Journal of Food Engineering 75 (2006) 565–573

www.elsevier.com/locate/jfoodeng

Solid–liquid extraction of caffeine from tea waste using

battery type extractor: Process optimization
Aynur Senol *, Ahmet Aydin
Istanbul University, Faculty of Engineering, Department of Chemical Engineering, 34320 Avcilar, Istanbul, Turkey

Received 27 September 2004; accepted 27 April 2005

Available online 14 July 2005

Abstract

This article deals with solid–liquid extraction of caffeine from tea waste containing 2% (w/w) caffeine using water and chloroform
as effective solvents. The extraction has been performed at isothermal conditions of 370 K for water and 293 K for chloroform in the
battery type extraction plant including both three and five extractors connected in series. An obvious difference in extraction behav-
ior has been observed for two solvents, distinguishing the divergent interactions attributed to the different mechanism of solvent–
caffeine aggregation. The high degree of separation of caffeine by chloroform is feasible with the efficiency ranging about two times
larger than water in terms of the solvent flow rates tested. The optimum process parameters were estimated through the graphical
interpretation of dependently changing variables, composition, flow rate and extraction degree. Details underlying some aspect of
selection of an appropriate differential equation for fitting the data are discussed.

2005 Elsevier Ltd. All rights reserved.

Keywords: Solid–liquid extraction; Caffeine; Solvents; Tea waste; Process optimization

1. Introduction from tea waste, including both solid–liquid and liquid–

Caffeine is classified as a natural product belonging to
a group of alkaloids, i.e. nitrogen-containing ring com-
pounds of plant origin that usually have a bitter taste
and some biological activity. Caffeine (C8H10N4O2;
1,3,7-trimethylxanthine) is one of three methylxanthines
(caffeine, theophylline and theobromine) in tea and rep-
resents the overwhelming bulk of this component. As a
weak organic base it stimulates respiration and the cen-
tral nervous system. Because its ingestion results in
wakefulness it is the principal ingredient of No-Doz ta-
bles. In general, a tea leaf contains 2–4.5% caffeine. Tea
waste is obtained during the production of black tea,
where leaves are plucked and treated in a four-step pro-
cess, i.e. withering, rolling, fermentation and firing. It
may use of a series of techniques in isolating caffeine
*
Corresponding author. Fax: +90 212 5911997.
E-mail address: senol@istanbul.edu.tr (A. Senol).
liquid extractions. Usually, the caffeine is extracted from
tea waste on multi-stage counter-current extraction tech-
niques (Treybal, 1968). The plant is broadly subdivided
into three sections, namely: pre-treatment, extraction
and post-treatment sections. In the pre-treatment sec-
tion, tea waste, lime and water are mixed at prefixed ra-
tios and then cooked at elevated temperature. Cooking
helps in the loosing of the tissues and in efficient extrac-
tion of caffeine. Caffeine is extracted from tea waste by a
suitable solvent. Subsequently, the solvent is recovered
and recycled back to the system and crude caffeine is ob-
tained. Crude caffeine is recovered from the miscella
stored in the balancing tank by removing all the solvent
through evaporation. Extraction is carried out in a con-
tinuous mode. Decaffeinated tea waste from the extrac-
tor moves to the desolventizer for removing the
entrapped solvent by heating. In the post-treatment sec-
tion crude caffeine is first dissolved in hot water to sep-
arate it from wax, and then is decolourised with

0260-8774/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.04.039
566 A. Senol, A. Aydin / Journal of Food Engineering 75 (2006) 565–573
Nomenclature
C0 initial concentration of caffeine in tea waste
(1000 mg/50 g tea)
CE concentration of caffeine in extract relative to
the extractor (mg/ml)
CE* concentration of caffeine in the extract leav-
ing the battery (mg/ml)
C 0E
concentration of caffeine in the extract at the
battery outlet (mg/100 ml)
CR concentration of caffeine in the raffinate (mg/
50 g tea)
E individual extraction degree
E* overall (total) extraction degree
Ec
cumulative extraction degree
F0 optimization factor
m0 initial amount of caffeine in 50 g tea waste
(1000 mg)
m0
overall initial amount of caffeine in the bat-
tery system (mg)
activated charcoal and filtered. The caffeine solution is
then concentrated and allowed to crystallize. Finally,
the caffeine is purified by crystallization with ethyl
acetate.
1.1. Solvent extraction of caffeine from tea
Extraction of certain solids can be performed by uti-
lizing the different chemical properties of various sol-
vents. In the case of decaffeinated tea, a decaffeination
process reduces the caffeine content. The current com-
mercially available methods for decaffeinating black
tea are solvent based extraction using ethyl acetate or
methylene chloride, and extraction using supercritical
carbon dioxide (under pressure). For teas to be labelled
decaffeinated, the caffeine content should not exceed
0.4% by dry weight. Two basic decaffeination processes
are used recently, i.e. direct and indirect solvent extrac-
tion methods (Zubrick, 2001). In the direct solvent
extraction process, decaffeination is accomplished by di-
rect application of methylene chloride, ethyl acetate or
carbon dioxide to the softened tea leaves. (Caffeine is
sparingly soluble in water at ambient temperatures, i.e.
22 mg/ml at 298 K, 180 mg/ml at 353 K, and 670 mg/
ml at 373 K; while the solubility of caffeine in chloro-
form or methylene chloride is quite high about nine
times larger than water at room temperature.) In the
indirect extraction process, the initial polar solvent used
in the extraction of caffeine is hot water often with car-
bonate salts (CaCO3, Na2CO3 or NaCl) added to con-
trol the pH and polarity, and to ensure that acidic
components of the tea leaf such as tannins (polyphenols)
are in the ionic form and thus more soluble in water and
mR amount of solute in the raffinate (mg)
n number of extractors
P
Or volume ratio ( V E
;i =V s )
Q solvent flow rate (l/h)
Vs space volume of extractor (ml)
VE volume of extract in the extractor alone (ml)
V E
volume of extract quitted the battery system
(ml)
Greek symbols
s overall extraction time (h)
WR leaching degree of solid phase (mR/m0)
Subscripts
max maximum
min minimum
mod modeled value of performance
opt optimum
that the caffeine will be present as the free base. Hot
water swells the tea leaves to release caffeine and other
compounds such as tannins. Various solvent extraction
processes have been devised in which caffeine is removed
from an extract of water-soluble substances produced by
steeping the tea leaves in hot water. Usually an organo-
chlorine solvent is used to selectively extract the caffeine
from the water which retains most of the other organic
compounds. In liquid–liquid extraction, the compound
being extracted should have a favorable distribution
coefficient in the extracting solvent. The extraction of
caffeine from aqueous solution was generally done using
chloroform (Birdwhistell & OÕConnor, 1971; Helmkamp
& Johnson, 1968; Pavia, Lampman, & Kriz, 1976) or
methylene chloride (Landgrebe, 1993; Mayo, Pike, &
Butcher, 1989; Nimitz, 1991; Williamson, 1989), sol-
vents known as possible human carcinogens. Murray
and Hansen (1995) suggest a less toxic alternative for
treatment of tea leaves through the use of water/1-pro-
panol/sodium chloride ternary system, being a suitable
replacement for the more traditional water/organochlo-
rine solvent systems. However, it has been found that
the crude caffeine obtained through the Murray–Hansen
method after evaporation of 1-propanol was highly con-
taminated with tannins and sodium chloride. Hampp
(1996) introduced an additional cleaning/extraction
step, which is commonly performed in organic synthesis.
It consists of a wash with a 10% aqueous NaOH solu-
tion to extract tannins and sodium chloride from 1-pro-
panol and subsequent drying with sodium sulfate
anhydrous prior to evaporation.
Saldaña, Mazzafera, and Mohamed (1999) have
extensively studied the extraction of caffeine from maté
 A. Senol, A. Aydin / Journal of Food Engineering 75 (2006) 565–573
tea leaves using an organic solvent (methylene chloride),
water and carbon dioxide. However, the use of chemical
solvents involves the risk of leaving toxic residues in the
extracted products while the use of water results in a
nonselective extraction and the loss of valuable flavor
components. Carbon dioxide, which has a low critical
temperature (304 K) and is nontoxic, has become a uni-
versally attractive alternative solvent in the extraction of
natural products (Saldaña et al., 1999). Recently, super-
critical techniques under pressure that combine solvent
extraction and stripping operations in a single process
are gaining considerable attention for separating and
recovering caffeine from tea leaves. There are several
studies on a decaffeination of tea by a supercritical car-
bon dioxide extraction (Chang, Chiu, Chen, & Chang,
2000, 2001; Sebald, Schulmeyer, & Forster, 1996;
Udayasankar, Manohar, & Chakkalingam, 1986).
Decaffeination of guarana seeds in a microextraction
column was studied using water saturated by CO2
(Saldaña, Zetzl, Mohamed, & Brunner, 2002). Further,
decaffeination of coffee has been processed at 260 bar
and 313 K in a batch type high pressure extractor using
a supercritical fluid extraction (Udayasankar et al.,
1986). The apparent diffusion coefficient at supercritical
state was found to be about 2.5 · 106 cm2/s. A compre-
hensive study on the kinetic and equilibria of tea infu-
sion relative to various teas, has been fulfilled by Spiro
and co-workers (Spiro & Lam, 1995).
Generally, the extraction processes depend upon the
plants and solvents selected. A microwave-assisted
extraction (MAE) method has been reported for the
extraction of tea polyphenols and tea caffeine from
green tea leaves using a solvent mixture of ethanol and
water (Pan, Niu, & Liu, 2003). Recently, it has been
developed a process for isolating tea polyphenol and
caffeine from green tea leaves using extraction with
water, followed by ultrafiltration with a CA–Ti compos-
Fig. 1. Experimental battery plant of three extractors (B3) for solid–liquid extraction of caffeine from tea waste.
567
ite ultrafiltration membrane, adsorption by a resin and
finally elution by a mixed solvent system (Li, Wang,
Ma, & Zhang, 2005). Process considerations dealing
with the competition between various solvent extraction
methods for caffeine still remain a challenging problem,
because such systems show extremely nonideal behavior
of a complex aggregation.
The objective of this study has been to investigate the
solid–liquid extraction of caffeine from tea waste includ-
ing 2% (w/w) caffeine in a pilot scale battery type extrac-
tion system using different in nature pure extractants,
water and chloroform. The effect of the extraction power
of both solvents on the number of extraction stages has
been discussed. A graphical interpretation of optimum
conditions has been also evaluated. Results were corre-
lated in terms of a linear differential approach.
2. Experimental
Solid–liquid extraction of caffeine from tea waste has
been studied at isothermal conditions using both hot
water and chloroform as effective solvents. Extraction
experiments were performed in a battery type system
including both three (B3) and five (B5) serially connected
extractors. Each extractor was equipped with steam jack-
et, and filled with a standard amount of 50 g solid tea
including initial caffeine concentration C0 = 1000 mg/
50 g tea waste. So, the space volume (or the volume of ex-
tract) in each extractor has been arranged to 500 ml.
Characterization of extraction efficiency of the battery
plant is intimately connected to the number of leaching
stages. Along with a consideration of these factors, a
500 ml extract portion quitted the battery system has
been the norm for one leaching stage. The battery extrac-
tion system and the associated control equipment, as well
as the flow chart are depicted in Fig. 1. Experimental
568 A. Senol, A. Aydin / Journal of Food Engineering 75 (2006) 565–573
runs were conducted to determinate the extraction effi-
ciency of chloroform at 293 K, as compared with the
water one at 370 K. Tests covering the influence of the
overall extraction time (or flow conditions) on the bat-
tery efficiency were performed using the flow rates of
0.25, 0.5, 0.75, 1.0 and 1.5 l/h for both solvents. How-
ever, the analysis pertaining to the performance of B5
battery system was restricted with the extraction effi-
ciency of water. A constant extraction temperature of
369–370 K for hot water has been maintained through
overheated steam of about 376 K. Analytical grade chlo-
roform (Merck, 99%), and deionized and redistilled
water were used in experiments.
The caffeine content in the extract phase has been
analyzed on the basis of formation of insoluble perio-
dide between caffeine and iodine solution, and the fol-
lowing titration of excess I2 with Na2S2O3 solution
(Snell & Ettre, 1969). The caffeine amount in the raffi-
nate phase was obtained though the Soxhlet extractor.
3. Results and discussion
3.1. Criterion of extraction degree
The results were interpreted in terms of extraction de-
gree, leaching degree of solid phase, extraction time and
volume ratio. (1) Individual extraction degree (E = mE/
m0) is the ratio of the caffeine amount in the solvent
phase of extractor (mE) to the initial caffeine content
in 50 g tea waste (m0 = 1000 mg). (2) Overall (total)
extraction degree (E
¼ mE
=m0
) is defined as the ratio
of the total amount of caffeine in the 500 ml extract quit-
ted the system ðmE
Þ to the overall initial Pcaffeine content
in the solid phase of battery ðm0
¼ m0;n Þ; n is the
number of extractors in the battery system. The super-
script * designates the overall quantity attributed to
the battery plant.
R s (3) Cumulative
P (integral) extraction
degree, Ec
¼ 0 E
;i ds ¼ i E
;i , where s is the extrac-
tion time (h), ‘‘i’’ denotes the number of 500 ml extract
portions withdrawn from the battery. (4) Leaching de-
gree of solid phase, WR = mR/m0; mR represents the
amount of residual
P caffeine in the raffinate. (5) Volume
ratio, Or ¼ ð i V E
;i Þ=V s , is the ratio of the overall vol-
ume of extract leaving the battery system to the space
volume (Vs) of extractor alone. V E
designates the vol-
ume of extract portion at the battery outlet attributed
to one leaching stage. Here V E
¼ V s ¼ 500 ml. (6)
Overall extraction time, s ¼ ðnV s þ V E
Þ=Q, where Q is
the flow rate of solvent (l/h), and n is the number of
extractors. Because s is intimately connected to Q, the
analysis was made in terms of flow rate as independent
variable. The optimum extraction degree and flow rate
conditions relative to the battery system can be evalu-
ated in terms of a newly-proposed optimization factor
(F0) defined as F 0 ¼ Ec
=WR1 ¼ C 0E
=C R1 , where C 0E
is
the caffeine concentration of 500 ml extract quitted the
system (mg caf/100 ml), CR1 is the concentration of caf-
feine in the raffinate (mg caf/50 g tea) and ‘‘1’’ denotes
the quantity referred to the first extractor.
3.2. Effect of extractant on the extraction degree of
caffeine
Study of the extraction system containing three
extractors (B3) in the battery plant (Figs. 2 and 3; Table
1), tested for both water and chloroform solvents, reveals
that the extraction degree of caffeine is remarkably
dependent on the nature of solvent, and the number of
500 ml extract portions (Or) withdrawn from the system,
varying asymptotically towards a maximum limit at low
flow rates of solvent. The solvent extraction affinity of
water to caffeine is rather low with Ec* ranging of about
38% for the first 500 ml extract portion (Or = 1) to 85.4%
for Or = 3, in contrast to the chloroform exhibiting 2.5
times larger Ec
value (Figs. 2 and 4). It is visible in Figs.
2 and 3 that the same remarks hold for the composition
range of extract in each extractor related to two solvents.
Referring to Fig. 3 and Table 1, it can be argued that the
highest strength of the caffeine solvation by chloroform
yields the flow condition of 0.5 l/h promoting proba-
bly the largest distribution ratio corresponding to the
plateau in the loading curve. Besides this fact, a simul-
taneous co-extraction of tannins (polyphenols) and caf-
feine in hot water deservedly may occur, that presumably
decreases the extraction degree in contrast to chloroform
being inactive to extract tannins (Table 1). Accordingly,
3.0
I-Extractor
II-Extractor
2.4 III-Extractor
VE*,500 ml extract
1.8
CEn (mg/ml)
1.2
0.6
0.0
0 1 2 3 4
Or (ml/ml)
Fig. 2. Comparison of extraction isotherms for water in terms of
extract composition in each extractor (CE,n) depending on the volume
ratio (Or); Q = 0.5 l/h; V E
¼ 500 ml; B3 battery system.
 A. Senol, A. Aydin / Journal of Food Engineering 75 (2006) 565–573 569

8.0 85.4% for Or = 3. This could be attributable to the high

polarity of chloroform (dipole moment, l = 1.16 debyes)
I-extractor
having only a hydrogen-donating group in the structure
II-extractor
III-extractor
capable of intermolecular H-bond formation with caf-
6.0 VE*, 500 ml extract feine. This specific structure is presumably responsible
for an increased mass transfer rate, in contrast to water
capable of intramolecular H-bonding.
Fig. 4 summarizes the influence of volume ratio (Or)
CEn (mg/ml)

4.0 on Ec
i.e., the uncontrollably change of the curve slope

with increasing the number of the solvent leaching
stages. The large differences among Ec
and Or values
for caffeine extraction in different extractants indicate
2.0 that the nature of solvent is a critical factor in the stud-
ied extraction process (Table 1). It is essential that this
phenomenon will have a significant impact on the imple-
mentation of a selected extraction method. The notice-
0.0
ably lower Ec
value for water against the first extract
0.0 0.5 1.0 1.5 2.0 portion of 500 ml at the battery outlet (Ec
¼ 0.38 at
Q (l/h) Or = 1) as compared to Ec
¼ 0.89 at Or = 1 for chloro-
Fig. 3. Variation of the extract concentration in each extractor (CE,n) form, may be attributed to the formation of intramolec-
with flow rate (Q) of chloroform for B3 battery system; Or ¼ 1ðV E
¼ ular bonded species between water and tannins
500 mlÞ. (polyphenols) in the aqueous phase presumably lowly
capable (if not incapable) of dipole–dipole physical
interaction with caffeine. It is also recognized that a ben-
Table 1
eficial factor for the extraction of caffeine from tea waste
Variation of overall and cumulative extraction degrees ðEc
Þ with flow
rate (Q) and extraction time (s) for chloroform and water solvents by chloroform is the formation of the soluble aggregated
using a battery system of three extractors (B3) caffeine–chloroform dipole species of a high polarity.
P a However, a preliminary analysis including liquid–liquid
Q (l/h) i V E ;i (ml)

Or s (h) C E
b (mg/ml) E* Ec

extraction between chloroform and aqueous tea may in-
Solvent: water
0.5 500 1 4.0 2.281 0.380 0.380 volve the assumption that caffeine is the only counterion
1000 2 5.0 1.700 0.283 0.663 exchanged at 293 K. As evident from Fig. 5, the concen-
1500 3 6.0 1.142 0.190 0.854 tration of 500 ml extract for chloroform obtained in the
Solvent: chloroform
0.5 500 1 4.0 5.325 0.888 0.888
1000 2 5.0 0.522 0.087 0.975 Ec*,max
1500 3 6.0 0.111 0.019 0.994 1.0
k' k
1.0 500 1 2.0 4.130 0.688 0.688
1000 2 2.5 1.212 0.202 0.890
1500 3 3.0 0.413 0.069 0.959 0.8
1.5 500 1 1.3 3.884 0.647 0.647
1000 2 1.7 1.348 0.220 0.867
1500 3 2.0 0.450 0.075 0.942 0.6 l'
Ec*

a
Overall volume of extract quitted the battery system.
b
Concentration of caffeine in 500 ml extract at outlet of the battery
system. l
0.4

water
this would call for the assumption of interacting through
0.2 chloroform
a caffeine–chloroform aggregation. These findings,
among other factors are comprehensively confirmed by
the results from Fig. 4, manifesting the fact that different
0.0
extraction mechanisms control caffeine extraction from
0 1 2 3 4 5
tea waste depending on the solvation degree of solvent.
Consequently, the results in Table 1 reveal that the Or (ml/ml)
extraction of caffeine from tea waste by chloroform is Fig. 4. Variation of cumulative extraction degree with volume ratio
highly efficient with a cumulative extraction degree (Ec
) (Or) for B3 battery system relative to water and chloroform solvents;
about 99.5%, as compared. to water yielding Ec
= Q = 0.5 l/h; Ec
;max ¼ 1.
570 A. Senol, A. Aydin / Journal of Food Engineering 75 (2006) 565–573

9.0 tannins, but its highly toxic effect as a suspected carcin-

water (B5) ogen makes this solvent questionable in nature.
chloroform (B3) Nevertheless, the situation being reached at moderate
modeled (Eqs.1 and 3) flow rate conditions of solvents would call for assump-
Eq. 3 tion that chloroform is a more valuable extractant com-
6.0
prising simultaneously both effective extraction and
CE* (mg/ml)

recovery of caffeine.

3.3. Graphical interpretation of optimum leaching

conditions

3.0 The optimum number of extractors (i.e., the number

Eq. 1
of leaching stages) for caffeine extraction from tea waste
may be obtained through the graphical interpretation of
the equilibrium curve, Ec
¼ f ðOr Þ, given in Fig. 4. How-
ever, the analysis should cover the evaluation of condi-
0.0 tions for estimating simultaneously maximum
0.0 0.5 1.0 1.5 concentration level of extract at the battery outlet and
Q (l/h) minimum residual caffeine in the raffinate phase at the
first extractor.
Fig. 5. Variation of the extract concentration with flow rate (Q) for
water (B5) and chloroform (B3); Or ¼ 1ðV E
¼ 500 mlÞ. Observed vs.
The regions reflecting the asymptotically linear sec-
modeled values for water (Eq. (1)) and chloroform (Eq. (3)). tions l and l 0 for water and chloroform, respectively,
are attributed to an extraction power of both solvents
at a highly low degree (Fig. 4). Conversely, the corre-
sponding k and k 0 linear sections reproduce the extrac-
tion behaviors of solvents at extremely large loading
240 regime by reason of an excess amount of solvent pre-
water (B5)
sumably favoring an undesirable concentration range
chloroform (B3)
of extract and a long extraction time. So, the conditions
modeled (Eqs. 2 and 4)
attributed to these linear regions are practically not
appropriate for an effective extraction process. The
CR1 (mg caf/50 g tea)

180 intersection of the asymptotical drawing lines to these

sections at the intercepting points m and m 0 for each
curve, respectively, should provide the conditions of
optimum extraction stages in terms of Ec
and Or vari-
Eq. 4 ables, regarding the concentration levels of caffeine C E

120 and CR1 in extract and raffinate, respectively. The goal
was to determine the most suitable extract composition
ðC E
Þ for caffeine recovery against practically permissi-
Eq. 2
ble minimum concentration range of caffeine at the first
extractor, CE1  0.01 mg/ml and WR1  0.10. A graphi-
60
cal interpolation of conditions attributed to the inter-
0.0 0.5 1.0 1.5 cepting points results in the following optimum ranges:
Q (l/h) Q = 0.5 l/h, Ec
 0.89–0.95; Or = 1 for chloroform,
reflecting the most appropriate concentration levels of
Fig. 6. Variation of the caffeine concentration in the raffinate with flow caffeine C E
and CR1 for a battery system of three extrac-
rate (Q) for water (B5) and chloroform (B3); Or ¼ 1ðV E
¼ 500 mlÞ.
Observed vs modeled values for water (Eq. (2)) and chloroform (Eq.
tors (B3). Conversely, the Or dependence of Ec
for
(4)). water is very much different as compared with chloro-
form, reflecting the tendency toward two additional
extraction stages (Or,opt = 3) to be added to B3 system
B3 battery system is larger than that for water in the B5 required for performing a significant extraction degree
system. Conversely, the caffeine contents in the raffinate of Ec
 0.85–0.90, and relatively small compositions
of the first extractor attributed to chloroform and water of extract and raffinate in the first extractor of
are relatively of the same ranges, as depicted in Fig. 6. CE1 = 0.021 mg/ml and WR1 = 0.12. However, the
Consequently, this property is an advantage for the extraction processed by water in the system of five
treatment of tea waste by chloroform being inactive to extractors (B5) at a given Q = 0.5 l/h (Or = 1), shows
 A. Senol, A. Aydin / Journal of Food Engineering 75 (2006) 565–573
rather low concentration levels of CE1 = 0.019 mg/ml
and WR1 = 0.11. The caffeine content in the raffinate
(CR1) has been defined through Soxhlet extractor.
3.4. Evaluation of results for B5 battery system
Traditionally, a commercial method dealing with so-
lid–liquid extraction of caffeine by hot water is still gain-
ing considerable attention as the first step in the overall
process of separating and recovering caffeine from tea
waste. Therefore, the effect of flow rate of water on
the extraction degree in the optimized battery system
of five extractors (B5) is critically discussed. Results
were correlated in terms of homogeneous differential
equation relative to the extract ðC E
Þ and raffinate
(CR1) compositions, cumulative extraction degree
ðEc
Þ, leaching degree of solid (WR1), and optimization
factor (F0) considering a volume ratio Or = 1.
Study of the extraction system containing five extrac-
tors (Figs. 5 and 6) reveals that the extract composition
ðC E
Þ continually decreases with increasing flow rate of
water accompanying by a maximum limit of C E
;max ¼
3.371 mg/ml at the water flow condition approaches 0
(i.e. Q ! 0 or overall extraction time, s ! /). Con-
versely, the results in Fig. 6 suggest that the caffeine com-
position in the raffinate of the first extractor (CR1)
increases proportionally with water rate, and closely
approaches a minimum value of CR1,min = 103.13 mg
caf/50 g tea for an infinite extraction time s ! /
(Q ! 0). These concepts can be verified by the results
from Fig. 7 for both Ec
and WR1 variables, manifesting
the fact that for the flow rate condition approaches 0
0.6
Ec*
ΨR1 (50 g tea)
modeled ED = Ec* ; ΨR1
0.4
Eq. 5
ED
0.2
Eq. 6
0.0
0.00 0.25 0.50 0.75 1.00
Q (l/h)
Fig. 7. Variation of extraction degree ðED  Ec
; WR1 Þ variables with
flow rate (Q) of water related to the B5 battery system; Or ¼ 1ðV E
¼
500 mlÞ. Comparison with estimates due to Eqs. (5) and (6).
571
(Q ! 0; s ! /), the controlling factor of extraction is
the solvation degree of solvent regarding the observed
Ec
;max and WR1,min limits.
The composition data of the considered B5 battery
system were interpreted in terms of a linear homoge-
neous differential equation, LHDE (Blum, 1972). The
analysis of its explicit form results in the following func-
tion between dependently changing concentration vari-
ables (C E
and CR1) and flow rate of water (Q).
C E
¼ C E
;max expð0.225QÞ ðC E
;max ¼ 3.371Þ ð1Þ
C R1 ¼ C R1;min expð0.377QÞ ðC R1;min ¼ 103.13Þ ð2Þ
Similar approaches have been derived for chloroform
attributed to B3 battery system and Or = 1. Variation of
the extract and raffinate compositions, C E
and CR1 with
flow rate of chloroform is defined by Eqs. (3) and (4),
respectively.
C E
¼ C E
;max expð0.323QÞ ðC E
;max ¼ 6.053Þ ð3Þ
C R1 ¼ C R1;min expð0.420QÞ ðC R1;min ¼ 111.98Þ ð4Þ
The same remarks hold for the variation of the
extraction degree variables Ec
and WR1 with flow rate
of water evaluated for Or = 1 and B5 battery system
(Fig. 7). The analysis of the explicit form of both equa-
tions results in:
Ec
¼ Ec
;max expð0.225QÞ ðEc
;max ¼ 0.337Þ ð5Þ
WR1 ¼ WR1;min expð0.377QÞ ðWR1;min ¼ 0.103Þ ð6Þ
The corresponding limits of Ec
;max ¼ 0.337 and
WR1,min = 0.103 at an infinite overall extraction time
s ! /(Q ! 0) have been evaluated through graphical
interpolation of data given in Fig. 7.
3.5. Improving the optimum conditions for extraction by
b5 system
To develop a new conceptual definition of optimum
extraction conditions for caffeine recovery from tea
waste by water using B5 solid–liquid extraction system,
it requires an interpretation of F0 = f(Q1) curve both
graphically and analytically (Fig. 8). The simultaneous
impact of process controlling factors, such as Ec
, WR,
m0
, s and Q can modify the number of extraction stages.
Thus, for a given battery system of five extractors, this
requires quantitative knowledge of Ec
;max and WR1,min
so that the optimum values of F0 factor and water rate
can be quantified. Because the overall extraction time
(s) and the flow rate of water (Q) are inversely related
through the function ðs ¼ ð5V s þ V E
Þ=QÞ for the B5
battery system, the analysis of optimum extraction con-
ditions in terms of F0 factor have been evaluated using
Q1 as independent variable. To reduce the complexity
of the optimization problem, an uncoupling and an
independent dealing only with the derivatives (slopes
of the curve) relative to the variation of F0 = f(Q1)
572 A. Senol, A. Aydin / Journal of Food Engineering 75 (2006) 565–573
4.0
LHDE: Linear Homogeneous Differential Equation
NDE: Nonhomogeneous Differential Equation
F0,max
3.0 d homogeneous differential equation (NDE). The explicit
c
m F 0 ¼ F 0;max ½1  expð0.616=QÞ
LHDE: F0 = (E c*/ ΨR1) mod
F0
2.0
b
1.0
observed
a NDE LHDE (Eqs. 5 and 6)
NDE (Eq. 7)
0.0
0.0 1.0 2.0 3.0 4.0
Q -1 (h/l)
Fig. 8. Estimation of optimum extraction conditions through graph-
ical interpolation of the observed (F) curve against Q1 for water and
B5 battery system; Or = 1. Comparison with estimates due to Eq. (7).
function will be processed. However, the conditions
attributed to chloroform and B3 battery system will
not be pursued here.
Referring to Fig. 8, it can be concluded that in the
case of an extraction process realized at an infinite
extraction time (Q1 ! /), the extractability of hot
water closely approaches its maximum limit in terms
of F0 factor, i.e. F 0;max ¼ Ec
;max =WR1;min ¼ 3.27. How-
ever, it is not convenient to proceed an effective extrac-
tion process related to the region reflecting the
asymptotically linear section (cd) due to the extremely
long extraction time. Conversely, the corresponding lin-
ear section (ab) reproduces the extraction behavior of
hot water in B5 battery system at extremely small F0 fac-
tors presumably favoring an undesirable flow regime
and small extraction degree ðEc
Þ. So, the conditions
attributed to (ab) and (cd) regions are practically not
convenient for an effective extraction process. The inter-
section of the asymptotical drawing lines to these sec-
tions at the intercepting point m should provide the
conditions of optimum extraction in terms of F0, Ec
,
WR, m0
, s and Q variables, respectively. A graphical
interpolation of conditions attributed to the m point
through drawing a parallel line to the axis, i.e. the part
relative to the extremely derivative changes in the slope
of the curve, results in the following optimum range:
F0,opt = 2.07–2.30; Q1
opt ¼ 1.33–1.68; Qopt = 0.6–0.75 l/h.
Consequently, a similar graphical analysis of the extrac-
tion data for the other solvents will separate the location
of the optimum point.
The extraction data from Fig. 8 were fitted in terms of
a linear homogeneous differential equation (LHDE),
where the modeled F0 values were obtained through
Eqs. (5) and (6) for ðEc
Þmod and (WR1)mod, respectively.
Similarly, the F0 estimates due to the function
F0 = f(Q1) were also correlated with respect to a non-
form of NDE is given by Eq. (7).
ð7Þ
where, F 0;max ¼ Ec
;max =WR1;min ¼ 3.27 is the maximum
possible limit for the system studied. Fig. 8 illustrates
the consistency of predictions achieved for both LHDE
and NDE defined by Eqs. (5)–(7). In fact, both ap-
proaches proved to be reasonably accurate yielding rela-
tive mean errors of 0.45% for LHDE and 6.5% for Eq. (7).
4. Conclusions
5.0
The isothermal extraction of caffeine from tea waste
in a battery system of three or five extractors has been
elucidated depending on the flow rate of chloroform
and water used as effective solvents. Characterization
of the extraction efficiency of battery system is inti-
mately connected to the solvation degree of extractant
with Ec
value for chloroform ranging about two times
larger as compared to the water one. Water exhibits a
moderate extraction power with a remarkable maximum
of F0 factor, F0,max = 3.27.
The way to formulate the optimization problem
including F0 factor and Q as dependent design variables
has been discussed. The evaluated efficiency results give
evidence of two critical factors, i.e. the flow rate and sol-
vation degree of solvents, to affect significantly the mag-
nitude of extraction degree. Figs. 5–8 summarize the Ec

and F0 factors, being overly sensitive to the extractant
loads and the leaching stages. The proposed Ec
, WR1
and F0 approaches, Eqs. (5)–(7), appear to be an
improvement in data fit for a moderate scale battery
extraction system. The best fits display LHDE approach
for Ec
and F0 reproducing the data with an average er-
ror of 0.5%. Much research remains to be done, above
all in a commercial-scale battery system.
Acknowledgements
The authors thank the ‘‘Research Fund of Istanbul
University’’ and Prof. Emin Ulusoy for the technical
support of this study.
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