Energy Convers. Mgmt Vol. 39, No. 11, pp.

1203±1206, 1998
# 1998 Elsevier Science Ltd. All rights reserved
PII: S0196-8904(97)10007-3 Printed in Great Britain
0196-8904/98 $19.00 + 0.00

LIQUEFACTION OF SUNFLOWER STALK BY USING

SUPERCRITICAL EXTRACTION

M. ERZENGIN and M. M. KUÈC° UÈK

Y. Yil University Educational Faculty, 65080, Van, Turkey

(Received 23 September 1996)

AbstractÐSun¯ower stalk mill was converted to liquid products by using some organic solvents (metha-
nol, ethanol and acetone) with catalyst (% 10 NaOH) and without catalyst in an autoclave at di€erent
temperatures, 523 and 563 K. The liquid products were extracted by liquid±liquid extraction (benzene
and diethyl ether). The yields of supercritical methanol, ethanol and acetone extractions were 40.00,
45.60 and 47.80%, respectively, at 563 K. In the catalytic runs, the methanol and ethanol extractions
were 58.03 and 54.17%, respectively, at 563 K. The yields of supercritical methanol extraction have
been increase from 38.52 to 58.03% as the temperature increased from 523 to 563 K in the catalytic
run. # 1998 Elsevier Science Ltd. All rights reserved

Sun¯ower stalk Supercritical ¯uid extraction Biomass liquefaction Thermochemical pro-

cess.

INTRODUCTION
Considerable attention is currently focused on development of synthetic fuels from non-pet-
roleum feedstocks. The major feedstock candidates are coal, oil shale and biomass. Potential
products include alcohol fuels, alcohol±gasoline blends and equivalents of commercial materials
currently derived from petroleum (diesel, jet fuel, etc.). There are many advantages and disad-
vantages of biomass. The advantages of biomass are: (1) minimal environmental problem, (2)
high hydrogen content, (3) low contamination (sulphur, etc.) and (4) renewable supply. The dis-
advantages of biomass are: (1) high oxygen content, (2) land use competition, (3) environmental
problems (mining, processing) and (4) high contamination. Biomass use will concentrate on
waste streams (industrial, agricultural, urban) and surplus agricultural crops. Agricultural and
forest residues and energy crops will play an increasingly important role. Eventually widespread
use of renewable biomass sources appears inevitable with the main question being primarily one
of timing [1].
Several approaches have been proposed for the production of liquid fuels from biomass: (1)
alcohol production via fermentation (grain, sugar factory wastes, etc.), (2) biogas production by
anaerobic fermentation (urban refuse, industrial wastes, etc.), (3) direct liquefaction and (4)
indirect liquefaction. The ®rst two are biochemical conversions so the latter two are thermo-
chemical conversion processes. Direct liquefaction processes attempt to produce a product with-
out going through the gas phase. The product, however, contains an appreciable amount of
oxygenated compounds, thus leading to quality and stability problems. Current research in this
area is aimed at eliminating the oxygen. Indirect liquefaction methods convert the biomass to a
synthesis gas and then recombine components to form quality hydrocarbon fuel products, free
of oxygenated compounds.
Thermochemical liquefaction of biomass is basically a process whereby it is heated with a cat-
alyst under pressure at temperatures up to 673 K. This procedure converts the biomass to a mix-
ture of gas (2±10%), char (5±40%) and oil (up to 40%), on a weight basis.
The liquefaction of biomass depends on its chemical composition and re¯ects the responses to
temperature and solvent of the main components, cellulose, lignin and hemicelluloses, as has
been shown for wood of di€erent species [2, 3]. These studies have been based on the early work
of Appell et al. [4]. They reported that a variety of lignocellulosic materials could be converted
partly into a fuel oil by reaction with carbon monoxide and water at elevated temperature in
the presence of sodium carbonate as a catalyst. The development of liquefaction techniques for
1203
1204 M. ERZENGIN and M. M. KUÈC° UÈK: LIQUEFACTION OF SUNFLOWER STALK

conversion of biomass to oil has been studied by many investigators [5±7]. In each case, com-
plete conversion of lignocellulosic material occurred to produce an oil fraction, a water-soluble
fraction and a residual gaseous fraction. The black, moderately viscous oil, obtainable in yields
of 35±45% of wood, was, to a ®rst approximation, qualitatively similar to that reported by
other investigators using varied raw materials [8±10]. The residual oxygen content was 15±20%,
and the carbon content was 70±75%.
At lower temperatures (573±673 K), the formation of carbon dioxide and methane and, at
higher temperatures (>773 K), carbon dioxide, carbon monoxide and smaller quantities of
methane are the predominant species. In wood liquefaction, any oxygen removed should ideally
be in the form of carbon dioxide and not carbon monoxide. Also, methane is an undesirable
product, since it lowers the hydrogen/carbon ratio in the substrate. Thus, it would appear that
the lower temperature range would be more desirable. The lower temperatures would also
favour non-equilibrium products, such as volatile liquids, if the temperature increase is
rapid [7, 11].
Various agricultural residues, such as grain dust and sun¯ower stalk, are available in Turkey
as the source of biomass energy and chemicals. The amount of sun¯ower produced annually in
Turkey is estimated to be about 8,500,000 tonnes. The method in the present study was based
on conversion to liquid products of sun¯ower stalk at elevated temperatures and pressure in an
autoclave. The conversion products obtained from the liquefaction were fractionated into ben-
zene fraction and diethyl ether fraction constituents with liquid±liquid extraction.

EXPERIMENTAL
The sun¯ower stalk samples were taken from Van (Turkey). The samples were dried in air
and ground in a Thomas±Wiley mill to pass through a screen of 0.6 mm aperture and extracted
with petroleum ether. It was uniformly mixed before application for experiments.
All the runs were performed in a 0.250 l cylindrical autoclave, made of 316 stainless steel, and
its dimensions were 30 mm i.d., 60 mm o.d. and 375 mm height. The sample was loaded from
the bolt hole with M 1235  1.5 into the autoclave, and the hole was plugged with a screw bolt
after each run.
In a typical run, the autoclave was loaded with a 10.0 g sample and a solvent or solution con-
taining the desired quantities of catalyst and/or water.
The autoclave was supplied with heat from tan external heater, and the power was adjusted
to give an approximate heating time of 90 min. The temperature of the reaction vessel was
measured with an iron±constantan thermocouple and controlled at 600 25 K for 75 min.
Reactions occurred during the heating period.
After each run, the gas was vented, and the autoclave contents were poured into a beaker. All
the rest of the oil and solids were removed from the autoclave by washing with used solvent.
The products were recovered by washing with the solvent (100 ml). The obtained mixture was
then ®ltered in a 30 ml glass crucible, with a medium frit, to separate the solvent and insoluble
materials. The preweighed ®lter was dried to constant weight in an oven at 378 K.
The liquefaction product was recovered by evaporation in a rotary evaporator at temperatures
of 303±377 K and reduced pressure (about 11 kPa) to remove the solvent. The liquefaction mix-
ture was added to the water (200 ml) and extracted with benzene (4  50 ml) and then with
diethyl ether (4  5 ml) by using a solvent±solvent extraction procedure in a separating funnel.
Upon removal of the solvents, the yields of the extractions were determined.
Methanol, ethanol or acetone as solvents and methanol or ethanol with sodium hydroxide
(10%) as catalyst were used in the experiments.
Supercritical ¯uid liquefaction of sun¯ower stalk was performed at two conversion tempera-
tures: 523 and 563 K.

RESULTS AND DISCUSSION

The conversion scheme of biomass to liquid product was given in a previous study [3].
Chemical analysis results of the sun¯ower stalk are shown in Table 1. The yields of the
supercritical solvent extractions and catalytic conversions are shown in Table 2.
 M. ERZENGIN and M. M. KUÈC° UÈK: LIQUEFACTION OF SUNFLOWER STALK 1205

Table 1. Chemical analysis of sun¯ower stalk

Components (wt% of dry, ash and
extractive free)
Lignin 18.00
a-cellulose 13.40
Cellulose 62.61
Soxhelet extractives (% daf)
With petroleum ether (b.p 40±608C) 0.51
Ash (wt%) 3.67
Moisture (wt%) 6.00
Higher-heating value (MJ/kg)

Table 2. The yields of supercritical gas extraction: conver-

sion* (wt% of dry, ash and extractive free)
At 523 K At 563 K
Solvent
Methanol 22.27 40.00
Ethanol 37.68 45.60
Acetone 39.50 47.80
Catalytic solvent
Methanol + 10% NaOH 38.52 58.03
Ethanol + 10% NaOH 35.94 54.17
*As percent of used sample

Supercritical ¯uid extraction was performed in the autoclave above the critical temperature
and pressure of the solvent. The yield of soluble materials increases with increasing pressure [3].
Table 2 shows that the yields of supercritical gas extraction increase with increasing temperature
in agreement with the theory of gas extraction [12].
The yields of supercritical liquefaction with methanol, ethanol or acetone were 22.27, 37.68
and 39.50% at 523 K and 40.00, 45.60 and 47.80% at 563 K, respectively. The yields of conver-
sion increased with the temperature increase from 523 to 563 K, as listed in Table 2.
Temperature appears to have a signi®cant e€ect on the extraction in all runs.
Table 2 shows that there is a signi®cant di€erence in percentage conversion yield for the
methanol and catalytic methanol runs. The methanol solubles increased from 22.27 to 38.52%
(523 K) and from 40.00 to 58.03% (563 K) with 10.0% NaOH catalyst. The catalyst appeared
to have a positive e€ect on the percentage yields in the catalytic run, but the e€ect is not signi®-
cant in the catalytic ethanol run.
The fractionation of products obtained from supercritical gas extraction is given in Tables 3
and 4. In the fractionation (liquid±liquid extraction), benzene, diethyl ether and water were used
as solvents. Insolubles in these solvents were called tarry materials.
When wood or biomass is heated, there is an attack on the glycosidic linkages which then
leads to dehydration, decarboxylation and decarbonylation and cleavage of the molecules into
smaller fragments which are soluble. Finally, gaseous compounds are formed. Lignin reactions

Table 3. The yields of extracts from supercritical gas extractions at 523 K (wt% of dry, ash and extractive free)
Benzene-solubles Diethyl ether-solubles Tarry material Water-solubles
Solvent
Methanol 1.60 0.62 3.55 16.55
Ethanol 3.06 2.00 13.20 19.43
Acetone 10.71 1.58 9.7 17.51
Solvent + catalyst
Methanol + 10% NaOH 3.33 0.88 7.30 27.01
Ethanol + 10% NaOH 6.21 3.95 5.14 20.64
1206 M. ERZENGIN and M. M. KUÈC° UÈK: LIQUEFACTION OF SUNFLOWER STALK

Table 4. The yields of extracts from supercritical gas extractions at 563 K (wt% of dry, ash and extractive free)
Benzene-solubles Diethyl ether-solubles Tarry material Water-solubles

Solvent
Methanol 7.54 1.86 5.32 25.28
Ethanol 8.22 3.02 16.43 17.93
Acetone 13.00 1.92 11.77 21.07
Solvent + catalyst
Methanol + 10%
NaOH 11.90 2.76 21.32 22.00
Ethanol + 10% NaOH 12.97 3.35 19.26 18.60

include fragmentation of a- and b-ether linkages and carbon±carbon bond cleavage, leading to
the formation of soluble and gaseous products.
Assuming that the hemicelluloses decompose early in the temperature pro®le of the reaction
with wood, the lignin initially associated with the hemicellulose fraction will ®nd itself in a free
state. Structural rearrangements will then take place and the elevated temperature will lead to
an increase in the mobility of the free lignin. With increasing reaction temperatures, conden-
sation is enhanced, and the thermal decompositions lead to volatiles. The free radicals formed
during decomposition of cellulose and lignin at the higher temperature have a random tendency
to form condensed macromolecules, leading to an acetone-insoluble fraction. In most cases,
hydrogen gas was used in this study to stabilize the free radicals and avoid these condensation
reactions, although condensation reactions apparently occurred in the reactions.

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