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J.

of Supercritical Fluids 50 (2009) 225–228

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The Journal of Supercritical Fluids


journal homepage: www.elsevier.com/locate/supflu

Extraction of caffeine from tea stalk and fiber wastes using supercritical
carbon dioxide
Hacer İçen, Metin Gürü ∗
Gazi University, Eng.&Arch. Fac., Chemical Engineering Dep., 06570-Maltepe-Ankara, Turkey

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

Article history: The purpose of this study was to investigate obtaining of caffeine from tea plant wastes by supercritical
Received 26 February 2009 carbon dioxide extraction. Experiments were carried out with tea stalk and fiber wastes of Turkish tea
Received in revised form 11 June 2009 plants that has no economical value. Stalk and fiber wastes were supplied from tea factories. These wastes
Accepted 17 June 2009
were ground, sieved and dried at 105 ◦ C temperature in an oven. Parameters affecting caffeine leaching
from tea wastes were determined to be, extraction time, extraction temperature, carbon dioxide flow rate,
Keywords:
process pressure and particle size. The maximum yield of caffeine from tea stalk wastes and fiber wastes
Caffeine
were 14.9 mg/g tea stalk and 19.2 mg/g tea fiber, respectively. The yield increase had been recorded as
Extraction
Supercritical carbon dioxide
61.9% and 65.5%, respectively, in comparison with the chloroform extraction of tea stalk and fiber wastes.
Tea stalk
Tea fiber © 2009 Elsevier B.V. All rights reserved.

1. Introduction bon dioxide at high pressure. Cost of extraction processes depend


upon the product efficiency, the price of plant and solvents selected.
Caffeine is natural component of tea, coffee, guarana and cacao. Several investigations were reported for extraction by super-
Since it acts as stimulants of the central nervous, muscle and cir- critical carbon dioxide from guarana [5,6], coffee beans [7], mate
cular systems, this compound has become a valuable agent for [8], green tea [9,10]. Also, methylxanthines were extracted from
human body. Although caffeine has been extensively consumed guarana seeds, mate leaves and cocoa beans using supercritical car-
in pharmaceuticals, soft beverages, etc., it creates health risks in bon dioxide and ethanol [11]. Furthermore, the extraction of tea
children, pregnants and some patients. Therefore, obtaining of caf- polyphenols and tea caffeine from green tea leaves were investi-
feine and decaffeination of tea and food become highly important. gated by the microwave-assisted extraction method [12]. Some of
It can be synthesized from chloroacetic acid or uric acid. In addi- these studies had been focussed on decaffeination of food [6,13,14].
tion, caffeine has been extracted from plants such as cacao, tea, The present experimental study was carried out on the stalk and
guarana and coffee. Extraction of caffeine was performed in two fiber wastes of Turkish black tea factories by supercritical carbon
ways; namely through conventional and supercritical methods. dioxide extraction. The nature of the raw materials makes leaching
Conventional method is based on extraction from the filtrate of of caffeine from tea stalk and fiber wastes economic and commer-
water–plant system by means of chlorinated hydrocarbons at atmo- cially feasible. They have no economic value other than being used
spheric pressure. Caffeine had been extracted from Turkish tea as very low grade fuel. The purpose of this study was to investi-
fiber and stalk wastes by conventional technique in the previous gate the influence of operational conditions on extraction yield. The
study [1]. Caffeine isolation using dichloromethane as the solvent yield was compared with the yield of chloroform extraction in the
results in trace amounts of extract [2]. Two types of Indian black tea specified conditions which had been reported in a previous study
products, decaffeinated tea and instant tea, with a low content of [1].
caffeine were produced, after treatment with ethanol and chloro-
form, respectively [3]. Also, biological treatments were applied to
coffee pulp to improve its content of cellulose and antinutritional 2. Materials and methods
factors such as total phenols, tannins, and caffeine [4]. Supercritical
method has been carried out with humidified plant by means of car- The mixture of Turkish black tea fibers and stalks wastes
employed in this study was provided by tea factory. These wastes
were separately ground using a cutting mill and classified accord-
ing to particle size by means of sieves. Sample of tea wastes was
∗ Corresponding author. Tel.: +90 312 5823555; fax: + 90 312 2308434. dried at 105 ± 2 ◦ C temperature for 2 h. Mean particle size was
E-mail address: mguru@gazi.edu.tr (M. Gürü). determined by Malvern Mastersizer E particle analyzer. Deionized

0896-8446/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2009.06.014
226 H. İçen, M. Gürü / J. of Supercritical Fluids 50 (2009) 225–228

Fig. 1. Flow diagram of the supercritical extraction set-up.

water was used in the extraction and analysis. Caffeine (99.99%) rate of 10 g/min, pressure of 200 bar and mean particle size of
for calibration was purchased from Merck. Food grade carbon diox- 0.387 mm were fixed through the time experiments. The relation-
ide (99.99%) used throughout the supercritical fluid extraction was ship between the yield as mg caffeine per g dried tea stalk wastes
bought from Oksan in Turkey. HPLC grade acetonitrile (Merck) was and extraction time is shown in Fig. 2. The yields increased expo-
used as mobile phase solvent. nentially with increasing time up to 7 h and up to 4200 g CO2 and
As shown in Fig. 1, the supercritical fluid extraction apparatus did not vary with further increase in the time and CO2 . Therefore,
used was a semi-continuous flow high pressure system obtained extraction time of 7 h was a reasonable choice and it was recorded
from Applied Separations’ Spe-ed SFE oven model. The whole sys- as a constant parameter in the further experiments. In the simi-
tem consists mainly of a compressor, a syringe pump, a changeable lar work, it was recommended as 7 h from mate tea leaves (Ilex
extraction vessel, a collecting vessel and a wet gas flowmeter. A paraguariensis) by Saldana et al. [8].
24 ml of extraction vessel was packed with 5 g of tea wastes and To investigate the effect of carbon dioxide amount on the caf-
moistened with 10 g deionized water. After the vessel had been feine yield, extraction time of 7 h, temperature of 55 ◦ C, pressure
tightly closed, the connecting valves (V1 and V2 in Fig. 1) were of 200 bar and mean particle size of 0.25 mm were kept constant
opened, and decompression valve (V3 ) was closed for extraction through out the experimental study. As can be seen from Fig. 3,
period. Liquid CO2 contained in the siphoned cylinder was pumped the caffeine extraction increased exponentially with increasing car-
continuously through the system. Meanwhile, extraction vessel was bon dioxide flow rate up to 11 g/min and did not vary significantly
pressurized to a designated pressure and heated uniformly in the at 12 g/min. So, CO2 flow rate of 11 g/min was fixed in the further
system oven so that CO2 could attain the desired temperature. experiments. It was determined the CO2 flow rate of 11.5 g/min for
Also, outlet valve was heated to 130 ◦ C in order to prevent plug- extraction of caffeine from green tea [9].
ging due to decrease in CO2 pressure. At the end of the extraction To determine the extraction temperature giving higher yield, a
period, the connecting valves (V1 and V2 in Fig. 1) were closed and fixed extraction time of 7 h, CO2 , flow rate of 11 g/min, pressure
the extraction vessel was depressurized by gradually opening the of 200 bar and mean particle size of 0.387 mm were used and the
decompression valve (V3 ). Then residue of waste tea sample was
removed. Experiments were carried out minimum two times and
arithmetic means and error bars of repeatable results were given
on the graph.
Standard caffeine solutions at different concentrations were
analysed by means of HPLC (Dionex P680) equipped with UVD
170U detector and Acclaim 120 C18 column as described previously
[15] and results were used as calibration graph. Caffeine sample
extracted was diluted with hot deionized water, filtered under vac-
uum, cooled and analysed for caffeine by HPLC. 4 ␮l of the sample
were injected into the instrument. It was determined at 272 nm
wavelength, 30% (v/v) acetonitrile solution for mobile phase and
0.8 ml/min flow rate.

3. Results and discussion

The effect of processing parameters, namely extraction time,


carbon dioxide flow rate, temperature, pressure and particle size
were investigated and conditions giving higher caffeine yield were
recorded. Firstly, in order to determine the effects of total CO2 and
extraction time on the yield, extraction experiments were carried
out for extraction time varying between 1 and 10 h. Other parame- Fig. 2. Effect of total CO2 and extraction time on the caffeine yield; 10 g CO2 /min,
ters such as extraction temperature of 55 ◦ C, carbon dioxide flow 55 ◦ C, 200 bar, 0.387 mm mean particle size.
H. İçen, M. Gürü / J. of Supercritical Fluids 50 (2009) 225–228 227

Fig. 5. Effect of pressure on the caffeine yield; 7 h, 11 g CO2 /min, 60 ◦ C, 0.387 mm


mean particle size.

Fig. 3. Effect of carbon dioxide amount on the caffeine yield; 7 h, 0.387 mm mean
ticle size of three groups at the optima of the previous study. As
particle size, 55 ◦ C, 200 bar.
shown in Fig. 6, extraction yield decreased with increasing particle
size as a result of the hindrance of transportation of soluble agents
temperature giving the maximum caffeine extraction at these con- from tea wastes to the solvent due to the decrease in specific sur-
ditions was found by changing the temperature between 55 and face area. Similar variation was also obtained with the conventional
75 ◦ C. Fig. 4 shows the effect of extraction temperature on the method [1]. We predict that extraction time will decrease further
caffeine yield. The caffeine yield increased with increasing tem- with decreasing particle size.
perature up to 60 ◦ C and then decreased for further increase in Experimental conditions giving maximum caffeine extraction
extraction temperature. The increase of temperature up to 60 ◦ C yield from the tea stalk wastes were recorded as extraction time
was effective to dissolve caffeine molecules and to increase caffeine of 7 h, temperature of 60 ◦ C, CO2 flow rate of 11 g/min, pressure of
yield. It is thought that the decrease in the yield at higher temper- 250 bar and mean particle size of 0.202 mm. The maximum caf-
atures arises from the drying of tea stalks and the lowering of the feine extraction from Turkish tea stalk wastes was determined as
density of CO2 as we go from 60 to 75 ◦ C. 14.9 mg/g tea stalk under these conditions. Extraction experiments
To specify the effect of pressure on the caffeine extraction were carried out also for Turkish tea fiber wastes and the maximum
yield, extraction time of 7 h, temperature of 60 ◦ C, CO2 flow rate caffeine extraction was recorded as 19.2 mg/g tea fiber at the same
of 11 g/min and mean particle size of 0.387 mm were fixed in the experimental conditions of tea stalk. Higher amounts of caffeine
experiments. It is evident from Fig. 5 that the caffeine extraction in tea fibers than tea stalks was an expected result, since caffeine
yield increased considerably with increasing pressure up to 250 bar content decreases as one moves down from fresh leaves to the
and then did not vary significantly at higher pressures. Solubility stem [16]. Operational conditions giving maximum caffeine yields
of CO2 was increased by increasing the pressure. By utilizing from by means of conventional [1] and supercritical extraction methods
these results, 250 bar pressure value was selected as a constant have been summarized in Table 1. As compared with chloroform
parameter in the following experiments. extraction of tea stalk and fiber wastes [1], the yield increases from
It is known that particle size affected caffeine yield. In order to the stalk and fiber wastes had been recorded as 61.9% and 65.5%,
see how to affect the yield, experiments were repeated with par- respectively.

Fig. 4. Effect of extraction temperature on the caffeine yield; 7 h, 11 g CO2 /min, Fig. 6. Effect of mean particle size on the caffeine yield; 7 h, 11 g CO2 /min, 60 ◦ C,
200 bar, 0.387 mm mean particle size. 250 bar.
228 H. İçen, M. Gürü / J. of Supercritical Fluids 50 (2009) 225–228

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