type of mixtures; when 40 wt% (salt-free base) of ethanol is
present in the mixture, NaCl solubility decreases approximately
55% at all temperatures, whereas in the case of Na3PO4 solubility
reduction is approximately 83% and more than 92% for Na2SO4. In
order to reduce the solubility of NaCl more than 85%, the ethanol
content in the mixture must be as high as 70 wt% (salt-free base).
Fig. 2 depicts the percent decrease in solubility for the studied salts,
as average values between the three studied temperatures. The
largest anti-solvent effect is observed for Na2SO4, a sudden 74%
60 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63
Fig. 2. Percent decrease in solubility of NaCl, Na2SO4 and Na3PO4 in glycerol:water 4:1
mass ratio mixtures with increasing concentration of ethanol (salt-free base) at aver-
aged studied temperatures.
decrease in solubility is observed when ethanol concentration
increased from 0 to 20 wt% (salt-free base). The anti-solvent effect
is less pronounced after this point, decreasing the solubility only an
extra 18% when the ethanol content doubles. Such pronounced
effect at low ethanol concentration is not observed for Na3PO4,
which solubility decrease is less abrupt at low ethanol content. NaCl
solubility behaves less sensitive to the presence of ethanol (only
32% solubility decrease at 20 wt% of ethanol) showing almost a
linear dependence.
As it was already mentioned, the results show that the dissolved
mass of the three inorganic salts studied decreased as alcohol
concentration increased. Same behavior on inorganic potassium
salts was observed by H ajek and Skopal [9]. In their work, they
found that by increasing the amount of methanol, in the range of
10e35 wt%, a greater yield of precipitated monopotassium phos-
phate (KH2PO4) was achieved. Ooi et al. [10] found similar results
when performing chemical and physical treatments to recover
crude glycerol from glycerol residue and evaluating the pH effect;
they also report lower NaHSO4 and Na2SO4 solubility than NaCl in
the system. Manosak et al. [13] who perform a three stage physic-
chemical refining process of crude glycerol, report salt precipitation
when using H3PO4 during the acidification step, whilst no salt
precipitation was observed when H2SO4 was added to the crude
glycerol at similar conditions, which is in agreement with this
results.
3.2. Temperature effect on salts solubility
The effect of temperature on solubility behavior of the three
studied salts, NaCl, Na2SO4 and Na3PO4 in binary glycerol:water
mixtures (mass ratio 4:1) and ternary systems
glycerol þ water þ ethanol (alcohol concentration in salt-free base
up to 70 wt% in mass for NaCl and up to 40 wt% for Na3PO4 and
Na2SO4). Small differences in the amount of dissolved salt with
temperature increments in the experimental range from 293 to
313 K are observed in Fig. 1 for all the samples.
In the case of NaCl, the small dependence of solubility with
temperature in pure water is well known; for glycerol þ water
mixtures Carr et al. [23], report a slight solubility change with
temperature. In this study, similar behavior is observed when
ethanol is present in the mixture, i.e. no substantial variation of salt
solubility is observed at different temperatures. In the binary
glycerol þ water system (mass ratio 4:1) NaCl solubility increases
15% varying from 9.894 ± 0.049 to 11.382 ± 0.014 (g/100 g solution)
when temperature goes from 293 to 313 K. For the same temper-
ature range, in the glycerol þ water þ ethanol system the solubility
increment with temperature is between 3 and 11% (in the studied
alcohol concentration range).
The solubility of Na2SO4 in pure water increases with temper-
ature up to 305.15 K, and then slightly decreases with further rise in
temperature up to 343.15 K [24]. On the other hand, in this study,
the Na2SO4 solubility values measured in the glycerol þ water bi-
nary system exhibits an small decrease (8%) in solubility from
3.037 ± 0.008 down to 2.793 ± 0.002 (g/100 g solution) when
increasing 20 in temperature. The same negative dependence in
observed in the ternary system glycerol þ water þ ethanol, with
decreasing solubility differences between temperatures as the
alcohol concentration increases.
In the literature, the solubility increment of sodium phosphate
salts (Na3PO4, Na2HPO4, NaH2PO4) in water with temperature is
reported [25,26]. Contrary, the solubility values measured as
anhydrous Na3PO4 in the glycerol þ water system show an small
negative dependence (11%) from 1184 ± 0,012 down to
1051 ± 0,014 (g/100 g solution) in the studied temperature range. In
the ternary system glycerol þ water þ ethanol, the same negative
dependence in observed, also with decreasing solubility differences
between temperatures as the alcohol concentration increases.
However, the possible existence of ionic species of phosphate salts
in solution has to be considered, and may be the subject of future
studies.
3.3. Effect of type of alcohol on salts solubility
To investigate the effect of different types of alcohols on sodium
salts solubility, the behavior of NaCl and Na2SO4 was compared
when methanol, ethanol and isopropyl alcohol were added to
glycerol þ water mixtures. NaCl was studied at glycerol þ water
mass ratios of 2:1, 4:1 and 9:1, and Na2SO4 at glycerol þ water mass
ratios of 2:1 and 4:1. All the experiments were carried out at 303 K.
In Fig. 3 the results for NaCl in glycerol þ water þ alcohol ternary
system can be observed. The best anti-solvent effect was obtained
when isopropyl alcohol was added to the mixture. Almost 90% of
solubility decrease is observed for the glycerol:water 2:1 and 4:1
mass ratios, when isopropyl alcohol reaches 70 wt% (salt-free base).
Similar anti-solvent efficiency is observed when ethanol was used,
reaching comparable solubility values at equivalent concentrations.
Methanol shows the poorest anti-solvent performance compared
with ethanol and isopropyl alcohol, allowing a greater amount of
NaCl solubilized in the whole alcohol concentration range. Meth-
anol addition decreases the NaCl solubility in 74%, 67% and 61% at
glycerol:water mass ratio of 2:1, 4:1 and 9:1 respectively. At the
highest alcohol concentration present in the mixture, the measured
solubility values seem to be independent of the original glycerol:-
water mass ratio, for all the studied alcohols. At the highest alcohol
concentration (70 wt% salt-free base) the NaCl solubility averaged
for the three glycerol þ water mass ratios (i.e. 2:1, 4:1 and 9:1) is
3.343 ± 0.014 (g/100 g solution) for methanol, 1.560 ± 0.043 (g/
100 g solution) for ethanol, and 1.233 ± 0.028 (g/100 g solution) for
isopropyl alcohol, regardless of the initial glycerol:water mass ratio
present in the ternary system.
Fig. 4 shows solubility values for Na2SO4 in the glycerol:water
mixtures with 2:1 and 4:1 mass ratio with the addition of 0e40 wt%
of alcohol (salt-free base). As it can be observed, there are no sig-
nificant differences in Na2SO4 solubility values depending on the
type of added alcohol in the complete range of alcohol
 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63
Fig. 3. Alcohol antisolvent effect on NaCl solubility in glycerol:water mixtures at
different mass ratios a) 2:1, b) 4:1 and c) 9:1 with increasing concentration of ethanol
(salt-free base), methanol and isopropyl alcohol at 303 K.
61
Fig. 4. Alcohol antisolvent effect on Na2SO4 solubility in glycerol:water mixtures with
2:1 mass ratio (solid line) and 4:1 mass ratio (dash line) with increasing concentration
of ethanol, methanol and isopropyl alcohol at 303 K.
concentration studied. When alcohol concentration was as high as
40 wt% (salt-free base), solubility of Na2SO4 reaches almost the
same value, independently of the type of alcohol used and the
initial glycerol:water mass ratio of the mixture, with an average
value of 3.166 ± 0.722 (g/100 g solution). The obtained results are in
agreement with Manosak et al. [13] who report lower ash content
in treated crude glycerol with addition of isopropyl alcohol, against
ethanol and methanol.
3.4. Effect of water content on salts solubility
An important variable on solubility of inorganic salts in the
studied mixtures is the water content. Fig. 5 shows experimental
solubilities of NaCl in glycerol þ water mixtures with increasing
glycerol content in the mixture at 298.15 K reported by Carr et al.
[23] and compared with NaCl solubility values obtained in this
work at 303 K (due to the low temperature dependence of NaCl
solubility, the small temperature difference is neglected for com-
parison purposes). It can observe than the obtained values are in
accordance with the literature and the solubility of NaCl decreases
with the reduction of water content in the mixture.
Figs. 3 and 4 show solubility values for NaCl and Na2SO4 at 303 K
with increasing alcohol concentrations for different glycerol:water
mass ratios. For both salts, the reduction of the amount of water
present in mixture decreases the solubility of the inorganic salt.
This can be observed by larger solubility values at smaller glycer-
ol:water ratios. This behavior is expected considering that NaCl
solubility is almost four times higher in water than in pure glycerol
at 298.15 K [27]. This effect is larger in absence of alcohol in the
mixture. NaCl solubility decreases from 12.728 ± 0.023 (g/100 g
solution) to 8.473 ± 0.083 (g/100 g solution) when glycerol:water
mass ratio varied from 2:1 to 9:1 in absence of alcohol. Such dif-
ferences in solubility became smaller as the amount of alcohol
added to the system increased.
For Na2SO4 similar behavior was observed. In absence of alcohol,
62 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63
Fig. 5. NaCl solubility in glycerol þ water mixtures with increasing concentration of
glycerol (salt-free base). Data from Carr et al. at 298 K and this work at 303 K.
solubility decreased from 5.215 ± 0.033 (g/100 g solution) to
2.958 ± 0.053 (g/100 g solution) when mass ratio glycerol:water
varied from 2:1 to 4:1. Also in this case, as alcohol concentration
increased, differences between solubility values decreased, more-
over no significant differences were detected when alcohol con-
centration increased up to 40%.
4. Conclusions
This work investigated the solubility of three different inorganic
sodium salts (NaCl, Na2SO4 and Na3PO4) in glycerol:water mixtures
when alcohols were added to the system to act as anti-solvent. The
influence over the salts solubility of different types of alcohols,
temperature, glycerol:water mass ratio and amount of water pre-
sent in the system was studied.
The highest solubility values were found for the NaCl systems at
all the glycerol:water mass ratios studied in the temperature range
of 293e313 K, followed by Na2SO4, and being Na3PO4 the less sol-
uble salt.
The antisolvent effect of ethanol in glycerol:water 4:1 mass ratio
systems is more significant for the system with Na2SO4, decreasing
more than 92% its solubility, 83% reduction in the case of Na3PO4
and only 55% for NaCl, when 40 wt% of ethanol (salt-free base) is
present at 303 K. The same trend is also observed at 293 and 313 K,
for all systems. NaCl exhibit a linear solubility dependence on
alcohol concentration in the mixture. Overall, a decrease in sodium
salts solubility was observed, when alcohol concentration increases
in the ternary glycerol þ water þ alcohol mixtures.
Small temperature dependence was found on solubility
behavior of the three sodium salts studied in the glycerol þ water
and glycerol þ water þ alcohol mixtures in the temperature range
of 293e313 K. NaCl solubility shows a small increment with tem-
perature with and without ethanol in the mixture, whereas Na2SO4
and Na3PO4 solubility with and without ethanol, exhibit a small
negative dependence with increasing temperature.
Out of the three alcohols studied as anti-solvent, best results
were obtained when isopropyl alcohol was added to the
glycerol þ water mixture for all the glycerol þ water mass ratios
studied. Although a little less efficient, ethanol addition has a
comparable anti-solvent effect, achieving similar solubility values
at equal composition in the mixture. Methanol shows the poorest
anti-solvent performance.
When the glycerol:water mass ratio in the system increased, a
decrease of NaCl and Na2SO4 solubility was observed in the ex-
periments. This effect becomes less significant when the ethanol
concentration increased in the mixture, reaching at the highest
ethanol concentrations studied, the same salt solubility values
independently of the original glycerol:water mass ratio.
Acknowledgments
The authors acknowledge Ma. Paula Sappia and Mayra B. Falco
for their collaboration in this work and FONCYT (PICT N
2014e2263) and SeCyT-UNC for financial support
References
[1] International Energy Agency, Renewables, Market Analysis and Forecast from
2018 to 2023, 2018, 2018. accessed October 18, 2018, https://www.iea.org/
renewables2018/transport/.
[2] H. Fukuda, A. Kondo, H. Noda, Biodiesel fuel production by transesterification
of oils, J. Biosci. Bioeng. 92 (2001) 405e416, https://doi.org/10.1016/S1389-
1723(01)80288-7.
[3] S. Saka, D. Kusdiana, Biodiesel fuel from rapeseed oil as prepared in super-
critical methanol, Fuel 80 (2001) 225e231, https://doi.org/10.1016/S0016-
2361(00)00083-1.
[4] P. Bondioli, From oil seeds to industrial products: present and future oleo-
chemistry, J. Synth. Lubr. 21 (2005) 331e343, https://doi.org/10.1002/
jsl.3000210406.
[5] M. Hunsom, C. Autthanit, Adsorptive purification of crude glycerol by sewage
sludge-derived activated carbon prepared by chemical activation with H3PO4,
K2CO3 and KOH, Chem. Eng. J. 229 (2013) 334e343. https://doi.org/10.1016/j.
cej.2013.05.120.
[6] S. Kongjao, S. Damronglerd, M. Hunsom, Purification of crude glycerol derived
from waste used-oil methyl ester plant, Korean J. Chem. Eng. 27 (2010)
944e949.
[7] A. Javani, M. Hasheminejad, K. Tahvildari, M. Tabatabaei, High quality potas-
sium phosphate production through step-by-step glycerol purification: a
strategy to economize biodiesel production, Bioresour. Technol. 104 (2012)
788e790, https://doi.org/10.1016/j.biortech.2011.09.134.
[8] Y. Xiao, G. Xiao, A. Varma, A universal procedure for crude glycerol purifica-
tion from different feedstocks in biodiesel production: experimental and
simulation study, Ind. Eng. Chem. Res. 52 (2013) 14291e14296, https://
doi.org/10.1021/ie402003u.
[9] M. Ha jek, F. Skopal, Treatment of glycerol phase formed by biodiesel pro-
duction, Bioresour. Technol. 101 (2010) 3242e3245, https://doi.org/10.1016/
j.biortech.2009.12.094.
[10] T.L. Ooi, K.C. Yong, K. Dzulkefly, W.M.Z. Wan Yunus, A.H. Hazimah, Crude
glycerine recovery from glycerol residue waste from a palm kernel oil methyl
ester plant, J. Oil Palm Res. 13 (2001) 16e22.
[11] E.N. Hidawati, a M.M. Sakinah, Treatment of glycerin pitch from biodiesel
production, Int. J. Chem. Environ. Eng. 2 (2011) 309e313.
[12] C. Tianfeng, L. Huipeng, Z. Hua, L. Kejian, Purification of crude glycerol from
waste cooking, Oil Based Biodiesel Product. Orthogonal Test Method 15
(2013) 48e53.
[13] R. Manosak, S. Limpattayanate, M. Hunsom, Sequential-refining of crude
glycerol derived from waste used-oil methyl ester plant via a combined
process of chemical and adsorption, Fuel Process. Technol. 92 (2011) 92e99,
https://doi.org/10.1016/j.fuproc.2010.09.002.
[14] R.W.M. Pott, C.J. Howe, J.S. Dennis, The purification of crude glycerol derived
from biodiesel manufacture and its use as a substrate by Rhodopseudomonas
palustris to produce hydrogen, Bioresour. Technol. 152 (2014) 464e470,
https://doi.org/10.1016/j.biortech.2013.10.094.
[15] R. Dhabhai, E. Ahmadifeijani, A.K. Dalai, M. Reaney, Purification of crude
glycerol using a sequential physico-chemical treatment, membrane filtration,
and activated charcoal adsorption, Separ. Purif. Technol. 168 (2016) 101e106,
https://doi.org/10.1016/j.seppur.2016.05.030.
[16] S. Sadhukhan, U. Sarkar, Production of purified glycerol using sequential
desalination and extraction of crude glycerol obtained during trans-
esterification of Crotalaria juncea oil, Energy Convers. Manag. 118 (2016)
450e458, https://doi.org/10.1016/j.enconman.2016.03.088.
[17] Y. Asakuma, Y. Murakami, M. Konishi, Anti-solvent effect of crystallization by
feeding ethanol under microwave radiation, Cryst. Res. Technol. 49 (2014)
129e134, https://doi.org/10.1002/crat.201300327.
[18] E.W. Bazi, C. Porte, I. Mabille, J. Havet, Antisolvent crystallization : effect of
ethanol on batch crystallization of a glycine, J. Cryst. Growth 475 (2017)
232e238, https://doi.org/10.1016/j.jcrysgro.2017.06.021.
[19] M.S. Ardi, M.K. Aroua, N.A. Hashim, Progress, prospect and challenges in
glycerol purification process: a review, Renew. Sustain. Energy Rev. 42 (2015)
1164e1173, https://doi.org/10.1016/j.rser.2014.10.091.
 A.R. Velez et al. / Fluid Phase Equilibria 497 (2019) 55e63
[20] Oficcial Methods of Analysis of the Association of Official Analysis Chemist,
AOAC, 1999.
[21] C.H. Fiske, Y. Subbarow, The colorimetric determination of phosphorus, J. Biol.
Chem. 66 (1925) 375e400.
nicos Y sus Aplicaciones Analíticas, Editorial
[22] M. Silva, J. Barbosa, Equilibrios Io
Síntesis S.A., Madrid, Spain, 2002.
[23] A.R. Carr, R.E. Townsend, W.L. Badger, Vapor pressures of glycerol-water and
glycerol-water-sodium chloride systems, Ind. Eng. Chem. 17 (1925) 643e646,
https://doi.org/10.1021/ie50186a043.
[24] P. Bharmoria, P.S. Gehlot, H. Gupta, A. Kumar, Temperature-Dependent Sol-
ubility Transition of Na 2 SO 4 in Water and the E Ff Ect of NaCl Therein :
63
Solution Structures and Salt Water Dynamics, 2014, https://doi.org/10.1021/
jp507949h.
[25] H. Stephen, T. Stephen, Solubilities of Inorganic and Organic Compounds, first
ed., Pergamon Press, 1963.
[26] A.J. Panson, G. Economy, C.-T. Liu, T.S. Bulischeck, W.T. Lindsay Jr., Sodium
phosphate solubility and phase relations basis for invariant point chemistry
control, J. Electrochem. Soc. 122 (1975) 915e918, https://doi.org/10.1149/
1.2134369.
[27] PubChem, Compound Summary for CID 5234, accessed November 11, 2017,
https://pubchem.ncbi.nlm.nih.gov/compound/sodium_
chloride#section¼Melting-Point.