Escolar Documentos
Profissional Documentos
Cultura Documentos
Abstract
In this work, a review of the Brazilian scientific production in the past 10 years in the field of supercritical fluid is presented. The historical
facts associated with the previous edition of the Brazilian Meeting on Supercritical Fluids are discussed. Because of the importance of the
other South America countries contribution to the filed, a summary of the research published in the past 5 years by all South America countries
is also presented.
In the past 5 years (19992003) 82 papers from South American countries were published in journals indexed in the Web of Science data
base. Of these, 26 papers were related to the use of supercritical fluids as an analytical tool. Supercritical extraction from a variety of vegetable
raw material contributed with 38 papers and the petroleum industry added 2 papers to the field. Reactions contributed with 3 publications
while thermodynamics and fundamental studies were responsible for 13 publications. The Brazilian contribution represented 5384% of the
publications in the above areas.
2004 Elsevier B.V. All rights reserved.
Keywords: Brazil; High pressure phase equilibria; Process parameters; Reaction under supercritical conditions; Solubility data; Supercritical fluids; Supercritical
fluid extraction
1. Historical facts
The first Brazilian Meeting on Supercritical Fluids
(EESPN94) was held in August 2223, 1994. It was organized by LASEFI (Lab Physical Separations), DEA (Department of Food Eng)/FEA (College of Food Engineering), UNICAMP (State University of Campinas), with the
intent of being a space to discuss the research being done
in Brazil. At that time the six invited speakers were R.
Dorhn (Technische Universitat Hamburg, Harburg, TUHH)
from Germany and L.E.D.N. Sutter (Liquid Carbonic Industrias S.A.), E. Cassel (PEQ, COPPE/Federal University of
Rio de Janeiro, UFRJ), J.V. Oliveira (DEQA/Federal University of Santa Catarina, UFSC), F.M. Lancas (Institute of
Chemistry, IQ/University of Sao Paulo, USP), and G.L.V.
Coelho (Department of Chemical Technology, DTQ/Federal
Rural University of Rio de Janeiro, UFRRJ) from Brazil.
EESPN94 was sponsored by FAEP (UNICAMP Research
Foundation), FAPESP (State of Sao Paulo Science Founda
Corresponding author. Tel.: +55 19 3788 4033; fax: +55 19 3788 4027.
E-mail address: meireles@fea.unicamp.br (M.A.A. Meireles).
0896-8446/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2004.11.003
110
Table 1
Numbers of publications related to supercritical fluids originating in South America
Field
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
Total
Analytical methods
ExSS
Reactions
Thermodynamics and fundamentals
Total
8
9
8
25a
2
11
12
19
11
42b
8
2
3
13
5
6
2
13
7
13
2
8
30
6
7
1
2
16
4
10
1
2
17
4
8
2
14
66
74
4
40
184
a
b
Table 2
Experimental data obtained in SFE units using laboratory scale extractor vessel (VE > 50 mL) in Brazil
Raw material
Volatile oil
VE 106
(m3 )
385
dB 103
(m)
64
HB 103
(m)
130
Oleoresin
26.4
10.5
305
29
0.080.11
170
60
60
100
203
39.6
165.5
97.5
n.a.
Caffeine,
theobromine and
cocoa butter
Methylxanthines
50
50
Target component
Black pepper
Buriti
Mauritia exuosa
Chamomileb
Coal
Chamomilla
recutita L.
Rauschert
Cocoa beanse
Theobroma cacao
Cocoa beansc
Theobroma cacao
Anise seedb
T
( C)
30
80140
QCO2 105
(kg/s)
1.236.12
1100
3040
150300
0.121.05
0.212.38
590
4055
200300
3043
75
.4
0.270.54
370
3040
100200
3.336.66
n.a.
40
0.851.18
410
325400
70125
4.67
n.a.
n.a.
0.32
60.0
70
400
9.5
n.a.
n.a.
0.3152.00
60.0
5070
400
F 103 (kg)
P (bar)
Yielda
(%)
3
.110.7
4
.77.8
2
.54.33
[143]
[136]
300
46
180
115
n.a.
383.3
50
152248
2.2
47
Gingerb,c
Zingiber ofcinale
Roscoe
Zingiber ofcinale
Roscoe
n.a.
Oleoresin
232
27.6
387
80
0.390
350
2535
200250
5.90
Oleoresin
243
28.3
387
80
1.02
339
3040
150250
5.26.0
Caffeine
50
n.a.
n.a.
0.6301.00
60.0
4070
100400
9.50
1
.932.65
2
.13.0
98d
[156]
9.5
Cocoa butter
Guarana seedsc
[133]
[162]
Theobroma cacao
Ginger
[128]
2
.28.5
37
.466.4d ,
13.9 29.9, 2748
20d
Cocoa beans
Ref.
[135]
[137]
[140]
[126]
[137]
Guarana seeds
n.a.
Caffeine
50
n.a.
n.a.
0.6301.00
100.0
4070
400
15.67
98
Lippia sidoidesb
Lippia sidoides
Cham.
Ilex paraguariensis
Volatile oil
220
21.6
600
120
0.334
546
1025
66.778.5
0.623.16
[138]
Methyl-xanthines
50
n.a.
n.a.
0.3152.00
40
4070
400
9.5
1
.473.11
98d
Volatile oil
200
n.a.
n.a.
25
n.a.
125
2040
100200
1.67
235
28.3
375
56
n.a.
238
4555
200300
2.03.3
Passiora edulis
Fatty acids
carotenoids
Fatty acids
208
80
130
500
0.181.19
2400
4470
200300
25
0
.201.50
1
.765.29
1128
[127]
Palm
Majorana hortensis
Moench
Elaes guineensis
Spirulina
Spirulina maxima
370
50
130
173f
0.301.18
940
2070
150180
3.3
Thymus vulgaris
50
n.a.
n.a.
1012
0.130.32
200240
40
200
1.45.7
Turmericc
Curcuma longa L.
Oleoresin
50
17.6
198
20
0.2
750
2530
250300
1124
Curcuma longa L.
Oleoresin
232
27.4
375
126
0.69
30
300
0.84
0
.300.95
0
.511.93
4
.522.5
77
[131]
Thyme
Stevia rebaudiana
Bertoni
Stevia rebaudiana
Bertoni
232
27.6
387
62
0.83
270
1030
120200
5.05.6
235
28.3
375
6982
0.98
400
1645
120200
4.82
Mate leaves
Marjoram
Turmericc
b,c
Stevia leaves
Stevia leaves
a
b
c
d
f
[137]
[151]
[4]
[66]
[149]
[165]
[130]
[55]
111
0
.381.63
0
.123.
[137]
B
(kg/m3 )
191
dp 103
(m)
0.3550.71
Botanic name
(or variety)
Pimpinella anisum
L.
Peper nigrum L.
200360
1.122.20
n.a.
[74]
4070
143
n.a.
1
n.a.
Isoflavones
n.a.
References
Soybean flour
Rosemary
Pupunha
Nutmeg
Black pepperb
The authors are grateful to FAPESP for the financial support (1999/01962-1). P.T.V. Rosa thanks CAPES for the pos
doctorate fellowship (AUX-PRODOC-046/02-7).
34.7
7
200300
69.6
Extract
58
n.a.
n.a.
n.a.
913
2831
20
Fatty acids
29
29
44
250300
[125]
3050
120
0.60
1.57.0
0.901.50
90
1724
Volatile oil fatty
acids
35
21
100
23
[57]
4550
688
0.301.45
n.a.
0.121.15
150300
29
Oleoresin
26.4
10.5
305
3060
[159]
485685
0.080.11
0.38
1.425.67
1.5
Baccharis dracunculifolia
Piper nigrun
L.
Myristica
fragrans
Houttuyn
Guilielma
speciosa
Rosmarinus
ofcinalis
IAC-12 variety
Baccharia
Volatile oil
n.a.
n.a.
90120
Yielda
QCO2 105
(kg/s)
P (bar)
dp 103
(m)
F 103
(kg)
HB l03
(m)
dB 103
(m)
VE 106
(m3 )
Target
component (m3 )
Botanic name
(or variety)
Raw material
Table 3
Experimental data obtained in SFE units using small extractor vessel (VE < 50 mL) in Brazil
[154]
1100
0.2
Acknowledgments
[148]
4060
215
Ref.
T ( C)
B (kg/m3 )
112
113
114
[50] G. Stuart, R. Machado, J.V. Oliveira, A.C. Uller, E.L. Lima, Hybrid
artificial neural network applied to modeling SCFE of basil and
rosemary oils, Cienc. Tecnol. Aliment. 17 (1997) 501.
[51] A.M. Souza, J.V. Oliveira, F.W. Tavares, Estudo da seletividade capacidade em sistemas solido-gas, Cienc. Tecnol. Aliment. 17 (1997)
506.
[52] C. Dariva, J.V. Oliveira, J.C. Pinto, M.G. Vale, E.B. Caramao,
Statistical analysis of the SCFE of a Brazilian mineral coal, Cienc.
Tecnol. Aliment. 17 (1997) 512.
[53] M.D.A. Saldana, R.S. Mohamed, P. Mazzafera, Supercritical carbon
dioxide extraction of methylxanthines from mate tea leaves, Braz.
J. Chem. Eng. 17 (2000) 251.
[54] R. Gerszt, F.L.P. Pessoa, M.F. Mendes, Phase behavior of sterols
and vitamins in supercritical CO2 , Braz. J. Chem. Eng. 17 (2000)
261.
[55] A. Pasquel, M.A.A. Meireles, M.O.M. Marques, A.J. Petenate, Extraction of stevia glycosides with CO2 + water, CO2 + ethanol, and
CO2 + water + ethanol, Braz. J. Chem. Eng. 17 (2000) 271.
[56] E.A. Silva, L. Cardozo-Filho, F. Wolff, M.A.A. Meireles, Modeling
the supercritical desorption of orange essential oil from a silica-gel
bed, Braz. J. Chem. Eng. 17 (2000) 283.
[57] M.E. Araujo, N.T. Machado, L.F. Franca, M.A.A. Meireles, Supercritical extraction of pupunha (Guilielma speciosa) oil in a fixed
bed using carbon dioxide, Braz. J. Chem. Eng. 17 (2000) 297.
[58] F.T. Mizutani, A.L.H. Costa, F.L.P. Pessoa, Stochastic simulation
of supercritical fluid extraction processes, Braz. J. Chem. Eng. 17
(2000) 307.
[59] A.L. Chassagnez-Mendez, N.C.F. Correa, L.F. Franca, N.T.
Machado, M.E. Araujo, A mass transfer model applied to the supercritical extraction with CO2 of curcumins from turmeric rhizomes
(Curcuma longa L), Braz. J. Chem. Eng. 17 (2000) 315.
[60] W. Baumann, S.V. Rodrigues, L.M. Viana, Pigments and their solubility in and extractability by supercritical CO2 I: The case of
curcumin, Braz. J. Chem. Eng. 17 (2000) 323.
[61] R. Eggers, A. Ambrogi, J. von Schnitzler, Special features of SCF
solid extraction of natural products: deoiling of wheat gluten and
extraction of rose hip oil, Braz. J. Chem. Eng. 17 (2000) 329.
[62] J.M. del Valle, S. Bello, J. Thiel, A. Allen, L. Chordia, Comparison
of conventional and supercritical CO2 -extracted rosehip oil, Braz.
J. Chem. Eng. 17 (2000) 335.
[63] A.L.H. Costa, F.P.T. da Silva, F.L.P. Pessoa, Parameter estimation
of thermodynamic models for high-pressure systems employing a
stochastic method of global optimization, Braz. J. Chem. Eng. 17
(2000) 349.
[64] S. Waintraub, C.N. Fonseca, G.M.G. Soares, E.A. Campagnolo,
Conversion of a deasphalting unit for use in the process of supercritical solvent recovery, Braz. J. Chem. Eng. 17 (2000) 355.
[65] E.P. Martins, D.A.G. Aranda, F.L.P. Pessoa, J.L. Zotin, Hydrogenation of diesel aromatic compounds in supercritical solvent environment, Braz. J. Chem. Eng. 17 (2000) 361.
[66] S.A.B.V. de Melo, G.M.N. Costa, R. Garau, A. Casula, B. Pittau,
Supercritical CO2 extraction of essential oils from Thymus vulgaris,
Braz. J. Chem. Eng. 17 (2000) 367.
[67] F. Augusto, A.L.E. Lopes, C.A. Zini, Sampling and sample preparation for analysis of aromas and fragrances, Trac-Trend Anal. Chem.
22 (2003) 160.
[68] V. Arancibia, M. Valderrama, K. Silva, T. Tapia, Determination
of chromium in urine samples by complexation-supercritical fluid
extraction and liquid or gas chromatography, J. Chromatogr. B 785
(2003) 303.
[69] L. Olenka, E.S. Nogueiran, A.N. Medina, M.L. Baesso, A.C. Bento,
E.C. Muniz, A.F. Rubira, Photoacoustic study of PET films and
fibers dyed in supercritical CO2 reactor, Rev. Sci. Instrum. 74
(2003) 328.
[70] V.G. Zuin, J.H. Yariwake, C. Bicchi, Fast supercritical fluid extraction and high-resolution gas chromatography with electroncapture and flame photometric detection for multiresidue screen-
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
115
116
[128]
[129]
[130]
[131]
[132]
[133]
[134]
[135]
[136]
[137]
[138]
[139]
[140]
[141]
[142]
[143]
[144]
[145]
[165]
[166]
[167]
[168]
[169]
[170]
[171]
[172]
[173]
[174]
117
[175] S.A.B.V. de Melo, G.M.N. Costa, A.M.C. Uller, F.L.P. Pessoa, Modeling high-pressure vapor-liquid equilibrium of limonene,
linalool and carbon dioxide systems, J. Supercrit. Fluids 16 (1999)
107.
[176] S.A.B.V. de Melo, P. Pallado, G.B. Guarise, A. Bertucco, Highpressure vapor-liquid equilibrium data for binary and ternary systems formed by supercritical CO2 , limonene and linalool, Braz. J.
Chem. Eng. 16 (1999) 7.
[177] E. Cassel, J.V. Oliveira, A.M.C. Uller, M. Rogalski, Solid-fluid
phase equilibrium modeling for binary systems containing carbon
dioxide, J. Supercrit. Fluids 13 (1998) 69.
[178] S.V. Rodrigues, D. Nepomuceno, L.V. Martins, W. Baumann,
Isothermal pressure dependence of the solubility of some triazines
in supercritical CO2 , Fresenius J. Anal. Chem. 360 (1998) 58.
[179] D.E. Wetzler, P.F. Aramendia, M.L. Japas, R. Fernandez-Prini,
Thermal diffusivity in supercritical fluids measured by thermal lensing, Int. J. Thermophys. 19 (1998) 27.