PURIFICATION OF THE GLYCEROL PHASE AFTER

TRANSESTERIFICATION OF VEGETABLE OILS

Martin Hjek, Frantiek Skopal

Martin Hjek, Department of Physical Chemistry, Faculty of Chemical
Technology, University of Pardubice, Studentsk 573, 532 10 Pardubice,
Czech Republic,
Phone: +420 466 037 055, Fax: +420 466 037 068,
e-mail: martin.hajek2@upce.cz

Keywords: biodiesel, glycerol phase, high fatty acids

ABSTRACT
The glycerol phase is a side product of biodiesel production, which contains
also many another materials (soaps, rests of catalyst, water, esters ) formed
by process of biodiesel production. The content of glycerol in this side product
(glycerol phase) is 30-60 %. The target is to gain single components in more
usable form by easy purification and treatment of the glycerol phase. In this
paper, it is presented haw to gain glycerol (purity 90 %) and mixture higher
fatty acids with esters (1:1) or only mixture of fatty acids (purity 99 %). The
side product of this treatment is potash-phosphate fertilizer. The optimal
conditions of preparation of fatty acids mixture and glycerol were investigated.
INTRODUCTION
Glycerol is tribasic alcohol which has a very wide utilization in many branches
(food industry, pharmacy, cosmetic industry, production of plastic materials
and explosives).
Nowadays, glycerol is created during production of soaps (it is a side product)
which are produced by saponification of vegetable oils or animal fats
(triglycerides). During their production, the triglycerides are divided by
hydroxide into salts of fatty acids (soaps) and glycerol [1]. Glycerol is possible
to be produced from propene [2]. Another possibility to gain glycerol is by
production of biodiesel (it is a side product), which is produced by
transesterification of vegetable oils and animal fats. In the EU, the production
of biodiesel was 7.56 millions tons in 2008. The utilization of side product will
be convenient for better economic aspect of overall biodiesel production.
Biodiesel production: after transesterification and distillation off excess
alcohol, the reaction mixture is separated to two phases. The lighter ester
phase contains the main product - biodiesel and the heavier phase (called as
a glycerol phase - GP) contains all other products. The glycerol phase
consists, except glycerol, of many other chemical substances: water, organic
and inorganic salts, a small amount of esters and methanol, traces of
glycerides and colors. The exact composition of the raw GP depends on the
transesterification and the separation conditions of biodiesel preparation, but
usually glycerol concentration is in the range of 30-60 %. For other utilizations,
it is important to gain glycerol in more concentrated form.
The usage of glycerol gained from biodiesel production process is, e.g., in
production of docosahexaenoic acid through fermentation of the microalga
44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009 1
Schizochytrium limacinum. The optimal conditions of preparation were
investigated. According to authors, glycerol is a promising feedstock for
production of acid from heterotrophic algal culture [3]. Dasaria studied the
preparation of 1,2-propandiol from glycerol with the help of several metal
catalysts. Copper-chromite catalyst was identified as the most effective
catalyst for the two-step hydrogenolysis of glycerol to propylene glycol [4].
THEORY
In our technology of biodiesel production, the transesterification is catalyzed
by potassium hydroxide. The reaction is stopped by the gaseous carbon
dioxide, which neutralizes the catalyst excess. The potassium carbonate and
bicarbonate are formed by neutralization [5].
For other utilizations, it is important to gain the single component (glycerol,
fatty acids and other materials) from the GP in more usable form.
The addition of strong acid forms the soaps (presented in the GP from the
saponification of oil during biodiesel production) to higher fatty acids (2) and
carbonates to carbon dioxide (3). The other products of these reactions are
the salts of inorganic acid.
The other possibility of treatment of the GP is the saponification of esters
remains by strong alkali material to soaps in the first step (1). The formed
soaps are neutralized together with carbonates in the next step (2).
Saponification: R-COOCH
3
+ OH
-
R-COO
-
+ CH
3
OH (1)
Neutralization: R-COO
-
+ H
+
R-COOH (2)
K
2
CO
3
+ KHCO
3
+ 3 H
+
3 K
+
+ 2 CO
2
+ 2 H
2
O (3)
Then, the GP is divided to two phases: lighter phase containing organic
substances (fatty acids and esters) called organic phase OP and heavier
bottom phase containing polar substances (glycerol, water and inorganic
salts), called as pure glycerol phase PGP.
EXPERIMENTAL METHODS
Chemicals
Raw glycerol phase with different compositions (Tab. I), potassium hydroxide
pure (solid 83 wt.%). Methanol (technical). Sulphuric acid (96 wt.%),
hydrochloric acid (36 wt.%), phosphoric acid p.a. (85 wt-%), acetic acid, all
Lach-Ner, Czech Republic. Demineralized water.
Tab. I: The composition of glycerol phase (in wt.%)
glycerol soaps KHCO
3
K
2
CO
3
water methanol esters
I 56.36 17.10 1.04 0.8 14.00 1.9 8.8
II 51.32 21.81 0.53 0.79 11.68 4.6 9.27
III 58.89 16.82 0.82 0.96 14.11 2.2 6.2

Procedure of experiments
The constant amount of the raw glycerol phase (500 g) was put into the batch
glass reactor (1 l) and diluted by chosen amount of methanol.
44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009 2
Neutralization: The concentrated acid was slowly added to reach pH ca 3
4 and the mixture was stirred for 15 min. The acid formed potassium
carbonates and bicarbonates to carbon dioxide and soaps to fatty acids. The
formed coagulation of salt was filtered off by a frit and excess of methanol was
distilled off (at the temperature 60 C, pressure ca 3 kPa and took 50 min).
The distilled methanol can be used again for the dilution of the raw GP. Then,
the heterogeneous reaction mixture was cooled to the temperature 25 C and
optimum amount of water was added for better and faster separation [6].
Then, the mixture was poured into the separation funnel where the separation
of phases began. After a perfect separation of the reaction mixture to the
upper organic phase and the lower pure glycerol phase both phases were
analyzed. Many samples of the raw glycerol phase with different composition
were tested with different acids.
Saponification of esters in the raw GP is another possibility; only higher
fatty acids are gained in the OP. The raw GP was put into the batch glass
reactor and tempered to 25 C. The potassium hydroxide was solved in
methanol and this solution was added to reactor and the saponification of
esters started. After saponification, the reaction mixture was neutralized by
concentrated acid. Following process is the same as in neutralization.
Analytical methods
The yields of phases were defined and determined as the weight ratios of the
phase to raw glycerol phase. The yield of formed precipitate was defined as
the weight ratio of experimentally determined to theoretical calculated value
(from the known composition of the raw GP) multiplied by 100. The density of
the OP was determined by pycnometric method.
The determination of acid number (an) was carried out by alkalimetric
titration by the ethanolic solution of KOH with visual detection of equivalence
point. The used method is described in EN 14214.
In the PGP, there are solved traces (after filtration) of strong acid (H
3
PO
4
)
and its salt (KH
2
PO
4
). The determinations of both components were carried
out within one alkalimetric titration by potassium hydroxide in water. The result
of this determination was a two-step titrimetric curve. It was found that
phosphoric acid was titrated to dihydrogenphosphates in the first step and
these dihydrogenphosphates were titrated in the second step. Reaction:
The first step: H
3
PO
4
+ KOH KH
2
PO
4
+ H
2
O
The second step: KH
2
PO
4
+ KOH K
2
HPO
4
+ H
2
O
The mass fractions of the potassium carbonate, potassium hydrogen
carbonate and soaps in the GP were determined by acidimetric titration by
hydrochloride acid in methanol with potentiometric indication. For calculation
of amount of soaps and potassium hydrogen carbonate, it was necessary to
determine the volume of escaped carbon dioxide after the addition of strong
acid to the sample of GP. The detailed description of determination is in [7].
In both glycerol phases, glycerol was determined by iodometric titration
and the amount of water by Karl-Fisher titration. Methanol and esters were
determined by GC with FID.
44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009 3
RESULTS AND DISCUSSION
Purification without saponification
The neutralization of alkali materials in the GP (soaps and carbonates) was
carried out with three strong concentrated inorganic acids (sulphuric,
hydrochloric and phosphoric) and one organic acid (acetic acid).
The pure glycerol phase contains in average ca 84 wt.% of glycerol, ca
12 wt.% of water and remainders after neutralization (acid and salt), the exact
composition (including precipitate yield) is stated in Tab. II. The yield of this
phase was varied in the interval 60-65 %. The organic phase contains mixture
of esters and high fatty acids (Tab. III) and its composition is almost the same
as with usage of all three inorganic acids: the weight ratio of esters and higher
fatty acids is 1:1.
Tab. II: The composition of the PGP and yield precipitate with different acids
acid
yield of
precip.[%]
glycerol
[wt.%]
acid
[wt.%]
salt
[wt.%]
water
[wt.%]
methanol
[wt.%]
sulphuric 99.8 88.1 0.19 0.1 10.8 0.55
hydrochloric 50.6 80.5 0.07 7.6 11.5 0.46
phosphoric 87.1 81.9 0.18 1.8 15.2 0.52
acetic 0 82.3 0.45 12.2 4.2 0.48
Tab. III: The composition of the OP with different acids
acid
yield of OP
[%]
density
[g/cm
3
]
fatty acids
[wt.%]
esters
[wt.%]
others
[wt.%]
sulphuric 26.0 0.899 53.4 46.1 0.5
hydrochloric 24.1 0.899 50.7 48.9 0.4
phosphoric 30.9 0.899 52.3 47.4 0.3
acetic 31.2 0.952 43.3 56.3 0.4

The coagulation, which can be filtered off, was formed during usage of
inorganic acids. The potassium acetate was solved in the reaction mixture and
the filtration was impossible. The formed precipitates of salts of sulphuric and
hydrochloric acid were very hardly filterable and filtration took long time (2 3
hours). The well filterable crystallic precipitate of salt (KH
2
PO
4
) was formed
only when the phosphoric acid was used for the neutralization (filtration took
ca 10 min). After removing of methanol, the separation of phases was the
fastest (ca 30 min) with H
3
PO
4
contrary to the separation time of HCl, which
took 3 hours; H
2
SO
4
and CH
3
COOH took 10 hours each. The next advantage
of phosphoric acid usage is that phosphor is a biogenous element and thus
potassium dihydrogenphosphates can be used as fertilizer without other
purification. Therefore, the phosphoric acid was used for other purifications
with saponification only.
44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009 4
The effect of methanol amount (calculated as weight ratio of methanol to
raw GP) on the yield of formed precipitate (KH
2
PO
4
) was investigated; this
dependence is depicted in fig. 1. The yield of precipitate is increasing with
increasing amount of methanol, because KH
2
PO
4
is insoluble in methanol.
Therefore it is better to use higher amount of methanol for dilution of GP (ca
26-30 wt.%).

Fig.1: The dependence of yield of formed precipitate on methanol amount
Y = 0.3042w
met
+ 84.74
R
2
= 0.987
88
89
90
91
92
93
94
95
96
10 15 20 25 30 35
amount of methanol - w
met
[wt.%]
y
i
e
l
d

o
f

p
r
e
c
i
p
.

-

Y

[
%
]


Purification with saponification
The OP contains ca 50 wt.% of ester. In order to gain higher fatty acids only,
the ester in the GP was at first (prior to neutralization by addition of acid)
saponificated by potassium hydroxide to soap; the molar ratio of KOH to
esters was 1:1.
After the reactions, the concentration of glycerol in the PGP is ca 84 wt.%
and the rest is especially water (contains no esters). The organic phase
contains 95 wt.% of higher fatty acid and a small amount of esters. Therefore
the saponification did not proceed totally. In the next experiments, the molar
ratio of KOH to ester was enhanced to 1.2:1. The composition of the PGP is
almost the same, but the OP contains only mixture of higher fatty acids
(contains no esters).
The results of the analyses of both phases after the separation are stated
in Tab. IV (the pure glycerol phase) and Tab. V (the organic phase) for both
molar rations.
44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009 5
Tab. IV: The composition of the pure glycerol phase
molar ratio
KOH:esters
yield
[%]
glycerol
[wt.%]
H
3
PO
4
[wt.%]
KH
2
PO
4
[wt.%]
water
[wt.%]
methanol
[wt.%]
others
[wt.%]
1:1 61.5 84.7 0.21 2.18 12.1 0.46 0.35
1:1.2 62.8 85.1 0.25 2.62 11.1 0.37 0.56
Tab. V: The composition of the organic phase
molar ratio
KOH:esters
yield
[%]
density
[g/cm
3
]
acid number
[mgKOH/g]
fatty acid
[wt.%]
esters
[wt.%]
others
[wt.%]
1:1 23.2 0.88 190 95 4.8 0.2
1:1.2 19.9 0.88 199 99.5 0 0.5

CONCLUSION
The treatment of the glycerol phase was investigated. It was described how to
gain glycerol with purity ca 86 wt.% and the mixture of esters with fatty acids
or only higher fatty acids with purity 99 wt.%. The first step (to gain fatty acids)
is saponification of esters remainder by potassium hydroxide to soaps. The
next step is neutralization of soaps to higher fatty acids and carbonates to
carbon dioxide by concentrated phosphoric acid. Another product of
neutralization is potash-phosphate fertilizer (KH
2
PO
4
). The process of
purification is easy and environmental friendly.
Acknowledgements
This work has been funded by the research project MSM0021627502 of the
Czech Ministry of Youth and Sport.

References
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[3] C. Zhanyoui, P. Denver, W. Zhiyou: A laboratory study of producing
docosahexaenoic acid from biodiesel-waste glycerol by microalgal
fermentation, Process Biochemistry 42, 15371545, 2007.
[4] M. Dasaria, P. Kiatsimkula, W. Sutterlinb: Low-pressure hydrogenolysis of
glycerol to propylene glykol, Applied Catalysis A: General, 281, 251-231,
2005.
[5] F. Skopal, K. Komers, J. Machek, I. Koropeck: 2001. Zpsob vroby
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44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009 6