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J.

of Supercritical Fluids 59 (2011) 5360

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The Journal of Supercritical Fluids


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

Extraction of caffeine from Robusta coffee (Coffea canephora var. Robusta) husks using
supercritical carbon dioxide
J. Tello, M. Viguera, L. Calvo

Department of Chemical Engineering, Universidad Complutense de Madrid, 28040 Madrid, Spain

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].

Numerous studies have reported the effects of caffeine con-sumption in


humans, such as the well-known stimulant effect of low doses of caffeine on
the nervous system, which enhances concentration capacity and counteracts
tiredness. However, in more sensitive individuals (or under bigger doses of
caffeine), this effect could generate episodes of insomnia, anxiety, nervousness, irritability, hostility and mood swings. Some other reported

Corresponding author. Tel.: +34 913944185. E-mail


address: lcalvo@quim.ucm.es (L. Calvo).

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].

On the other hand, the low solubility of xanthines in super-critical CO 2 ,


due to its apolar character, makes the addition of polar cosolvents (such as
water or ethanol [13,15,1820]) to the compressed gas an interesting practice.
Cosolvent effects are due to specific chemical (hydrogen bonds and acidbase
interactions) or physical interactions (dipoledipole or dipole-induced dipole)
between the cosolvent and solute, and also to a possible interac-tion between
the solvent and the cosolvent, affecting solvent-solute

54

J. Tello et al. / J. of Supercritical Fluids 59 (2011) 5360

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.

interactions. These effects result in accelerating and making the extraction


easier [15]. Regarding the operational conditions, the solvent power of

2. Materials and methods

supercritical CO2 is highly dependent on pressure and temperature, variables


that can be independently modified. Thus, different authors have reported

2.1. Materials

higher yields when work-ing at high pressures, due to the enhanced CO 2


solvent power, and when working at higher temperatures [14,16,2022].

Whole coffee husks of C. canephora var. Robusta were obtained from


Manaus (Brazil). They were previously characterised in Natraceutical group
by standard methods, with a fat content of 1.0%, a moisture content of 16.4%
and a caffeine concentration of 1.1%. This material was stored in dry
conditions at room temper-ature during the investigation. Pressurised liquid
carbon dioxide (99.998% in purity) was kindly donated by Carburos Metlicos
S.A. Caffeine, 99.99% in purity and used in the solubility experiments, was
provided by the Natraceutical Group. The packing agents were round
perforated plastic beads, with an average diameter of 2 mm. They were also
used to create the inert bed in the net caffeine sol-ubility measurement
experiment. Redistributors were made from a stainless steel mesh with same
area as the cross section of the extractor.

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.

Whole coffee husks with a natural humidity of 16%.


Whole coffee husks with a humidity of 32%.
Whole coffee husks with a humidity of 48%.
Whole coffee husks with a humidity of 64%.
Ground coffee husks (32% humidity) loaded with redistributors.

6.Ground coffee husks (32% humidity) loaded


with redistributors and packing agents (36%,
w/w).

J. Tello et al. / J. of Supercritical Fluids 59 (2011) 5360

55

7. Ground coffee husks (32% humidity) loaded with redistributors and


packing agents (50% w/w).

were performed using standard caffeine solutions at different concentrations.

2.3. Apparatus description and extraction process

2.5. Measurement of caffeine solubility

Supercritical fluid extraction was conducted using the lab-oratory scale


system previously described by Calvo et al. [33], consisting of a CO2 feeding
line, a 50 mL capacity 316 ss extrac-tor, a pressure control device and a
sample collection system, as shown in Fig. 1.
The CO2 was fed from the pressured container in the liq-uid phase, then
cooled in a temperature-controlled bath (Selecta, Frigiterm-30) to 258 K and
impelled by a cooled-head mem-brane pump (Milroyal D, Dosapro Milton
Roy). This refrigeration prevented pump cavitation in the pressurisation
process. The pres-surised CO 2 is pre-heated in a coil located inside a heating
jacket prior to entering the vessel. The vessel is also thermally conditioned by
another heating jacket; both with a temperature control of 1 K and recorded
by a type K thermocouple placed inside the reactor in direct contact to the
fluid and the solid. Pressure was read by a Bourbon manometer with an
accuracy of 5 bar. The control of the pressure and flow rate was achieved by
both a heated micro-metering valve (Tescom, Serie 26-1700) and the pump. A
safety rupture disk set at 380 bar prohibited the pressure from exceed-ing the
prescribed values. The amount of CO 2 per unit of time was determined in a
mass flow meter (Alicat Scientific, M-10SLPM-D) connected at the end of
the line with an accuracy of 0.5 g/min.

To measure the solubility of net caffeine in pure CO 2 , a given amount of


caffeine was charged in the extractor on an inert bed made of plastic beads.
The rest of the operation was performed as described in Section 2.4.

2.6. Determination of results


Extraction yield data were expressed as the percentage of total extract
obtained with respect to the initial content of fats and caf-feine.
Extract

Extraction Yield (%) :

(g)

[Fats (g) + Caffeine (g)]initial

100

Caffeine yield data were expressed as the percentage of caffeine in the


extracts (obtained from purity data) with respect to the initial content of
caffeine.

Caffeine Yield (%) : Extract (g) Caffeine content (%) Initial


Caffeine (g)

2.7. Experimental standard deviation


Coffee husks, previously weighed and adequately pre-treated, were loaded
in the extractor, forming a fix bed. When using whole husks 8.01 0.28 g
were used. When using milled coffee husks, the quantity of 15.75 1.64 g
was loaded into the extractor. Redistribu-tors made of stainless steel mesh
having the same size of the cross section of the extractor, were introduced
approx every 1.5 cm in the tests done with the ground material. Then, the
extractor was closed and pre-heated. After that, the CO 2 was pumped in, and,
once the desired pressure was reached, the back pressure regulator (BPR) was
opened, providing a continuous flow through the bed. After the valve, the
CO2 was depressurised, the solvent power of the super-critical fluid dropped
and the extract precipitated in a previously weighed glass flask. When the
established treatment time was over, the apparatus was depressurised, the
extract weighed and the cof-fee husks unloaded. The total amount of CO 2
circulated was read by the mass flow meter.

Since caffeine is a solid product, part of it stuck to the walls of the


equipment. To recover it, after each experiment, a washing pro-cedure was
conducted. To do this, a portion of cotton was soaked in 40 mL of ultrapure
water and loaded in the extractor. Then, CO 2 at 323 K was flown through the
extractor at a pressure of about 60 bar (container pressure) with a flow rate of
23 g/min for 20 min. The procedure was repeated twice. The collected water
with the corre-sponding dissolved caffeine was placed in an oven at 323 K.
Once the water was evaporated, the precipitate was weighted, properly
labelled and stored for its subsequent composition and purity anal-ysis.
Similar washing methods with polar solvents were previously used by
Saldana [34].

To assess the reproducibility of the results, two experiments were repeated


six times each, establishing an experimental stan-dard deviation of 9% in
extraction yield and 7% in caffeine purity. All data are the average of at least
two experiments.
3. Results and discussion
This section first presents the effect of pre-treatment of the raw material on
the yield of the extraction process. Thus, the initial moisture content and the
particle size of the raw material were explored. The use of agents to prevent
the agglomeration of the bed was then investigated to enhance contact.
Regarding the variables that affect the extraction process, different values of
pressure, tem-perature and operational times combined with different CO 2
flow rates were studied.
Caffeine extraction from coffee husks is shown as a curve rep-resenting
the yield results versus the circulated CO 2 mass. Caffeine solubility data were
obtained to assess the outcome of our col-lection procedure, comparing our
results with those previously reported by other authors [35,36]. Finally, a
study of the compo-sition of the extracts in terms of caffeine purity was done.

3.1. Caffeine solubility measurement


In order to verify the reliability of the experimental data obtained with our

2.4. Analysis of caffeine content on the extracts

apparatus, a measurement of the solubility of net caffeine in pure CO 2 at 333


K and 200 bar was done, comparing the results obtained with those previously
reported by Johannsen and Brunner [35] and Saldana et al. [36]. The results
are shown in Fig. 2. Our result closely agreed, validating our extraction and
washing procedure.

The determination of caffeine in the extracts was performed by HPLC


following the protocols stated by Ic en and Gr [12]. Briefly, extracts were
diluted with ultrapure hot water, filtered under vacuum, cooled and analyzed
by means of an Agilent 1100 Series chromatograph equipped with an UV
visible detector set at 320 nm, and a C-18 column. The mobile phase used was
ace-tonitrile (30%, v/v) (Merck) at 0.8 mL/min flow rate. Calibrations

Caffeine solubility showed a direct relationship with operation conditions.


The higher the pressure was, the higher the amount of extracted caffeine. This
result was attributed to the increased density of the solvent and, consequently,
to its solvent power. On the contrary, the effect of temperature depended upon
the work-ing pressure, with retrograde behaviour at pressures lower than about
200 bar. This pressure, where the solubility isotherms cross,

56

J. Tello et al. / J. of Supercritical Fluids 59 (2011) 5360

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)

Fig. 2. Solubility of caffeine in supercritical CO 2 at different pressures and tempera-tures ( :


313 K, Johannsen and Brunner [35]; : 333 K, Johannsen and Brunner [35], : 353 K, Johannsen
and Brunner [35]; +: 313 K, Saldana et al. [36], 323 K, Saldana et al. [36], : 343 K, Saldana
et al. [36], and : 333 K, this work).

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

In light of these results, it can be concluded that the hydration of coffee


husks prior to the extraction process is a critical factor. This fact could be
attributable to the hydrolytic rupture of hydro-gen bonds which link the
caffeine to the natural matrix on which it is adsorbed, liberating it to be swept
out by the supercritical CO2 [39]. Furthermore, water could contribute to
swelling of the cell membrane, leading to the enhancement of solute diffusion
out of the plant tissues [11,40]. In fact, we observed an important volume
augmentation of the husks after wetting. Another indirect reason could be the
entrainer effect of the water dissolved by the CO 2 dur-ing the extraction,
facilitating the dissolution of polar compounds [40] such as caffeine.
Supporting this hypothesis, Iwai et al. noticed that solubility of caffeine in
supercritical CO2 was found to increase 22% when using CO 2 with saturated
water at 313.2 K and 150 bar [41]. Similarly, Park et al. found an important
increase (from 9% to 75%) on caffeine extraction yield from green tea, when
using CO2 wetted with 8.8% water [18].

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].

3.2. Effect of coffee husks initial moisture content


In industrial supercritical CO2 decaffeination processes, a previ-ous prewetting of the coffee beans is needed in order to make the process feasible
[9,38,39]. Similarly, we found that it was necessary to wet the coffee husks
prior to extraction, since hardly any caffeine was removed when working with
coffee husks as received, even at

3.3. Effect of grinding and use of packing and redistributors


In general, grinding is an operation that improves the extraction of
compounds because it decreases the particle size, augmenting the contact area
with the solvent [42,43]. However, it is a high energy cost operation, so it is
important to evaluate the need for this procedure.
In order to assess the impact of grinding the raw material, yields obtained
at fixed conditions in both whole and ground coffee husks were compared
(samples 2 and 5, in Fig. 3, respectively). The results show that grinding did
not improve the process performance, but also hindered the operation. This
could be because milling the cof-fee husks together with the addition of water
generated a very

30

Extraction Yield (%)

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).

J. Tello et al. / J. of Supercritical Fluids 59 (2011) 5360


Table 1
Experimental conditions to obtain increasing amounts of CO2 for Fig. 4.

100
90
80

Extraction Yield (%)

57

70
60
50

CO2 flow (g/min)

Time (min)

CO2 mass (g)

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

CO2 mass (g)


Fig. 4. Comparison between the extraction curves obtained for pure caffeine ( ) and for the total
extract from coffee husks (). Conditions: 333 K and 200 bar (broken line: linear fitting; solid
line: second grade polynomial fitting).

compact bed, so CO 2 would pass through preferential channels (probably


around the bed) without making efficient contact with the raw material. This
negative effect is common in beds made of finely ground raw materials [44].
To eliminate this negative effect, mesh was inserted together with the raw
material at different levels in the fixed bed to facilitate CO 2 radial
redistribution, as previously recommended [45]. We also studied mixing of
the ground husks with a packing material con-sisting of inert perforated beads
used in two different proportions by weight: 36% and 50% (samples 6 and 7
of Fig. 3, respectively). Its purpose was to increase the void fraction of the
bed facilitating the CO2 flow and contact. Our results showed that the use of
these agents improved the extraction yield compared to those samples in
which they were not employed, but, owing to the fact that the results obtained
were not better than those from the whole raw material, we opted to continue
the investigation with coffee husks without grinding, which would mean
important energy savings at the industrial scale.

3.4. Extraction curve


The course of the extraction process can be followed by deter-mining the
amount of extract against the time of extraction or the solvent used. If the
extractible compounds are easily acces-sible, the obtained curve presents two
different parts; the first one is a straight line (corresponding to a constant
extraction rate) while in the second part, the curves bends down, approaching
a limiting value which is given by the total amount of extractible substances
[46]. In cases of a low initial concentration of extract in the solid substrate or
an extract not readily available for the sol-vent, transport within the solid
dominates from the beginning of the operation. In this case, the extraction
curve does not show these two parts, but approaches an asymptote, given by
the distribution coefficient corresponding to the initial concentration of the
extract in the solvent [47]. Of the latter type are those obtained for the
extraction of caffeine from coffee husks using supercritical CO 2 . An example
obtained at 333 K and 200 bar is given in Fig. 4. The extrac-tion yield
increased at an ever-decreasing rate as the mass of CO 2 was increased.
Increasing amounts of CO2 flowing through the fixed bed were achieved by
increasing the CO2 flow rate and/or by using longer operational times (see
Table 1).

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

extraction from coffee husks. For example, a quantity of 150 g of CO 2 was


enough to achieve total extraction of pure caffeine if it was completely
accessible, while for coffee husks, this amount could only retrieve 15% of the
extractible compounds (that is, a mixture of caffeine, fats and other minor
compounds.)
The low extraction yield achieved may be attributed to two reasons. First
of all, it could be due to the capacity of caffeine to form complexes with
certain compounds naturally present in cof-fee husks (such as chlorogenic
acids) which would prevent its total removal [15,20] even in the presence of
water. Second, it could be related to the strong resistance of the internal mass
transfer.
3.5. Effect of operating conditions
The density of a supercritical fluid varies dramatically with operational
pressure and temperature. Thus, one of the most char-acteristic properties of
supercritical fluids is the wide range of densities that can be attained
depending on the pressure and temperature of work. Table 2 shows the
estimated density val-ues corresponding to the operational conditions used in
this work [48]. Consequently, and due to the direct relationship between the
density of a fluid with its solvation capacity, gases at supercritical conditions
can vary enormously in terms of solvent power by small variations of pressure
and/or temperature.
On the other hand, the change of these two variables gener-ates significant
changes in CO2 transfer properties, such as viscosity and diffusivity, which
therefore impact on the penetrability of CO2 into solid matrices. In general,
increasing the operational pressure generates an increment of viscosity and a
reduction of the self-diffusion coefficient, while an increase in temperature
causes the opposite effect. Finally, when it comes to plant materials, it is especially important to maintain the temperature in a certain range since it could
alter the properties of both the natural source and the solutes being extracted.
For all these reasons, when evaluating a supercritical fluid extraction process,
it is mandatory to study the impact of these two variables.

3.5.1. Effect of temperature on extraction yields


As discussed in Section 3.1, the impact of temperature on the solubility of
extractible compounds depends on the working
Table 2
Density of supercritical CO2 under the experimental conditions used in this work [48].

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

J. Tello et al. / J. of Supercritical Fluids 59 (2011) 5360

70

35

60

(%)

40

30
25

Yield

50

20

Extraction

Extraction Yield (%)

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).

pressure, which depends on whether the operation is carried out above or


below the crossover point.
In Fig. 5, extraction yields from wet and whole coffee husks using CO 2 at
300 bar with increasing temperature from 313 to 373 K are shown. The
solvent to feed ratio was kept fixed at 39 g CO 2 /g (experimental runs were
obtained at constant flow rates). Under the same treatment conditions, higher
yields were obtained when working at higher temperatures, as was expected
due to operating above the crossover point, leading to an enhancement in
caffeine solubility. This fact has been previously reported by Saldana et al.
[15], who concluded that the extraction yield of methylxanthines from various
natural sources at 400 bar (above the crossover point) increased with
increasing temperature, whereas when working at 100 bar, there was a
retrograde behaviour. This result also agrees with those obtained by Kim et al.
[11], whose caf-feine extraction yields from green tea leaves increased from
54% to 66% by increasing the working temperature from 313 to 353 K while
operating at 400 bar. Similarly, in the extraction of caffeine from coffee beans,
Saldana [34] found that by increasing the working temperature from 313 to
343 K, the amount of material extracted when working at 280 bar increased,
although much of the extract was the essential oil of coffee, which in green
coffee beans of the Robusta variety comprises between 9 and 13% (w/w) of
the raw material.

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

supercritical CO2 varied from 1.506 10 m /s to 1.992 10


working at a fixed pressure of 137 bar [50].

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).

Furthermore, the colour of the extracts was influenced by the working


temperature; thus, samples obtained at higher tempera-tures showed a dark
brown colour instead of the yellowish-green seen in the samples obtained at
lower temperatures. This colour transformation was possibly due to the
browning of some of the pigments naturally present in the coffee husks.

3.5.2. Effect of pressure on extraction yields


Pressure is another factor that sets the solvent capacity of supercritical
CO2 . As discussed in Section 3.1, an increment of the working pressure
causes an increase in the density of the com-pressed gas (see Table 3), which
in turn enhances the gas solvent capacity for the removal of the caffeine.
To check whether this trend was maintained in the extraction process,
different pressure values were explored maintaining a fixed temperature of
373 K and a solvent to feed ratio between the compressed gas and the coffee
husks of 53 g/g. Results are shown in Fig. 6.
Indeed, and as expected, an increase in the operating pressure
exponentially increased the efficiency of extraction. A raise in pres-sure from
100 to 300 bar, multiplied by ten the extraction yield. This result is consistent
with those found in literature. Thus, Saldana et al. [15] confirmed the effect
of variation of pressure on extraction yield: working at 100, 200 and 300 bar
resulted in the removal of 0.26%, 60% and 96% of the initial caffeine present
in guaran seeds, respectively. Moreover, Kim et al. [11] improved the yield of
caf-feine extracted from tea leaves from 3% to 28% when increasing the
operational pressure from 200 to 400 bar working at a fix tempera-ture of 323
K using compressed CO2 modified with water (7%, w/w). Similarly, Ic en
and Gr [12] reported increments on the extraction of caffeine from tea stalks
from 13.6 to 14.7 mg/g when augmenting the pressure from 150 to 200 bar at
333 K.

Table 3
Total extraction and caffeine yields obtained under different conditions.
T (K)

P (bar)

Solvent to raw material

Time (min)

Extract yield (%)

Purity of caffeine (%)

Caffeine yield (%)

120
105
120
100
105
300

24
28
35
29
65
59

63
74
61
65
64
77

27
39
40
36
78
84

mass ratio (gCO2 /g)


333
353
373
373
373
373

300
300
300
200
300
300

35
36
40
53
58
197

J. Tello et al. / J. of Supercritical Fluids 59 (2011) 5360

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

N.A., Datum not available.


a FAO Statistics [23].
b Data obtained from Ref. [1].

requires the use of much lower solvent to raw


3.6. Caffeine purity in the extracts
Along with the caffeine extracted, other
unidentified com-pounds naturally present in
coffee husks were recovered, primarily fatty
compounds. Table 3 shows the purity of selected
extracts obtained under different conditions.
The main component in all the extracts
obtained was caffeine, with an average value of
67%. This high selectivity of supercriti-cal CO 2
for caffeine in coffee beans has been previously
reported by Saldana [34]. This value was not
substantially altered when varying experimental
conditions. As a result, caffeine yields var-ied
proportionally to total extraction yields. In other
words, an increment in operational pressure,
temperature and solvent to raw material mass
ratio resulted in higher extraction rates, achieving
the removal of more than 80% of the initial
caffeine when working under the most extreme
conditions.
On the other hand, the rest of the compounds
were easily remov-able by simple water washing,
which generated two immiscible phases: a fatty
one with the vast majority of the undesirable
com-pounds, and an aqueous one in which the
caffeine was selectively soluble. After
evaporating this water, extracts had purity higher
than 94%.

3.7. Comparison with other natural sources


Table 4 shows a summary of the yields of
caffeine extracted from different natural sources
with pure supercritical CO2 . The oper-ational
conditions employed in the processes are also
included. The highest extraction yield of caffeine
obtained from coffee husks (about 84%) was a
good value, even though it was not as high as
those obtained in supercritical extraction from
guaran seeds and mat leaves.
However, compared to these other sources,
coffee husks present further advantages as a raw
material for the production of caffeine. First, the
world production of green coffee is higher than
that of the other natural sources cited, which
generates (as commented in Section 1) a large
quantity of husks rich in caffeine during the
manufacturing process. Second, the procedure

Yield (%)

Ref.

66
97
96
9
62
66
84
78

[16]
[15]
[15]
[17]
[12]
[12]
This work
This work

ratio (gCO2 /g)

(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

material mass ratios (60200 g CO 2 /g).


Consequently, this material is definitely an
interesting option for obtaining caffeine on an
industrial scale, as well as from an eco-nomical
and environmental point of view.

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
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rate or by increasing operational times. Optimum
relationships should be deducted through an economical analysis.
Regarding the operational conditions, it was
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Caffeine was not extracted pure, but in a


mixture of fats and small quantities of pigments,
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Thus, coffee husks are a very interesting
option as a raw mate-rial from an economic and
industrial point of view since they are an
abundant residue of the coffee industry with a
high caffeine content, most of which is simply
extracted. The low cost of the raw material and
the employment of moderate CO 2 ratios would
result in low production costs. However, an
exhaustive economi-cal analysis should be made
to establish if the combination of this benefit
together with the selling of the caffeine and the
husks could counterbalance the relatively high
installation costs.

Acknowledgement
The authors thank Natraceutical Group for the
financial support.

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