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Texto Cafeina
Extraction of caffeine from Robusta coffee (Coffea canephora var. Robusta) husks using
supercritical carbon dioxide
J. Tello, M. Viguera, L. Calvo
article
info
Article history:
Received 15 June 2011
Received in revised form 22 July 2011
Accepted 22 July 2011
Keywords:
Caffeine
Extraction
Coffee husks
Supercritical CO2
abstract
This work evaluated the technical feasibility of supercritical CO 2 extraction of caffeine from coffee husks, an abundant
residue of the coffee industry. Different pre-treatments (initial humidity and milling) and operational conditions (pressure,
temperature, time and flow rate) were studied in a CO 2 continuous flow laboratory-scale unit. While prior wetting of the
coffee husks was needed, milling was not required to extract the caffeine. The use of higher flow rates and/or operational
times resulted in higher extrac-tion rates. The process was favoured with increased operational pressure and temperature due
to higher solubility. The maximum extraction yield obtained of this alkaloid was 84% when working at 373 K and 300 bar,
using 197 kg CO2 /kg husks. After water washing, the caffeine was at least 94% pure. Compar-ing world production data, the
initial caffeine content and global extraction yield data of other natural sources, this process could be very advantageous for its
technological application.
2011 Elsevier B.V. All rights reserved.
0896-8446/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2011.07.018
1. Introduction
Caffeine (1,3,7-trimethylxanthine) is an alkaloid of the xan-thine group
widely known worldwide due to its occurrence in extensively consumed
beverages, drinks and food. Natural sources of caffeine include different
varieties of coffee beans (Coffea canephora, Coffea arabica), tea leaves
(Camellia sinensis), guaran seeds (Paullinia cupana), mat leaves (Ilex
paraguariensis), kola nut seeds (Cola nitida, Cola acuminata) and cocoa beans
(Theo-broma cacao) [1]. Despite the fact that tea is globally consumed more
widely than coffee, coffee is the main source of caffeine in daily consumption
given its generally higher caffeine content [2]. Other dietary factors that
contribute to daily overall caffeine consumption include foods like certain soft
and energy drinks, chocolate, candies and sweets, as well as that contained in
some medications [3], such as stimulants, diet aids, painkillers and cold
remedies [4].
physiological effects are stimulation of the gastric and urinary sys-tems and
increased heart rate and blood pressure [48].
These negative effects have led to an increasing consumption of
decaffeinated coffee, generating the development of various pro-cesses that
remove this alkaloid from coffee beans. Among these processes, organic
solvents with high toxicity (methylene chloride, ethyl acetate), Swiss water
decaffeination (which results in a less flavourful brew than other methods)
and the employment of carbon dioxide in supercritical conditions are
commonly used [9]. The lat-ter was successfully developed on an industrial
scale in the 1970s, based on Kurt Zosels patent [10], initially run by Cafe
HAG and General Foods [9]. Compared with other conventional methods,
this process showed better results, both in terms of generating a higher quality
product and for being a better process from an envi-ronmental point of view.
CO2 is a non-flammable and non-toxic solvent that can be easily removed
from the final product. These advantages have driven the subsequent
investigation of supercriti-cal extraction of caffeine from other natural
sources, such as tea leaves [11], stalks and fibre wastes from industrial tea
process-ing [12,13], guaran seeds [14,15], mat leaves [15], cocoa beans
[15,16] and coffee oil [17].
54
Fig. 1. High pressure apparatus used for the supercritical fluid extraction of caffeine from coffee husks. PI, pressure indicator; TI, temperatura indicator; TIC, temperature indicator and controller; TC,
temperature controller; BPR, back pressure regulator.
2.1. Materials
Among all the natural sources previously cited, coffee could be the most
important worldwide from an economical point of view. FAO estimated its
world production in 2009 at more than eight million tons [23]. In order to be
used and consumed, green cof-fee is processed by two different methods, the
wet or dry method. On average, for every ton of clean coffee produced, 1 ton
of husks are generated during dry processing, whereas, for wet process-ing,
0.28 tons of parchment husks, 2 tons of pulp and 22.73 tons of wastewater are
generated [24].
Obviously, this great amount of residues represents a serious source of
pollution and environmental problems. Recent efforts to solve this problem
include activities like the production of organic fertilisers [25], using these
residues as a substrate for the synthe-sis of biomass [26] and bio-ethanol [27],
for the production of a diversity of products through fermentation (citric acid
[28], pectins, pectic enzymes and vinegar [29]), as a natural source of anthocyanins [30], for the growth of mushrooms, as an adsorbent [27] and as a
source of caffeine by percolation with alcohols and water [31]. Alternatively,
coffee husks have been used for animal feed, because of their high cellulose
content, which can be metabolised by ruminants. However, given its structure
and its high content of lignin, silica [31], polyphenols, tannins (5% [26]) and
caffeine (1.3% [26]) [32], this use is limited. Thus, the most common final
use for husks is in coffee mills to provide the energy needed for the final
drying of the coffee beans [31].
The aim of this work was to evaluate the feasibility of extract-ing caffeine
from coffee husks using carbon dioxide at supercritical conditions, as a means
of using this residue to obtain high-value caf-feine that may be subsequently
used in the food, pharmaceutical, veterinary or cosmetic industries.
2.2. Pre-treatment
To evaluate the influence of the condition of the raw material on the
extraction rate, two different pre-treatments were performed. First, coffee
husks were ground by the commercial stainless steel blades of a coffee
grinder. Second, the material (raw or ground) was humidified to the desired
percentage of humidity (measured by weight) with ultrapure water. Thus, the
following pre-treatments were assayed:
1.
2.
3.
4.
5.
55
(g)
100
56
the most extreme conditions allowed by the apparatus (350 bar and 373 K)
(sample 1, Fig. 3).
Knowing the initial moisture content of the coffee husks pro-vided
(16.4%), higher hydration values were tested, i.e. 32%, 48% and 64%
(samples 2, 3 and 4, in Fig. 3, respectively). The results indicated that
increasing the amount of water up to 32% resulted in higher extraction yields,
but exceeding this percentage was not benefi-cial. For example, when the
water content was 64%, the extraction resulted in the removal of only 5% of
the extractible compounds originally present in the husks. Moreover, this high
moisture level generated a malfunction of the apparatus, with the formation of
ice crystals in the outlet valve of the extractor, which interrupted the normal
Solubility
(g/kgCO
2)
5
3
4
2
1
flow of CO2 . Because of this, coffee husks at 32% moisture were chosen as
the starting material for the following experiments.
0
100
150
200
250
300
350
400
Pressure (bar)
is known as the crossover pressure [37]. Below it, the caffeine sol-ubility
decreased as temperature increased. Above this value, an increase in
temperature increased solubility [17].
It is well-known that this behaviour is a consequence of the opposing
effects of the solvent density variation and the solute vapour pressure. Below
the crossover pressure (about 200 bar), small increases in temperature result
in drastic decreases in solvent density and consequently, on solvent capability.
As an example, at 180 bar, caffeine solubility decreases from 1.16 to 0.87
g/kg CO2 when augmenting the temperature from 323 to 343 K [36]. As the
process pressure moves away from the solvent crossover pressure, its density
become less sensitive to temperature changes and the effect that prevails is the
increase in vapour pressure. Thus, impor-tant growths on caffeine solubility
are seen over 200 bar in the isotherms as the pressure increases. This change
in the influence of temperature may also be seen in the isotherms obtained
The lower extraction yield obtained in the test conducted at 64% moisture
was presumably due to the preference of the caf-feine to remain soluble in the
excess aqueous phase, as suggested by Pourmortazavi and Hajimirsadeghi
[40].
with CO2 mixed with cosolvents, although in this case, the crossover pressure
acquires a higher value. For example, for mixtures of CO 2 isopropanol (5%)
or CO2 ethanol (5%), the crossover pressure increases to 210 and 230 bar,
respectively [37].
30
25
20
15
10
5
0
1
W (16,4%
moisture)
W (32%
moisture)
W (48%
moisture)
W (64%
moisture)
G (32%
moisture) + R
G (32%
G (32%
moisture) + R + moisture) + R +
P (36%)
P (50%)
Fig. 3. Effect of different pre-treatments on the extraction yields with supercritical CO 2 at 200 bar and 333 K with a mass ratio of 24 g CO2 /g husks (sample 1 extracted at 350 bar and 373 K) (W,
whole coffee husks; G, ground coffee husks; R, redistributors; P, packing).
100
90
80
57
70
60
50
Time (min)
0.6
2.5
2.4
5.8
180
120
180
120
116
295
436
702
saturated. (The curve was drawn based on the solubility value under the same
operating conditions. This comparison demonstrates the difficulty of caffeine
40
30
20
10
0
0
200
400
600
800
Fig. 4 also compares the extraction yield with the one that would result if
all the caffeine initially contained in the coffee husks would be fully
accessible, so compressed CO2 would leave the extractor
Pressure (bar)
60
100
150
200
250
300
300
300
300
300
300
300
Temperature (K)
373
373
373
373
373
373
363
353
343
333
323
313
Density (kg/m )
100
189
333
481
589
662
703
746
788
830
870
910
70
35
60
(%)
40
30
25
Yield
50
20
Extraction
58
40
30
15
20
10
10
5
303
323
343
363
383
50
100
Temperature (K)
Fig. 5. Influence of temperature on the extraction yield obtained from whole coffee husks at a
fixed pressure of 300 bar, a fixed water content of 32% and a total CO 2 mass of 320 g ( :
experimental data; solid line: linear fitting).
Another reason for this behaviour is the increase in the mass transfer rate
when increasing operational temperature, due to an improvement in the
diffusion coefficient [49]. Knaff and Schln-der showed that for a range of
only 10 K (from 323 to 333 K), the diffusion coefficient of caffeine in
8
m /s when
150
200
250
300
350
Pressure (bar)
Fig. 6. Influence of pressure on the extraction yield obtained from whole coffee husks at a fixed
temperature of 373 K, a fixed water content of 32% and a total CO 2 mass of 429 g ( :
Experimental data; Curve line: second grade polynomial fitting).
Table 3
Total extraction and caffeine yields obtained under different conditions.
T (K)
P (bar)
Time (min)
120
105
120
100
105
300
24
28
35
29
65
59
63
74
61
65
64
77
27
39
40
36
78
84
300
300
300
200
300
300
35
36
40
53
58
197
59
Table 4
Conditions used and caffeine extraction yields from several natural sources obtained using pure supercritical CO 2 .
Raw material
2009 world
a
production
Initial
caffeine (%)
Pressure
(bar)
Temperature
(K)
400
400
400
300
250
250
300
300
343
343
343
343
333
333
373
373
4.2
N. A.
0.8
3.9
3.9
3.9
8.3
8.3
0.60.8
b
4.3
b
0.80.9
b
2.8
1.16
0.92
1.1
1.1
Yield (%)
Ref.
66
97
96
9
62
66
84
78
[16]
[15]
[15]
[17]
[12]
[12]
This work
This work
(MM tons)
Theobroma cacao (cocoa beans)
Paullinia cupana (guaran seeds)
Ilex paraguariensis (mat leaves)
Camellia sinensis (tea leaves)
Camellia sinensis (tea stalks)
Camellia sinensis (fibre wastes)
Coffea canephora (coffee husks)
Coffea canephora (coffee husks)
Solvent to raw
material mass
4. Conclusions
The present study evaluated the technical
feasibility of extract-ing the caffeine naturally
present in Robusta coffee husks using CO2 under
supercritical conditions, as a novel use of this
common and abundant residue from the coffee
industry.
43.7
399
1140
102
924
924
197
58
References
The results revealed that to make the process
feasible, pre-treatment was required, consisting
of pre-wetting of the raw material up to 32%
moisture, which is close to that needed for cof-fee
beans (30%) and doubled the original amount of
water present in the coffee husks. Grinding the
coffee husks seemed to be a pro-cess that
hindered the removal of the compound of
interest, due to the strong compaction of the bed.
It seems that coffee husks were porous enough to
allow the circulation of the gas, easily extracting
the available caffeine.
On the other hand, the use of greater
quantities of CO2 resulted in a large increase in
the amounts of caffeine extracted, as the CO 2 did
not reach saturation. These greater amounts could
be achieved either by increasing the CO2 flow
rate or by increasing operational times. Optimum
relationships should be deducted through an economical analysis.
Regarding the operational conditions, it was
observed that the more extreme the operational
conditions were (pressure and tem-perature above
the crossover point), the higher the extraction
yields achieved. Pressure variation was more
effective, because it affected the density of the
supercritical fluid and, therefore, its sol-vent
capacity. Thus, 84% of the initial caffeine was
extracted, after treating the material for five hours
with 197 g of compressed gas per g of raw
material at 373 K and 300 bar. However, using a
ratio as low as of 58 g CO 2 /g, 78% of the initial
caffeine was recovered under the same
conditions. The remaining caffeine seemed to be
not remov-able under the conditions studied, due
to the strong interactions existing between
caffeine and the plant matrix and the important
limitations to internal mass transfer.
Acknowledgement
The authors thank Natraceutical Group for the
financial support.
60
[2] J.E. James, Caffeine mental performance and mood, in: D.H. Watson (Ed.), Performance
Functional Foods, Woodhead Publishing Ltd. and CRC Press, Cam-bridge, 2003, pp. 168
186.
[3] L.S. Lundsberg, Caffeine consumption, in: G.A. Spiller (Ed.), Caffeine, CRC Press, Boca
Raton, 1998, pp. 199224.
[4] B.D. Smith, T. White, R. Shapiro, The arousal drug of choice: sources and con-sumption
of caffeine, in: B.D. Smith, U. Gupta, B.S. Gupta (Eds.), Caffeine and Activation Theory,
CRC Press, New York, 2007, pp. 942.
[5] A. Smith, Effects of caffeine on human behavior, Food and Chemical Toxicology 40
(2002) 12431255.
[6] J.V. Higdon, B. Frei, Coffee health: a review of recent human research, Critical Reviews
in Food Science and Nutrition 46 (2006) 101123.
[7] P. Nawrot, S. Jordan, J. Eastwood, J. Rotstein, A. Hugenholtz, M. Feeley, Effects of
caffeine on human health, Food Additives and Contaminants 20 (1) (2003) 130.
[8] M.L. Nurminen, L. Niittynen, R. Korpela, H. Vapaatalo, Coffee, caffeine and blood
pressure: a critical review, European J. Clinical Nutrition 53 (1999) 831839.
[9] K. Ramalakshmi, B. Raghavan, Caffeine in coffee: its removal. Why and how? Critical
Reviews in Food Science Nutrition 39 (5) (1999) 441456.
[10] K. Zosel, Process for recovering caffeine, U.S. 3,806,619 (April 23, 1974).
[11] W.J. Kim, J.-D. Kim, J. Kim, S.-G. Oh, Y.-W. Lee, Selective caffeine removal from green
tea using supercritical carbon dioxide extraction, J. Food Engineering 89 (2008) 303309.
[12] H. Ic en, M. Gr, Extraction of caffeine from stalk and fiber wastes using super-critical
carbon dioxide, J. Supercritical Fluids 50 (2009) 225228.
[13] M. Ic en H., M. Gr, Effect of ethanol content on supercritical carbon dioxide extraction
of caffeine from tea stalk and fiber wastes, J. Supercritical Fluids 55 (2010) 156160.
[14] C.B. Mehr, R.N. Biswal, J.L. Collins, Supercritical carbon dioxide extraction of caffeine
from guaran, J. Supercritical Fluids 9 (1996) 185191.
[15] M.D.A. Saldana, C. Zetzl, R.S. Mohamed, G. Brunner, Extraction of methylxan-thines
from guaran seeds, mat leaves, and cocoa beans using supercritical carbon dioxide and
ethanol, J. Agricultural and Food Chemistry 50 (2002) 48204826.
[16] R.S Mohamed, M.D.A. Saldana, P. Mazzafera, Extraction of caffeine, theo-bromine and
cocoa butter from Brazilian cocoa beans using supercritical CO 2 and ethane, Industrial
and Engineering Chemistry Research 41 (2002) 67516758.
[17] A.B.A. de Azevedo, T.G. Kieckbusch, A.K. Tashima, R.S. Mohamed, Supercritical CO 2
recovery of caffeine from green coffee oil: new experimental solubility data and
modeling, Quimica Nova 31 (6) (2008) 13191323.
[18] H.S. Park, H.J. Lee, M.H. Shin, K.-W. Lee, H. Lee, Y.-S. Kim, K.O. Kim, K.H. Kim,
Effects of cosolvents on the decaffeination of green tea by supercritical carbon dioxide,
Food Chemistry 105 (2007) 10111017.
[19] C.J. Chang, K.-L. Chiu, Y.-L. Chen, C.-Y. Chang, Separation of catechins from green tea
using carbon dioxide extraction;, Food Chemistry 68 (2000) 109113.
[20] A.B.A. de Azevedo, P. Mazzafera, R.S. Mohamed, S.A.B. Vieira de Melo, T.G. Kieckbusch, Extraction of caffeine, chlorogenic acids and lipids from green coffee beans using
supercritical carbon dioxide and co-solvents, Brazilian J. Chemical Engineering 25 (03)
(2008) 543552.
[21] R.A. Jacques, J.G. Santos, C. Dariva, J. Vladimir Oliveira, E.B. Caramo, GC/MS
characterization of mate tea leaves extracts obtained from high-pressure CO 2 extraction, J.
Supercritical Fluids 40 (2007) 354359.
[22] H.S. Park, H.-K. Choi, S.J. Lee, K.W. Park, S.-G. Choi, K.H. Kim, Effect of mass transfer on the removal of caffeine from green tea by supercritical carbon dioxide, J.
Supercritical Fluids 42 (2007) 205211.
[23] Food and Agriculture Organization of the United Nations (FAO). FAO statistics.
<http://faostat.fao.org/site/567/default.aspx#ancor> (accessed 07.06.11).
[24] M. Saenger, E.-U. Hartge, J. Werther, T. Ogada, Z. Siagi, Combustion of coffee husks,
Renewable Energy 23 (2001) 103121.
[25] L.A. Duicela, R. Corral, R. Palma, F. Fernndez, B. Fischersworring, Reciclaje
de los subproductos de la finca cafetalera, Comunicaciones del Con-sejo Cafetalero
Nacional (COFENAC), IG-CT-034. <http://www.cofenac.org/ documentos/Compostajede-Subproductos.pdf>, 2003 (accessed 07.06.11).
[26] A. Pandey, C.R. Soccol, P. Nigam, D. Brand, R. Mohan, S. Roussos, Biotechno-logical
potential of coffee pulp and coffee husk for bioprocesses, Biochemical Engineering J. 6
(2000) 153162.
[27] B.M. Gouvea, C. Torres, A.S. Franca, L.S. Oliveira, E.S. Oliveira, Feasibility of ethanol
production from coffee husks, Biotechnology Letters 31 (2009) 13151319.
[28] V.S. Shankaranand, B.K. Lonsane, Coffee husk: an inexpensive substrate for production of
citric acid by Aspergillus niger in a solid-state fermen-tation system, World J.
Microbiology and Biotechnology 10 (1994) 165 168.
[29] R. Rathinavelu, G. Graziosi, Potential alternative uses of coffee wastes and by-products,
International
Coffee
Organization
Communications,
ED-1967/05.
<http://www.ico.org/documents/ed1967c.pdf>, 2005 (accessed 07.06.11).
[30] E.R.B.A. Prata, L.S. Oliveira, Fresh coffee husks as potential sources of antho-cyanins,
LWT-Food Science and Technology 40 (2007) 15551560.
[31] L.G. Elias, Chemical composition of coffee-berry by-products, in: J.E. Braham,
R. Bressani (Eds.), Coffee Pulp: Composition, Technology and Utilization, IDRC Pub., N
108e, International Development Research Centre, Ottawa, 1979, pp. 1116.
[32] J.B. Ulloa Rojas, J.A.J. Verreth, S. Amato, E.A. Huisman, Biological treatments affect the
chemical composition of coffee pulp, Bioresource Technology 89 (2003) 267274.
[33] L. Calvo, B. Muguerza, E. Cienfuegos-Jovellanos, Microbial inactivation and but-ter
extraction in a cocoa derivative using high pressure CO 2 , J. Supercritical Fluids 42 (2007)
8087.
[34] M.D.A. Saldana, Extraction of caffeine, trigonelline and chlorogenic acid from coffee
beans with supercritical CO 2 , M.Sc. thesis, Universidade Estadual de Campinas,
Campinas, Brazil, 1997.
[35] M. Johannsen, G. Brunner, Solubilities of the xanthines caffeine, theophilline and
theobromine in supercritical carbon dioxide, Fluid Phase Equilibria 95 (1994) 214226.
[36] M.D.A Saldana, R.S. Mohamed, M.G. Baer, P. Mazzafera, Extraction of purine alkaloids
from mat (Ilex paraguariensis) using supercritical CO 2 , J. Agricultural and Food
Chemistry 47 (1999) 38043808.
[37] U. Kopcak, R.S. Mohamed, Caffeine solubility in supercritical carbon dioxide/co-solvent
mixtures, J. Supercritical Fluids 34 (2005) 209214.
[38] Decaffeination of raw, green coffee beans using supercritical CO 2 .
<http://www.nd.edu/enviro/design/caffeine.pdf> (accessed 07.06.11).
[39] M. McHugh, V. Krukonis, Supercritical Fluid Extraction, 2nd ed., ButterworthHeinemann, Boston MA, 1994, pp. 294299.
[40] S.M. Pourmortazavi, S.S. Hajimirsadeghi, Supercritical fluid extraction in plant essential
and volatile oil analysis, J. Chromatography A 1163 (2007) 224.
[41] Y. Iwai, H. Nagano, G.S. Lee, M. Uno, Y. Arai, Measurement of entrainer effects of water
and ethanol on solubility of caffeine in supercritical carbon dioxide by FT-IR spectroscopy,
J. Supercritical Fluids 38 (2006) 312318.
[42] E.K. Asep, S. Jinap, T.J. Tan, A.R. Russly, S. Harcharan, S.A.H. Nazimah, The effects of
particle size, fermentation and roasting of cocoa nibs on supercritical fluid extraction of
cocoa butter, J. Food Engineering 85 (2008) 450458.
[43] B. Daz-Reinoso, A. Moure, H. Domnguez, J.C. Paraj, Supercritical CO 2 extrac-tion and
purification of compounds with antioxidant activity, J. Agricultural and Food Chemistry 54
(2006) 24412469.
[44] E. Reverchn, I. de Marco, Supercritical fluid extraction and fractionation of natural
matter, J. Supercritical Fluids 38 (2006) 146166.
[45] L. Wang, C.L. Weller, Recent advances in extraction of nutraceuticals from plants, Trends
in Food Science and Technology 17 (2006) 300312.
[46] G. Brunner, Supercritical fluids: technology and application to food processing,
J. Food Engineering 67 (2005) 2133.
[47] G. Brunner, Gas Extraction Steinkopff Darmstadt, Springer, New York, 1994, pp. 188198.
[48] E.W. Lemmon, M.O. McLinden, D.G. Friend, In: P.J. Linstrom, W.G. Mallard (Eds.),
Thermophysical Properties of Fluid Systems in NIST Chemistry Webbook, NIST Standard
Reference Database Number 69, National Institute of Standards and Technology,
Gaithersburg, MD. <http://webbook.nist.gov> (accessed 07.06.11).
[49] R. Feist, G.M. Schneider, Determination of binary diffusion coefficients of ben-zene
phenol, naphthalene and caffeine in supercritical CO 2 between 308 and 333 K in the
pressure range 80 to 160 bar with supercritical fluid chromatog-raphy (SFC), Separation
Science and Technology 17 (1982) 261270.
[50] G. Knaff, U. Schlnder, Diffusion coefficients of naphthalene and caffeine in supercritical
carbon dioxide, Chemical Engineering and Processing 21 (1987) 101105.