J.
of Supercritical Fluids 77 (2013) 100–102
Contents lists available at SciVerse ScienceDirect
The Journal of Supercritical Fluids
journal homepage: www.elsevier.com/locate/supflu
Biodiesel synthesis from vegetable oils with supercritical methanol
V.I. Anikeev ∗ , E.Yu. Yakovleva
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russian Federation
a r t i c l e i n f o a b s t r a c t
Article history: Transesterification reactions of sunflower, rapeseed, cottonseed and cameline oils in supercritical
Received 3 January 2013 methanol were studied in a flow reactor under equal conditions. It was found that the oil type produced
Received in revised form 13 February 2013 insignificant effect on the product composition (fatty acid esters) and oil conversion value.
Accepted 14 February 2013
Keywords:
Biodiesel
Transesterification reactions
Supercritical methanol
Flow reactor
Experiment
1. Introduction
The main products of vegetable oils transesterification with
lower alcohols are fatty acid esters (FAE) which appear environ-
mentally sound diesel fuel for power units of various types [1–5].
Natural oils extracted from plant raw materials (oil-plant crops)
consist of triglycerides (TG, or FAE) by ca. 97%, mono- and diglyc-
erides and free fatty acids (FFA).
For biodiesel applications, the purified product of vegetable
oil transesterification should contain more than 96% of fatty acid
methyl esters. The key characteristics of a diesel fuel include volatil-
ity, cetane rating, operation temperature interval, viscosity, sulfur
content, storage stability. For biodiesel quality estimation, The
European Committee for Standardization developed standards EN
590 and EN 14214.
Current processes for biodiesel synthesis by transesterification
of vegetable oils in lower alcohols are performed in the presence of
base, acid or enzyme catalysts [6]. In the base-catalyzed reactions,
initial raw material and alcohol must be free of water, because the
latter shifts the reaction towards saponification and thus compli-
cates the end products separation [6]. Besides, the FFA content in
the feedstock should be low [7–9], because FFAs react with base
catalysts to produce soap that inhibits FAE formation [10].
The reaction of homogeneous acid-catalyzed transesterification of
vegetable oils is less susceptible to the presence of water and FFA in
the feedstock, but proceeds at much lower rate. Low reaction rate
is the main shortcoming of this process.
∗ Corresponding author. Tel.: +7 3833269434.
E-mail address: anik@catalysis.ru (V.I. Anikeev).
0896-8446/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.supflu.2013.02.018
© 2013 Elsevier B.V. All rights reserved.
Besides homogeneous catalysts, biodiesel synthesis from veg-
etable oils is performed in the presence of heterogeneous catalysts
with acidic [11,12] (zeolites [13,14], modified oxides of zirconium
(TiO2 /ZrO2 , WO3 /ZrO2 , K2 O/ZrO2 ) [11,15–17] and titanium [14],
sulfated zirconium [14] and tin [18,19] oxides, ion-exchange resins
[14,20,21], etc. [1,7,22–24]), or basic [25,26] properties (alkali met-
als oxides and hydroxides, CaO, ZnO, SrO, MgO/Al2 O3 , zeolites, etc.).
Although heterogeneous catalysts have obvious advantages
for vegetable oils conversion processes over the homogeneous
ones, they suffer from poisoning and subsequent deactivation,
and have high pore diffusion resistance resulting in low reaction
rates.
Transesterification of plant raw materials with supercritical
alcohols [5,27–33] requires neither homogeneous, nor heteroge-
neous catalysts. The non-catalytic process is less susceptible to the
feedstock quality, provides a 90–98% conversion at short contact
times and therefore can be performed in a flow reactor that allows
considerable increase of the process efficiency. The process is free
of waste waters, because there is no need to wash out the reac-
tion product from homogeneous base or acid catalysts. Finally, the
biodiesel production cost becomes much lower.
The characteristics of the synthesized biodiesel (FAE types and
content) depend on the chemical composition of initial feedstock,
which in its turn depends on the oil-plant species, cropping area
and conditions. It was interesting to check this statement experi-
mentally.
Almost all vegetable oils contain triglycerides of different sat-
urated fatty acids C12:0–C20:0 (lauric, myristic, palmitic, stearic,
arachic acids), monounsaturated fatty acids C16:1–C20:1 (palmi-
toleic, oleic, eicosenoic acids), polyunsaturated fatty acids C18:2
and C18:3 (linoleic, linolenic acids) (Table 1).
 V.I. Anikeev, E.Yu. Yakovleva / J. of Supercritical Fluids 77 (2013) 100–102 101

Table 1 Table 3
List of the main fatty acids occurring in different vegetable oils. Product distributions at vegetable oils transesterification with supercritical
methanol. P = 200–204 atm, T = 329–331 ◦ C, MeOH/oil = 2.
Systematic name Notation in the text Gross formula
Oil type Product distribution (mol.%) Other products (%)
Saturated fatty acids
Lauric acid C12:0 C12 H24 O2 PAME SAME OAME LAME
Myristic acid C14:0 C14 H28 O2
Palmitic acid C16:0 C16 H32 O2 Rapeseed 4.36 17.2 15.86 65.6 16.3
Stearic acid C18:0 C18 H36 O2 Corn 6.01 9.8 17.45 66.7 9.1
Arachic acid C20:0 C20 H40 O2 Cameline 5.28 28.5 42.7 23.7 28.1
Monounsaturated fatty acids Sunflower 4.35 9.66 16.1 69.88 8.1
Palmitoleic acid C16:1 C16 H30 O2
Oleic acid C18:1 C18 H34 O2
Eicosenoic acid C20:1 C20 H38 O2
Erucic acid C22:1 C22 H42 O2 phase consisted of methanol, dissolved glycerol, and some amount
Polyunsaturated fatty acids of FAEs. The bottom (denser) phase included esters, glycerol, and
Linoleic acid C18:2 C18 H32 O2 unconverted oil (if any).
Linolenic acid C18:3 C18 H30 O2
For qualitative and quantitative analyses, the phases were sep-
arated by decanting; each phase was diluted by 6–8-times as large
volume of water and centrifuged. Since FAEs are water insoluble,
Table 2 presents the fatty acid content in seven vegetable oils,
they segregated into individual phase. In this way, the FAE volumes
which considered in literature as the most promising for biodiesel
in the top and bottom phases were determined.
production [5,33–37]. Among them, cameline oil produced from
During washing out the bottom phase, only glycerol and
Camelina sativa oil-plant crop is the least often used feedstock for
insignificant amount of methanol contained in this phase dissolved
biodiesel production. Note that we have found no reports in litera-
in water. Qualitative and quantitative chromatographic analysis of
ture on the conversion of this oil with supercritical lower alcohols.
the products of vegetable oil transesterification with supercritical
methanol was performed as described in [36].
2. Experimental

Transesterification of vegetable oils with supercritical methanol 3. Results and discussion

was performed in a laboratory setup using a tubular flow reactor as
described in details in ref. [36]. The reactor volume was ∼23.5 cm3 .
The reaction mixture was obtained by mixing two independent
flows of liquid reagents at the reactor inlet. The first flow was pure
methanol; it was fed to the mixer by a piston pump through a heat
exchanger, where it was heated to the reaction temperature. The
second flow was vegetable oil; it was fed directly to the mixer by
a syringe pump. The methanol/oil parameter was calculated as a
ratio of methanol to oil volume flow rates (cm3 /min) at the reactor
inlet.
For experiments in this work, refined edible oils, namely, rape-
seed, sunflower, corn and cameline, and methanol (>99.8%) were
used.
The reaction products were sampled at fixed time intervals.
After several minutes, the sampled mixture simultaneously sep-
arated into two phases: top and bottom ones. The top (less dense)
Experiments on transesterification of four vegetable oils with
supercritical methanol were performed at constant temperature,
pressure and volume ratio methanol/oil = 2.
Table 3 presents the results of quantitative analysis of product
composition (mol.%) at tranesterification of different oils. It uses
the following reaction product designations: PAME – palmitic acid
methyl ester, SAME – stearine acid methyl ester, OAME – oleic acid
methyl ester, LAME – linoleic acid methyl ester
Column “Other products” in Table 3 presents the total frac-
tion of C20 and heavier products (chromatographic percents). Real
amounts of these compounds were not detected owing to the lack
of respective calibration coefficients. However, the total fraction
of these compounds in the reaction products provides valuable
information on the reaction product distribution depending on the
vegetable oil type.

Table 2
Fatty acid content in vegetable oils (wt.%) by literature data.

Oil 12:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3 20:0 Дрyгиe Source

Cottonseed 28.7 0 0.9 13.0 57.4 0 0 0 [5,33]

22–26 2–3 15–22 47–58 0 [34]
0.5 0.9 20 3.0 25.9 48.8 0.3 [35]
Sunflower 6.4 0.1 2.9 17.7 72.9 0 0 0 [5]
5–7 3–6 14–40 48–74 [34]
6.5 0.1 4.5 21.0 68.0 [35]
Palm 42.6 0.3 4.4 40.5 10.1 0.2 0 1.1 [5,33]
40–47 3–6 36–44 6–12 [34]
2.5 40.8 3.6 45.2 7.9 [35]
Soybean 13.9 0.3 2.1 23.2 56.2 4.3 0 0 [5,33]
10–12 3–5 18–26 49–57 6–9 [34]
0.1 0.3 10.9 0.3 3.2 24.0 54.5 6.8 0.1 [35]
Rapeseed 3.5 0 0.9 64.1 22.3 8.2 0 0 [5,33]
2–6 4–6 52–65 18–25 10–11 [34]
0.1 5.1 2.1 57.9 24.7 7.9 0.2 ∼0.1 (C10 , C12 ,C14 ) [35]
6.6 1.5 53.1 38.1 0 0 [36]
Coconut 7.8 0.1 3.0 4.4 0.8 0 0 65.7 [5,33]
7.5–10.5 1–3.5 5–8 1–2.6 rest [34]
54.1 17.4 6.1 1.6 5.1 1.3 [35]
Corn 11.8 0 2.0 24.8 61.3 0 0.3 0 [5,33,35]
Cameline 5–7 2–2.5 12–20 14–22 35–39 12.5–16 (20:1) [37]
2–4 (22:1)
102 V.I. Anikeev, E.Yu. Yakovleva / J. of Supercritical Fluids 77 (2013) 100–102
Each oil demonstrated a ∼93–98% conversion under the speci-
fied conditions. According to the data presented in Table 3, all oils
showed qualitatively similar product compositions at almost com-
plete conversion, all other conditions being equal. The difference
is observed only in the amounts of the specified FAEs in the oils
transesterification products.
It is seen that the PAME content in the conversion products
of all oils is similar and varies within 4.4–6 mol.%. Quantitative
composition of cameline oil transesterification products differs
considerably from that of other oils. Indeed, the SAME and OAME
content in cameline oil conversion products 2–3-times exceeds
respective values for other oils, while the LAME content is three
times lower. The content of “other products” in cameline oil trans-
esterification products exceeds considerably that value for other
oils.
The amount of FAEs dissolved in methanol phase is similar for all
oils, except of cameline one. In the letter case, the FAEs content in
methanol phase 1.8 times exceeded respective value for other oils
that is explained by different esters’ composition and solubility in
methanol.
Transeterification of vegetable oils in supercritical methanol
without catalysts makes the process less susceptible to the oil type
and, consequently, more universal as it allows the biodiesel produc-
tion from a mixture of different vegetable oils, keeping practically
constant the product composition.
Note finally that, first, the method of oil conversion with super-
critical methanol showed efficient performance with all the studied
vegetable oils, and, second, the four studied oils demonstrated only
insignificant differences in reactivity and product composition.
The present work was performed under support from Russian
Fund for Basic Research (Project No. 12-08-00013).
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