Methylation of wood fatty and resin acids for production of biodiesel

Ayhan Demirbas
Sirnak University, Dean of Engineering Faculty, Deopartment of Mechanical Engineering, Sirnak, Turker
a r t i c l e i n f o
Article history:
Received 3 November 2010
Received in revised form 22 February 2011
Accepted 23 February 2011
Available online 9 March 2011
Keywords:
Biodiesel
Wood oil
Extractives
Fatty acids
Tall oil
a b s t r a c t
The purpose of the present paper is to evaluate the potentiality of the wood oil of Oriental spruce (Spruce
orientalis) for biodiesel production. Two methods have been applied for obtained wood oil with and with-
out solvent such as separation of crude tall oil from sulfate soaps by Kraft pulping process. Production of
biodiesel from wood oil follows two steps, rst extraction of oil using a solvent (acetone) and then base
catalyzed (KOH) or non-catalytic supercritical methanol transesterication. This paper studied the effect
of temperature on transesterication of wood oil to nd the optimum temperature of maximum biodiesel
yield. Transesterication of the wood oils were performed in a 100-mL cylindrical autoclave using
supercritical methanol. In a typical run, the autoclave was charged with a given amount of the wood
oil (2025 g) and alcohol (2050 g) with changed molar ratios at 500, 525, 550 and 575 K. The yield of
the biodiesel produced under optimal condition is 9698%.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
The world is presently confronted with three signicant prob-
lems: fossil fuel depletion, climatic changes, and environmental
degradation, which are continuously being exacerbated due to
increasing global energy consumption [13]. As a substitute for
petroleum, renewable fuels have been receiving increasing atten-
tion due a variety of environmental, economic, and societal bene-
ts. Long term increases of petrol prices have created in the
automotive fuel industry a new competitive environment based
on the development of more sustainable technologies. Recently,
renewable energy has focused attractive attention due to the
declining fossil fuel reserves and the increased concerns over
greenhouse gas emissions [47]. Sustainable and economic pro-
duction of biofuels have appeal to compensate the current need
of petroleum fuels and have potential in addressing energy produc-
tion with almost zero emission of greenhouse gases due to its
nobility of counterbalance capacity [811].
Wood consists of structural and nonstructural components. The
main components of wood are structural components. The struc-
tural components are holocellulose (cellulose + hemicelluloses)
and lignin, together with smaller amounts of pectic substances.
Nonstructural components of wood are the polysaccharides of
starch, wood extractives, proteins, some water-soluble organic
compounds and inorganic compounds (mineral matters) [12].
Carbohydrates (cellulose and hemicelluloses) are the principal
components of the cell wall. Cellulose is the main component of
the wood cell wall, typically 4050% by weight of the dry wood.
Cellulose is a linear polymer composed of repeating anhydroglu-
cose units. Hemicelluloses are a mixture of amorphous branched-
chain polysaccharides consisting of a few hundred sugar residues.
Lignin is an amorphous, insoluble organic polymer and is very dif-
cult if not impossible to isolate in a natural state. The basic chem-
ical structural unit is a methoxy-substituted propylphenol moiety,
bonded in an irregular pattern of ether and carboncarbon link-
ages. Lignin is a complex, high molecular weight polymer built of
hydroxyphenylpropane units [13,14].
The extractives are nonstructural or non-cell wall plant constit-
uents, which can be removed with neutral solvents. Despite their
normally being minor constituents of wood, the extractives are
important factors inuencing such properties of the wood as odor,
color, strength, density, heating value, light stability, decay and in-
sect resistance, ammability, hygroscopicity, permeability, ease of
pulping, paint ability, and texture [15,16]. The amount of extrac-
tives in wood varies from 2% to 10% by weight and includes a wide
variety of organic chemicals. Extractive content is important
parameter directly affecting the heating value (HV). Extractives
raised the HVs of the wood fuels [17].
The extractives are isolated from the wood meal (particle size
less than 0.7 mm diameter) using Soxhlet extractors, rst with
petroleum ether (b.p. 4060 C) and then with acetonewater
(9:1 v/v) for the successive isolation of lipophilic and more polar
extracts, respectively.
Extractives consist of fatty acids, triglycerides, fatty alcohols, re-
sin acids, waxes, sterols, steroid hydrocarbons, sitosterol, sitosterol
esters, stigmastanol, stigmastanol esters, fucosterol, terpenoid
alcohols, triterpene alcohols, diterpene aldehydes, phenolics, gua-
iacyl lignans, alkanes, proteins, monosaccharides (glucose and
fructose), disaccharides (sucrose) and derivates [16].
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.02.037
E-mail address: ayhandemirbas@hotmail.com
Fuel 90 (2011) 22732279
Contents lists available at ScienceDirect
Fuel
j our nal homepage: www. el sevi er . com/ l ocat e/ f uel
There is no solvent able to affect a complete removal of the
wood extractives. The permeability and miscibility with water of
acetone are good features. Acetone is also an excellent solvent
for fats and fatty acids in wood. The acetone extracts obtained from
the wood samples were fractionated into lipophilic (chloroform-
soluble) and polar (chloroform-insoluble) fractions [18].
The standard method for recovery of wood extractives is Soxh-
let extraction using acetone as solvent [19]. However, in recent
years supercritical uid extraction has been found to be a promis-
ing method for the recovery of extractable chemicals present in
wood [18]. The yields of Soxhlet extraction of biomass samples
are shown in Table 1.
Together with the fatty acids, the diterpenoid resin acids are the
major acidic constituents in the petroleum ether extract of Oriental
spruce wood. The resin acid fraction is composed of levopimaric,
palustric, dehydroabietic, abietic, neoabietic, pimaric and sandar-
acopimaric acids. Of these, the abietic-type resin acids are domi-
nated [16].
The minerals constitute the ash residue remaining after com-
bustion at a high temperature. The ash content is 0.20.5% by
weight for temperate woods and 0.52.0% by weight for tropical
woods. The most common constituents of the ash in wood are cal-
cium, potassium, phosphorus, magnesium and silica.
Most current research on oil extraction is considerably focused
on producing biodiesel from vegetable oils. Methods and sources
to convert renewable oils to biodiesel are increasingly attractive.
Supercritical uid extraction of wood oil is carried out to study the
effects of various parameters such as pressure, temperature, extrac-
tion time and solvent on the yield and composition of the oil [20].
1.1. Tall oil
Tall oil is a by-product of coniferous wood recovered in the
Kraft (or sulfate method) pulping process. The name tall oil origi-
nates from Swedish origin word tall-olje meaning pine oil [21]. Tall
oil is a yellow and black, odorous oily liquid. Chemically, tall oil or
liquid rosin is mixtures of several components mainly resin acids
and other terpenoids, fatty acids and triglyceride oils, and unsapo-
niables, and partially water and ash [22].
The rosin acid is made up of approximately 35% abietic acid
[23]. The abietic acid is a steroid acid with a fused ring structure
that cannot be processed into biodiesel. The fatty acid component
of tall oil is most desirable for making biodiesel. Tall oil has a free
fatty acid content of approximately 40% [23].
Crude tall oil is separated from recovered black liquor in the
Kraft pulping process. In the Kraft process the wood is digested un-
der pressure with sodium hydroxide and sodium sulde. The vola-
tilized gases are condensed to yield sulfate turpentine. During the
pulping the alkaline liquor saponies fats and converts the fatty
and resin acids to their sodium salts. Concentration of the pulping
solution (black liquor) prior to recovery of the inorganic pulping
chemicals allows the insoluble soaps to be skimmed from the sur-
face. Acidication of the skimmed soaps yields their respective tall
oil resin and fatty acids [24]. Fatty acids can be recovered from tall
oil by vacuumdistillation. There is a great economic value in chem-
icals material in by-product tall oils from the pulping industry.
1.2. Biodiesel from wood oils
Chemically, biodiesel is a fatty acid (m)ethyl ester. Biodiesel is
generally made of methyl esters of fatty acids produced by the
transesterication reaction of triglycerides with methanol in the
presence alkali as a catalyst [25]. Biodiesel is a petroleum diesel
replacement and renewable fuel that is manufactured from plant
oils and animal fats. But the production of biodiesel from edible
vegetable oils is currently much more expensive than petroleum
based diesel fuel, due to relatively high cost of vegetable oils.
Mostly biodiesel is derived from the vegetable oils using NaOH
or KOH catalytic transesterication methanol process. The purpose
of the transesterication process is to lower the viscosity of the oil
[26]. The cost of making biodiesel is mainly attributed to the feed-
stock cost, processing cost and an overhead cost of building the
processing facility.
Saka and Kusdiana [27] and Ozcanli et al. [28] have rstly pro-
posed that biodiesel fuels may be from vegetable oil via non-cata-
lytic transesterication with supercritical methanol. According to
the current literature, non-catalytic transesterication reactions at
high temperature and pressure conditions provide improved phase
solubility, decrease mass-transfer limitations, provide higher reac-
tionrates andmakeeasier separationandpuricationsteps. Besides,
the supercritical transesterication method is more tolerant to the
presence of water and free fatty acids than the conventional alkali-
catalyzed technique, and hence more tolerant to various types of
vegetable oils, even for fried and waste oils [2932].
Almost all commercial vegetable oils are obtained from edible
oils such as soybean oil and rapeseed oil. Therefore, biofuel is actu-
ally competing limited land availability with the food industry for
the same oil crop [33]. The use of foodstuffs as rawmaterials for bio-
diesel productionincreases the prices of edible oils. These factors in-
crease the risk of scarcity. In order to overcome these problems,
many researchers have begun searching for cheaper and non-edible
oils tobe usedas alternative feedstocks. Commonly acceptedbiodie-
sel raw materials include the oils from soy, canola, corn, rapeseed,
and palm. Newplant oils that are under consideration include mus-
tard seed, peanut, cotton seed, algae, wood and tall oil [3032,34].
2. Experimental
2.1. Preparation of samples
The wood samples of Oriental spruce (Spruce orientalis) were
used in the experiments. The air-dried samples were ground in a
Table 1
Yields from simple Soxhlet extractions of biomass samples by using different solvents (wt.% of dry basis).
Biomass sample Alcohol benzene Acetone Petroleum ether Diethyl ether Dichloro methane Acetone water
Oriental beech 2.7 1.6 0.9 1.5 1.4 2.2
Oriental spruce 1.4 2.5 0.4 0.3 0.2 3.1
Ailanthus 2.1 2.6 0.3 0.3 0.3 2.6
Tea waste 7.8 8.6 1.8 2.2 2.5 11.7
Wheat straw 8.0 6.8 3.7 2.9 6.3 7.2
Corncob 1.2 1.3 0.6 0.8 1.0 1.4
Olive husk 8.1 7.5 3.6 5.3 6.4 8.0
Hazelnut shell 3.4 3.9 2.8 2.6 2.5 4.2
Hazelnut kernelcoat 19.6 18.1 15.7 16.8 14.6 16.5
Corn stover 2.4 2.6 0.8 1.9 1.8 3.4
Tobacco stalk 10.6 9.4 4.1 5.0 8.7 11.1
Tobacco leaf 13.1 12.6 5.2 6.8 10.0 13.0
2274 A. Demirbas / Fuel 90 (2011) 22732279
ThomasWiley mill to pass a screen of 1.0-mm aperture. Oils were
obtained by extracting the wood samples with acetone in a Soxhlet
extractor for 18 h.
In addition, the oleoresin collected from the Oriental spruce
trees for the same experiments.
2.2. Methylation of resin acids with diazomethane (CH
2
N
2
)
Diazomethane (CH
2
N
2
) reacts with resin acids to give methyl
esters. The CH
2
N
2
is generally prepared in ethereal solution by
the action of alkali (a 30% solution of KOH) on a nitrosamide, e.g.
N-methyl-N-nitroso-p-toluene-sulfonamide or nitroso-methyl-
urea [35]. Resin acids were dissolved in methanol and ethereal
diazomethane added drop by drop into the sample until the sam-
ple just retained a faint yellow color. After the indicated time,
the reaction was stopped by evaporating the diazomethane under
an impinging stream of nitrogen.
2.3. Methylation of resin acids with supercritical methanol
The oleoresins were dissolved in methanol for recovering resin
acids. The solution was loaded from the bolt-hole into the auto-
clave, and the hole was plugged with a screw bolt after each run.
Methyl esterication (methylation) of the resin acids were per-
formed in a 100-mL cylindrical autoclave using supercritical meth-
anol according to earlier method. In a typical run, the autoclave is
charged with a given amount of the resin acids and methanol with
changed molar ratios. After each run, the autoclave is cooled, and
the autoclave is poured into a collecting vessel. All the rest of the
contents are removed from the autoclave by washing with metha-
nol. In a typical run, the autoclave was charged with a given
amount of the resin acid (2025 g) and methanol (2050 g) with
changed molar ratios at 503, 520 and 560 K.
2.4. Transesterication of the wood oils
Transesterication of the wood oils were performed in a 100-
mL cylindrical autoclave using supercritical methanol according
to earlier method [28]. In a typical run, the autoclave is charged
with a given amount of the wood oil and methanol with changed
molar ratios. After each run, the autoclave is cooled, and the auto-
clave is poured into a collecting vessel. All the rest of the contents
are removed from the autoclave by washing with methanol. In a
typical run, the autoclave was charged with a given amount of
the wood oil (2025 g) and alcohol (2050 g) with changed molar
ratios at 500, 525, 550 and 575 K.
The esterication of free fatty acids was carried out with the
acidic reagent which was 5% (w/v) anhydrous hydrogen chloride
in methanol. Methyl esters of the fatty acids were analyzed on a
12 m long, 0.2 mm i.d., capillary Carbowax PEG 20 glass column
on a HewlettPackard 5790 gas chromatograph.
2.5. Esterication of tall oil fatty acids
Crude tall oil was obtained from sulfate soaps through acidula-
tion with sulfuric acid and then extraction into hexane phase. The
samples were separated into free fatty and resin acids, and neutrals
by extraction of the free acids with 5% NaOH from hexane solution
of the sample. Fatty and resin acids were separated via esterica-
tion of fatty acids with HClmethanol method. The mixture of fatty
acid methyl esters and resin acids were separated by extraction of
resin acids with 5% NaOH. Fig. 1 shows the schema of fractionation
of Kraft pulping products into components.
3. Results and discussion
3.1. The yields of fatty and resin acids from spruce wood and oleoresin
Abietic acid is a model compound because it is a relatively com-
mon resin acid in coniferous wood. Linseed oil is a typical sample
because it contains triglycerides of fatty acids (linoleic, linolenic,
oleic and stearic acids) commonly found in wood. The linoleic acid
extraction yield decreased linearly as a function of temperature
(from 315 to 435 K), while the abietic acid extraction yield gener-
ally increased, but not linearly, as a function of temperature. The
average chemical composition of fatty acids in wood oil samples
is given in Table 2. Table 3 shows the average chemical composi-
tion of resin acids in spruce wood extractives. Table 4 shows the
average chemical composition of resin acids from oleoresin sam-
ples. The oleoresin was completely resolved in methanol.
Wood extractives play an important role in pulping processes.
Increased knowledge of wood resin will help to develop effective
methods for the deresination of wood pulp. There are numerous
Fig. 1. Two steps liquefaction process of resin acids of tall oil rosin.
Table 2
Average chemical composition of fatty acids in spruce wood oil samples.
Acid Carbon number:number
of double bond
Unsaturated bond % by weight
Palmitic 16:0 2.6
Stearic 18:0 0.7
Oleic 18:1 9c 13.8
Linoleic 18:2 9c, 12c 42.7
Linolenic 18:3 9c, 12c, 15c 1.8
Pinolenic 18:3 5c, 9c, 12c 26.8
Others 11.6
A. Demirbas / Fuel 90 (2011) 22732279 2275
advantages of removing valuable turpentine and tall oil precursors
from wood prior to pulping. Resinous extractives can consume pul-
ping chemicals, decrease penetration of pulping liquors, increase
organic loads on recovery furnaces and evaporators. In addition,
extractives contribute to signicant air and water pollution prob-
lems in the pulp and paper industry. Various aspects of wood
extraction have been studied for production of chemicals and fuels
and also for a better understanding of the nature and structure of
wood.
3.2. The yields of fatty and resin acids from tall oil
Chemical compositions of tall oils are given in Table 5. Crude
tall oil contains 4158% resin acids, 3347% fatty acids such as
oleic and linoleic acids, 510% sterols, alcohols and other neutral
components. Crude tall oil was fractioned to fatty acids, rosin
and pitch like residue. Two components, abietic acid and dehydro-
abietic acid, comprise about 70% of the rosin acid fraction of tall oil.
Tall oil is an abundant, inexpensive and chemically desirable
feedstock.
Tall oil rosin acid can be converted into biodiesel by initial
supercritical methanol esterication and ultimate hydrogenation
processes. Two steps liquefaction process of resin acids is shown
in Fig. 1. Viscous resin acid methyl esters can be used as diesel fuel
additives. Fig. 2 shows the schema of fractionation of Kraft pulping
products into components.
Hydrogenation of the rosin acid fraction achieves both goals.
The experiments were performed in a laboratory-scale batch reac-
tor using three commercial sulded NiMo and CoMo catalysts.
For each of the catalysts, three different factors were studied: tem-
perature, hydrogen pressure, and reaction time. Experiments probe
the effects of these variables on liquid product yield, cetane index,
hydrogen-to-carbon ratio, and degree of cracking.
Biodiesel production costs can vary widely by feedstock, con-
version process, scale of production and region. Average interna-
tional prices for virgin vegetable oils and yellow grease used as
feedstock for biodiesel production in 2007 are given in Table 6.
The cost of feedstock is a major economic factor in the viability
of biodiesel production. Nevertheless, the price of waste cooking
oil is 2.53.5 times cheaper than virgin vegetable oils, thus can sig-
nicantly reduce the total manufacturing cost of biodiesel [3640].
For biodiesel productionfromoily seeds, there are ve problems:
the collection of seed, separation of kernels by breaking the seeds,
the relatively lowyields of oil on the seed basis, esterication of free
fatty acids, and transesterication of the oil to biodiesel. First two
operations are too labor-intensive. In addition, the oil extraction
processes for all oil crops is highly energy intensive. Therefore, the
oily seeds are poor producers of biomass energy [41].
3.3. Transesterication with supercritical methanol
The variables affecting the biodiesel yield during transesteri-
cation reaction are reaction temperature, molar ratio of methanol
to the wood oil, reaction time, free fatty acid content and water
content.
3.3.1. Effect of temperature and reaction time on ester yield
The methanol transesterication reactions were carried out at
subcritical (at 450 K and 500 K) and supercritical (at 525 K, 550 K
and 575 K) conditions. It is evident that at subcritical state of alco-
hol, reaction rate is so low and gradually increased as either pres-
sure or temperature rises. It was observed that increasing the
reaction temperature, especially to supercritical conditions, had a
favorable inuence on the yield of biodiesel without any catalyst.
As the temperature increased, the yield improved signicantly.
As shown in Fig. 3, the yield of ester (biodiesel) sharply increased
at rst 3 min.
Fig. 4 shows a typical example of the relationship between the
reaction time and the temperature. The critical temperature and
the critical pressure of methanol are 512.4 K and 8.0 MPa, respec-
tively. It was observed that increasing reaction temperature, espe-
cially supercritical temperatures had a favorable inuence on
methyl ester conversion.
Transesterication can occur at different temperatures and the
temperature inuenced the reaction rate and yield of esters,
depending on the oil used (Fig. 4). It was observed that increasing
reaction temperature, especially supercritical temperatures had a
favorable inuence on methyl ester conversion.
The yields of biodiesel are relatively low even after reaction for
6 and 8 min. In the supercritical methanol transesterication
method, the yield of ester raises 8898% for rst 812 min.
3.3.2. Effect of methanol concentration on transesterication reaction
The molar ratio of methanol to wood oil is also one of the most
important variables affecting the yield of methyl esters. Higher
molar ratios result in greater ester production in a shorter time.
The samples of wood oil were transesteried 1:41 oilmethanol
molar ratio in supercritical conditions. In this reaction, an excess
of methanol was used in order to shift the equilibrium in the direc-
tion of the products.
3.3.3. Effect of free fatty acid and water content on transesterication
reaction
Water content is an important factor in the conventional cata-
lytic transesterication of wood oil. The yields of methyl esters
as a function of free fatty acid content in biodiesel production
(Fig. 5). In the conventional catalytic (NaOH or KOH) transesteri-
Table 3
Average chemical composition of resin acids in
spruce wood extractives.
Acid % by weight
Abietic 9.4
Dehydroabietic 33.7
Neoabietic 6.5
Pimaric 4.4
Isopimaric 11.9
Sandaracopimaric 6.4
Levopimaric 10.7
Palustric 17.0
Table 4
Average chemical composition of resin acids in
oleoresin samples.
Acid % by weight
Abietic 5.4
Dehydroabietic 44.2
Neoabietic 7.2
Pimaric 5.0
Isopimaric 9.3
Sandaracopimaric 6.7
Levopimaric 7.5
Palustric 14.7
Table 5
Chemical compositions of tall oil samples, % by weight.
Resin acids 4158
Fatty acids 3347
Unsaponiables 410
Water content 0.53
Ash content 0.11.0
2276 A. Demirbas / Fuel 90 (2011) 22732279
cation of fats and vegetable oils for biodiesel production, free fatty
acids and water always produce negative effects since the presence
of free fatty acids and water causes soap formation consumes cat-
alyst and reduces catalyst effectiveness. In catalyzed methods, the
presence of water has negative effects on the yields of methyl es-
ters. However, the presence of water affected positively the forma-
tion of methyl esters in the supercritical methanol method [29]. In
the supercritical region the dielectric constant of water is much
lower. For this reason, subcritical and supercritical water behaves
as an organic solvent and exhibits extraordinary solubility toward
organic compounds containing large nonpolar groups.
The total cost of biodiesel production including the feedstock,
operational and overhead cost is between $0.53/gal and $1.08/gal
when using tall oil or blends of feedstocks. The cost of producing
biodiesel from conventional feedstocks is signicantly higher than
Fig. 2. Schema of fractionation of Kraft pulping products into components.
Table 6
Average international prices for selected vegetable
oils and animal fats used as feedstock for biodiesel
production in 2007 (US$/ton).
Crude palm oil 543
Rapeseed oil 824
Soybeen oil 771
Rened cottonseed oil 782
Crude corn oil 802
Crude peanut oil 891
Crude tea seed oil 514
Waste cooking oil 224
Yellow grease 375
Algal oil 194
Tall oil 282
Poultry fat 276
0
20
40
60
80
100
0 2 4 6 8 10 12 14 16
F
a
t
t
y

a
c
i
d

a
l
k
y
l

e
s
t
e
r
,

%
Reaction time, min
Fig. 3. Plots for changes in fatty acids alkyl esters (biodiesel) conversion from
triglycerides as treated in supercritical methanol at 575 K. Molar ratio of wood oil to
methyl alcohol: 1:41.
A. Demirbas / Fuel 90 (2011) 22732279 2277
using tall oil blends. The cost of producing biodiesel from yellow
grease or soybean oil feedstock ranges from $1.46 to $2.40 per
gal [10,38]. The use of tall oil in the biodiesel feedstock reduces
cost from conventional feedstocks and makes biodiesel more com-
petitive with petroleum diesel.
4. Conclusion
A non-catalytic biodiesel production route with supercritical
methanol has been developed that allows a simple process and
high yield because of simultaneous transesterication of triglycer-
ides and methyl esterication of fatty acids.
The edible vegetable oil fuels were not acceptable because they
were more expensive than petroleum fuels. With recent increases
in petroleum prices and uncertainties concerning petroleum avail-
ability, there is renewed interest in vegetable oil fuels for diesel en-
gines. However there are large amounts of low-cost oils such as
restaurant waste and inedible vegetable oils that could be con-
verted to biodiesel.
The existing processing technology is available to make biodie-
sel from tall oil. The cost comparison of using tall oil as a biodiesel
feedstock is also favorable. The cost of producing biodiesel from
tall oil is half the selling price of petroleum diesel. The feedstock
cost is lower for tall oil than the crop and the oily seed biodiesel
feedstocks.
The fatty acids from tall oil could be used as a feedstock for pro-
ducing biodiesel. Tall oil, also known as liquid rosin, is a resinous
yellowblack oily liquid composed of a mixture of rosins, fatty
acids, sterols, high-molecular alcohols, and other alkyl chain mate-
rials; obtained as a byproduct in the treatment of pine pulp.
The parameters affecting on the methyl esters formation are
reaction temperature, pressure, molar ratio, water content and free
fatty acid content. It is evident that at subcritical state of alcohol,
reaction rate is so low and gradually increased as either pressure
or temperature rises. It was observed that increasing the reaction
temperature, especially to supercritical conditions, had a favorable
inuence on the yield of ester conversion. The yield of methyl ester
increased with increasing the molar ratio of oil to methyl alcohol.
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Y
i
e
l
d

o
f

m
e
t
h
y
l

e
s
t
e
r
,

w
t
%
Fig. 4. Changes in yield percentage of methyl esters as treated with subcritical and
supercritical methanol at different temperatures as a function of reaction time.
Molar ratio of wood oil to methyl alcohol: 1:41.
0
20
40
60
80
100
0 10 20 30
M
e
t
h
y
l

e
s
t
e
r
,

%
Free fatty acid content, %
Supercritical methanol alkaline catalyst
Fig. 5. The plots for yields of methyl esters as a function of free fatty acid content in
biodiesel production.
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