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Bookchapter Fkkksa07
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Perpustakaan Negara Malaysia
Cataloguing-in-Publication Data
CONTENTS
Preface
vii
31
62
vi
Content
125
137
157
Index
197
PREFACE
viii
Preface
viii
INTRODUCTION TO SEPARATION
PROCESSES
Noorhalieza Ali
Separating Agent(s)
Examples
Distillation(1)
Heat (ESA)
Petroleum refining
Extractive
Distillation(2)
Separation of
aliphatics from
aromatics
Absorption(3)
Liquid absorbent
(MSA)
Stripping(4)
Stripping vapour
(MSA)
Removal of benzene
from wastewaters
Liquid-liquid
Extraction(5)
Liquid solvent
(MSA)
Extraction of soybean
oil from soybeans
Supercritical Fluid
Extraction(6)
Liquid solvent
(MSA)
Recovery of
carotenoid from palm
oil
Drying(7)
Recovery of solvent
from polymer
Evaporation(8)
Heat (ESA)
Concentration of
sucralos
Crystallization(9)
Heat (ESA)
Fat fractionation in
vegetable oil refining
Leaching(10)
Liquid solvent
(MSA)
Extraction of sugar
from sugar beet
Reverse Osmosis(11)
Nonporous
membrane
Porous membrane
Desalination of
seawater
Dialysis(12)
Microporous
membrane
Separation of H2SO2
from nickel and
copper sulfates
Microfiltration(13)
Microporous
membrane
Protein concentrates
from skim milk
Ultrafiltration(14)
Nonporous
membrane
Separation of whey
from cheese
Pervaporation(15)
Nonporous
membrane
Dehydration of Ethyl
Alcohol
Gas permeation(16)
Liquid membrane
Liquid
Membrane(17)
Solid adsorbent
Extraction of organic
acids from wastewater
Adsorption(18)
Solid or liquid
adsorbent
Removal of Arsenic
from water
Chromatography(19)
Resin
Separation of salt
from glycerol.
Ion Exchange(20)
Centrifugal force
field
Recovery of heavy
metals
Centrifugation(21)
Thermal gradient
Separation of palm
kernel shell from palm
kernel
Thermal diffusion(22)
Separation of chlorine
isotopes
Electrolysis(23)
Concentration of
heavy water
Electrodialysis(24)
Desalination of sea
water
Electrophoresis(25)
Separation of
biochemicals
10
1.7
SELECTION
PROCESSES
OF
FEASIBLE
SEPARATION
11
Product
Conditions
Composition
Flow rate
Temperature
Pressure
Phase state
Required
purities
Temperatures
Pressures
Phase state
Property
differences that
may be exploited
Molecular
Thermodynamic
Transport
Characteristics of
separation operation
Ease of scale-up
Ease of staging
Temperature, pressure
and
phase-state
requirement
Physical
size
limitations
Energy requirements
Adsorption
Crystallization
Drying
Ease of staging
Easy
Easy
Easy
Easy
Repressurization
required between
stages
Easy
Not easy
Not convenient
12
13
Legislation
Hazard Evaluation
Waste Disposal
14
REFERENCES
2
SEPARATION METHODS IN THE
PHARMACEUTICAL
INDUSTRY
Siti Hamidah Mohd. Setapar
2.1
INTRODUCTION
16
phases are brought into contact with each other (Kilikian et al., 2000),
according to their partition coefficient (Chimuka et al., 2004). The
cost of liquid-liquid extraction is much lower than other more
sophisticated bioseparations method such as liquid chromatography
(Gu, 2000). The process design and its scale-up are easier than those
for other separation techniques, and liquid-liquid extractions can
minimise irreversible absorption losses and surface denaturation losses
when compared to absorption methods (Gerson, 1988).
Unfortunately, since liquid-liquid extractions are infrequently
used in the laboratory, they are often overlooked in process
development and scale-up (Gerson, 1988). However, some attempts
have been made to investigate the separation and purification
processes that are based on liquid-liquid extraction techniques,
especially the solvent extraction method as discussed thoroughly by
Soto et al. (2005). Hatton (1985) asserted that an important step in the
production of antibiotics is the recovery and concentration of the
product from the fermentation broth in which it is produced. He
further pointed out that the physicochemical properties which
distinguish the desired solute from other fermentation products must
be exploited in the selection of an appropriate separation technique for
this step; liquid-liquid extraction has been successfully employed in
the isolation of different bioproducts. The successful implementation
of liquid-liquid extraction in the separation and concentration of
bioproducts depends both on thermodynamic equilibrium constraints
and on process considerations such as relative flow rates and the
contacting patterns of the two phases. The partitioning behaviour of
bioproducts can be influenced strongly by solution properties like pH,
ionic strength, antibiotic concentration, and can also be modified
through the introduction of additives which interact with either the
solute and/or the solvent to cause effective changes in the solute
distribution between the phases.
The effectiveness of the liquid-liquid extraction process also depends
on the solvent selected for recovery of the solute from the
fermentation broth (Liu et al., 2004). Popular solvents employed in
17
18
2.2
19
2.3
Extraction using liquid membranes has been studied since the 1980s
and is one of the most advantageous separation techniques present
(Cascaval et al., 2001; Goto, 2006). The method entails transferring a
solute between two aqueous phases at different pH values, which are
separated by a solvent and a carrier layer.
20
Since its discovery two decades ago, the ELM has been studied for the
separation of metal ions, amino acids, and carboxylic acids from dilute
aqueous (e.g., Ho and Li, 1992). ELM extraction does not encounter
the equilibrium limitations of conventional solvent extraction
processes and can offer high selectivity of separation of solutes from
low concentration feeds (Ghosh et al., 1997).
However, ELM also suffers from some major drawbacks which make
the system difficult to operate commercially (Pellegrino and Noble,
1990):
21
2.4
22
2.5
CHROMATOGRAPHY
23
2.6
REVERSE MICELLE
24
2.7
CONCLUSIONS
25
Liquid
membrane
(Pellegrino
and Noble,
1990; Ghosh
et al., 1997;
Cascaval et
al., 2000)
Aqueous
two phase
system
(Verral,
1988; Yang
et al.,
1994)
Chromatography
(Kinugasa et al.,
1991; Pires et al.,
1996; Ghosh et al.,
1997; Kyung and
Jee, 2004)
Efficiency
Yield
/cycle
Very good
Can be poor
Low
Can be
high
Very good
Can be poor
Selectivity
Very good
Time
consumed
Toxicity of
Solvent
No
information
High
Can be
good
No
information
High
Denaturing
of product
Wastage of
solvent
Cost
Scale-up
potential
No
information
Very low
Low
possibility
Very low
Low
Very high
Moderate
(low stability)
Very high
Can be
good
Very high
Poor (limited to
laboratory)
Can be high
Very good
No
information
Can be low
Very good
No
No
No
Yes
No
Method
established
Conventional
solvent
extraction
(Kinugasa et
al., 1991;
Pires et al.,
1996; Ghosh
et al., 1997;
Nabais and
Cardoso,
1999; Liu et
al., 2001;
Naoe et al.,
2004
Good
Very good,
can be low
Reverse
micelle
extraction
(Pires et
al., 1996;
Ghosh et
al., 1997;
Naoe et al.,
2004;
Kyung and
Jee, 2004)
Very good
Moderate
Good
Long
Long
Short
Information not
available
High (because
of
demulsifies)
High
possibility
High
No
information
Low
Very good
Very good
Very low
26
REFERENCES
27
28
29
Naoe, K., Noda, K., Kawagoe, M. and Imai, M., 2004, Higher Order
Structure of Proteins Solubilized in AOT Reverse Micelles,
Coll. Surf. B., 38: 179-185.
Nishiki, T., Sato, I., Muto, A. and Kataoka, T., 1998, Mass Transfer
Characterization in Forward and Back Extractions of
Lysozyme by AOT-Isooctane Reverse Micelles across a Flat
Liquid-Liquid Interface, Biochem. Eng. J., l: 91-97.
Noh, K. H. and Imm, J. Y., 2005, One-Step Separation of Lysozyme
by Reverse Micelles Formed by the Cationic Surfactant,
Cetyldimethylammonium Bromide, Food Chem., 93: 95-101.
Ono, T., Goto, M., Nakashio, F. and Hatton, T. A., 1996, Extraction
Behaviour of Haemoglobin Using Reversed Micelles by
Diolyel Phosphoric Acid, Biotechnol. Prog., 12: 793-800.
Pellegrino, J. J. and Noble, R. D., 1990, Enhance Transport And
Liquid Membranes in Bioseparations, Tibtech., 8: 216-224.
Pires, M. J. and Cabral, J. M. S., 1993, Liquid-Liquid Extraction of a
Recombinant Protein with a Reverse Micelle Phase,
Biotechnol. Prog., 9: 647-650.
Regalado, C., Asenjo, J. A and Pyle, D. L., 1996, Studies on the
Purification of Peroxidase from Horseradish Roots Using
Reverse Micelles, Enz. Microb. Tech., 16: 332-339.
Rito-Palomares, M., Huddleston, J. G. and Lyddiatt, A., 1996, Phase
Recycling in Aqueous Two-Phase Partition Processes: Impact
Upon Practical Implementation of Protein Recovery from
Brewery Waste, Sep. Biotech., 3: 413-418.
Rodrigues, E. M. G., Milagres, A. M. F. and Jr, A. P., 1999, Xylanase
Recovery: Effect of Extraction Conditions on the AOTReversed Micellar Systems Using Experimental Design, Proc.
Biochem., 34: 121-125.
Shen, C. W. and Yu, T., 2007, Protein Separation and Enrichment by
Counter-Current Chromatography Using Reverse Micelle
Solvent Systems, J. Chromatography A, 1151: 164-168.
Soto, A., Arce, A. and Khoshkbarchi, M. K., 2005, Partitioning of
Antibiotics in a Two-Liquid Phase System Formed by Water
30
3
APPLICATION OF SUPERCRITICAL
FLUID IN THE EXTRACTION OF ACTIVE
COMPOUNDS FROM PLANT MATERIAL
Mohd Azizi Che Yunus
Wahyu B. Setianto
Zainuddin Abdul Manan
3.1
INTRODUCTION
32
33
34
35
Tc (oC)
45.5
Pc (bar)
37.1
36
Chlorotrifluoromethane
29.0
38.7
1,1,1,2-tetrafluoroethane
101.2
40.6
Propane
96.8
42.4
Trichlorofluoromethane
198.0
43.5
Trifluoromethane
25.9
46.9
Chlorodifluoromethane
96.4
48.5
Xenon
16.6
57.6
Dinitrogen Monoxide
36.5
71.7
Carbon Dioxide
31.0
72.9
Ammonia
132.4
111.3
Water
374.0
217.7
3.3
37
38
phase that possesses some of the properties of both a gas and a liquid.
At supercritical region, the characteristics of solvent is a strong
function of temperature and pressure, can change the property sharply
with very little change in pressure and temperature, able to control
density, polarity, viscosity and other properties of the fluids
continuously over a wide range. According to Mc Hugh and Krukonis
(1986) these unique characteristics make it possible for extraction to
take place rapidly. In supercritical fluid extraction, it is essential to
discuss the properties of supercritical fluids in details such as solvent
power; diffusivity/viscosity and competing factors effect hence it
influence the solubility of desired compounds particularly those
located remotely within solid matrices.
39
Table 3.2 Properties of supercritical carbon dioxide and ordinary gases and
liquid.
Region
Density
(g/ml)
Viscosity
(g/cm.s)
Gases
Supercritical
CO2
T c, P c
Tc, 6Pc
Liquids
(0.10.2) X 10-3
(13) X10-4
Diffusion
Coefficient
(cm2/s)
0.1 0.4
0.47
1.0
3 X 10-4
1 X 10-3
7 X 10-4
2 X 10-4
0.6 1.6
(0.23.0) X 10-2
40
41
0.5
313 K
323 K
333 K
0.4
0.3
0.2
0.1
0
15
20
25
30
35
40
45
50
Pressure, MPa
Figure 3.3 Effect of pressure on solubility of caffeic acid in supercritical
carbon dioxide at different temperature (Murga et al., 2005).
42
balance each other and the solubility remains relatively constant with
increasing temperature. As reported by Murga et al. (2003), the
behaviour of cross over pressure occurs in the extraction of ferulic
acid. At cross over pressure, the solubility of ferulic acid relatively
constant even though temperature was increased up to 50o C. The
phenomenon of cross over pressure was shown in Figure 3.4. Lee
(1994) study on the extraction of oil from evening primrose seed using
SC-CO2 determined that the pressure of 200 bar is a pressure at cross
over pressure.
43
44
Figure 3.5 Diffusivity of carbon dioxide in the supercritical fluid and near
critical region (Weatherly, 2005).
45
from the matrix sample into the bulk fluid of CO2. Meanwhile low
viscosity will allow supercritical fluids to penetrate matrices of desired
compounds with low permeability more rapidly than conventional
solvents because it does not exhibit surface tension limitation (Dean,
1993).
46
3.4
OPERATIONAL PARAMETERS IN SUPERCRITICAL
FLUID
Extraction parameters
Pressure
Temperature
Flow rate
Trapping
Collection technique
Trap size
Sorbent type
Modifier
Static or dynamic
Extraction mode
Extraction time
Restrictor temperature
Pressurized/depressurized
Collection
temperature
47
3.5
PRINCIPLES OF SUPERCRITICAL EXTRACTION
PROCESS
The principles of extraction from solids consist of two processes,
which can be represented as two-stage process namely the extraction,
and separation of the extract from solvent, (Figure 3.7). During the
extraction step, the solvent is first compressed to above critical
pressure before it flows through a fixed bed of solid particles in the
extractor and dissolves the extractable components of the solid. The
loaded solvent is removed from the extractor and fed to a precipitator.
In a large scale SFE process, the solvent is commonly recycled to
separation stage and solvent losses are compensated by make-up
stream (Brunner, 1994).
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48
49
Application
of SC-CO2
on Plant
Matrices
SC-CO2
Conditions
SC-CO2 outcomes
Ref.
Extraction of
evening
primrose oil
from the seed
of Oenothera
biennis L.
1.Temperature
ranges=40 to
60o C
2.Pressure
ranges = 20 to
70 MPa
3. CO2 flow
rate is 18 g/min
Favati
et al.
(1991)
Extraction of
oil from Oil
Palm fruits
1. Operating
temperatures
are 40o, 60o and
80o C.
2. Operating
pressures are
300, 400 and
500 bar
3. F = 2.4 kg/hr
Extraction of
oil from
evening
primrose seeds
1.100 P 300
bar, P = 100
bar
2. 20 T 50 o
C, T = 15 o C
3. Sample =
Bisuna
dan
(1993)
Lee et
al.
(1994)
50
Extraction of
tocopherols
from soyn
flakes, ricebran and
wheat germ
Extraction of
carotenoids
and lipids
from buriti
fruit (Mauritia
flexuosa)
Extraction of
Vit. E and
squalene from
Pandanus
odorus
Ridl./leaves
1.40 T 80,
T= 10 C,
2. P = 80, 100,
200 kg/cm2 ,
3. T= 180 min;
4. Sample = 4
g of ground
freeze dried
leaves
Extraction of
flavonoids of
Scutellaria
1. Temperature
was set at 40,
50, 60 and 70o
1. P = 20MPa
and 30 MPa
2. T = 313K
and 328 K
King et
al.
(1996)
De
Franca
et. al
(1999)
Hassan
et al.
(1999)
Lin et
al.
(1999)
C
2. Extraction
pressures was
set at 200, 300
and 400 bar
3. Methanol
was used as
modifier with
concentration is
5 and 10 %
Extraction of
lipids from
Pythirm
irregulare
1. Extraction
temperatures
are 40. 50 and
60o C
2. Extraction
pressure are
13.8, 20.6 and
27.6
3. Flow rate are
20, 50, 60, 100
and 400
mL/min
4. Moisture
content are 10,
20 and 30%
Extraction of
oleic
sunflower
seeds
P = 250 bar; T
= 40 and 60 o
C.
10
Extraction of
nimbin from
Azadirachta
indica A.
Juss/seeds
10 P 26
MPa, 308 T
333 K
0.24 F 1.24
ml/min
Sample = 2 g
51
Walker
et al.
(1999)
Kiriami
ti
et al.
(2001)
Tonthu
bthimth
ong
et al.
(2001)
52
11
Extraction of
essential oil
from Piper
nigrum
L./seeds
P = 160 and
200 bar; T = 40
o
C
Harchar
an S
(2002)
12
Extraction of
tocopherol
from olive tree
leaves
1. Extraction
pressures range
from 25 to 45
MPa
2. Extraction
temperature
range from 313
to 333K
3. Particle size
range from 0.25
to 1.50 mm
4. Solvent flow
rate from 0.5 to
1.5 L/min)
Lucas
de et
al.
(2002)
13
Extraction of
oleoresin from
pungent spice
paprika
powder
1. Extraction
pressure from
100 to 400 bar
2. Extraction
temperature
from 35o to 55o
C
3. Flow rate of
1.0 to 1.5 l/min
Daood
et al.
(2002)
53
14
Extraction of
Anacardic acid
and cardol
from Cashew
shell
40 T 60,
T= 10o C,
P = 30 MPa, F
= 5 liter/min
Wahyu
et al.
(2003)
15
Extraction of
oil from
ground black
pepper
1. Extraction
pressures are
90, 100 and 150
bar
2. Extraction
temperatures
are 40 and 50o
C
3. Solvent flow
rate are 1.1, 2.0
and 3.0 kg/hr
Perakis
et al.
(2005)
16
Decaffeination of
raw green
coffee beans
1. Extraction
pressure from
16 MPa to 22
MPa
2. Extraction
temperature
from 70 o C to
90 o C
3. Extraction
time is 10 hour
Zosel.
K
(1981)
17
Deacidification
1. Pressure
range from 20
Brunett
i
54
MPa and 30
MPa
2. Temperature
range from 40 o
C to 60 o C.
C.
2) CO2 selectivity also increased
significantly as the free fatty
acid concentration in oil
decreased.
et al.
(1989)
18
Separation of
triglycerides,
diglycerides,
free fatty
acids,
carotenes,
tocopherol and
tocotrienols
from crude
palm oil
The separation
of components
has been
achieved by
supercritical
fluid
chromatograph
y (SFC) by
using the
programmed
extraction
elution method
Choo
et al.
(1996)
19
Decaffeination of
guarana seeds
1. Extraction
temperatures
were 40o and
70o C
2. Extraction
pressures at
100, 200 and
400 bar
3. CO2 flow
rate is 5.7 and
9.4 g/min 4.
The weight of
sample is 3 g
with water
content of 40%
20
Concentration
of tocopherols
1. Pressure
ranging from
Saldana
et al.
(2002)
Lee et
al.
21
Isolation of
peppermint
oil/leaves
22
Improving the
value of rice
by product
1. 5000 P
10000 Psi,
P = 2500 Psi
2. 40 T 80o
C, T = 20 o C
23
Enhancement
for separation
of lauric acid
and oleic acid
in Palm kernel
oil
Solubility of
Antibiotic
penicillin G
27.6 P 48.3,
P = 6.9MPa
T= 80 o C; 30
t 60 min, t
= 10 min
24
Extraction
condition is:
1. 90 bar and
50o C and 120
bar and 40o C
1. Extraction
pressures from
100 to 350 bar
2.
Temperatures
from 313.5 to
333.15 K
55
(1991)
Reverc
hon
(1994)
Perretti
et al.
(2003)
Nik
Norulai
ni
et al.
(2004)
Gordill
o
et al.
(2001)
56
25
Extraction
kinetics of
Pre-pelletized
Jalapeno
Peppers
26
Sterilization of
Oil Palm Fruit
Fiber
1. Average
sample particle
size from 0.28
to 3.19 mm
2. Superficial
solvent velocity
from 0.14 to
2.62 mm/s
3. Extraction
condition:
40o C and 120
bar
40o C and 320
bar
1. extraction
temperature are
40, 50 and 70o
C
2. Extraction
pressure are
13.7 and 20.7
MPa
3. Extraction
time is 60 min
De
Valle
et al.
(2003)
Banana
(2005)
57
3.7. CONCLUSION
In the last four decades, there has been a tremendous interest in the use
of supercritical fluid as solvent for extraction, separation and removing
purpose. The intensive study on extraction of food components by
using supercritical fluid began in early 1970s. Many patents resulted
from these studies such as for the extraction of hops, decaffeination of
coffee and tea, tobacco and spices. There is little doubt that
supercritical carbon dioxide extraction is very promising at it offers
greater selectivity, efficiency and environmental benefits than
conventional methods. The bioactive properties of the extract are also
preserved as degradation due to prolonged exposure to harsh
extraction condition is avoided. At present, supercritical extraction is
more feasible for high value phyto-chemicals and neutral-ceuticals. As
expected the 21st century is a tertiary peak with mounting interest in
the possible development of new material especially on the medicinal
plant industry. Also, supercritical fluid technology has become an
interdisciplinary field utilized by chemical engineers, chemists, food
scientists, materials scientists, agronomists and researcher in
biotechnology and environmental control.
REFERENCES
58
Banana, A. A., 2005, Sterlization and extraction of palm oil fruit fiber
using supercritical carbon dioxide extraction. MS.c thesis.
Universiti Sains Malaysia, Penang, Malaysia.
Bisunadan, M.,1993, Extraction of oil from oil palm fruits using
supercritical carbon dioxide, MS.c thesis. Universiti Sains
Malaysia, Penang Malaysia.
Brunetti, L., Daghetta, A., Fedeli, E. and Zanderighi, L., 1989,
Deacidification of olive oils by supercritical carbon dioxide,
JAOCS, 66 (2): 209-217.
Brunner, G., Malchow, T., Sturken, K. and Gottschau, T., 1991,
Separation of tocopherol from deoderizer condensate by
countercurrent extraction with carbon dioxide, J. of
Supercritical Fluids, 4: 72-78.
Choo, Y. M., Ma, A. N., Yahaya, H., Yamauchi, Y., Bounoshita, M.
and Saito, M., 1996, Separation of crude palm components by
semi preparative supercritical fluid charomatography, JAOCS,
73(4): 523-525.
Daood, H. G., Illes, V., Gnayfeed, M. H., Meszaros, B., Horvath, G.
and Biacs, P. A., 2002, Extraction of pungent spice paprika by
supercritical carbon dioxide and subcritical propane. J. of
Supercritical Fluids. 23: 143-152.
De Franca, L. F., Reber, G., Meireles M. A., Machado, N. T. and
Brunner, G., 1999, Supercritical extraction of carotenoids and
lipids from buruti (Mauritia Flexuosa), a fruit from the
Amazon Region. J. of Supercritical Fluids, 14: 247-256.
De Valle, J. M., Jimenez, M. and De la Fuente, J. C., 2003, Extraction
kinetics of pre-pelletized jalapeno peppers with supercritical
CO2, J. of Supercritical Fluids, 25: 33-44.
59
60
61
62
4
REGENERATION TECHNIQUE FOR THE
SPENT BLEACHING CLAY: OIL
EXTRACTION AND ACTIVATION
Abu Hanipah Nawi
Mohd Azizi Che Yunus
Wahyu Bahari Setianto
Nik Norulaini Nik Abdul Rahman
Mohd Omar Abdul Kadir
4.1
INTRODUCTION
Malaysia has become the biggest palm oil producer and exporter with
total cultivated land area about 4.3 million hectares. It has the
capability to generate about 16.5 millions tonne of palm oil per year
(MPOB, 2007). In order to process the palm oil, it has 434 palm oil
mills operating throughout the Malaysia with 49 mills concentrating in
processing palm kernel and 66 mills for refinery process. In refinery
mill of crude palm oil, general processes of crude palm oil are
summarized in Figure 4.1.
Degumming
Alkali refining
Bleaching
Deodorization
64
4.2
65
4.2.2
OIL EXTRACTION
For oil extraction, 5 kg of the spent bleaching clay were collected from
the palm oil refinery mill in Seberang Prai, Penang. Experiments using
the adept technique were performed with an apparatus that consisted
of a SC-CO2 extractor (ISCO,Inc.,Lincoln,NE,USA,model SFX 220)
a carbon cylinder, a chiller and a high pressure syringe pump. 2.5 ml
of sample was put into the extractor and carbon dioxide will be chilled
into liquid form before the high-pressure pump pumped it at desired
pressure. Temperature and pressure used in the experiment were
controlled by software integrated with the extractor. Extractions were
performed at temperatures 40, 60 and 80-degree Celsius with pressure
variation at 200, 300 and 400 bar. For comparative study, experiments
using soxhlet extraction were also conducted with extraction time
varied from 4-hour to24 hours. The schematic flow diagram for
supercritical fluid extraction is given in Figure 4.2.
66
4.2.3
REGENERATION
3UHVVXUH
LQGLFDWRU
&RROHU
3UHVVXUH
UHJXODWRU
0HWH ULQJ
YDOYH
([WUDFWRU
2 YHQ
3XPS
&2
F\OLQGHU
3UHVVXUH
LQ GLFD WRU
: HWJDV
P HWHU
$QDO\WH
UHFHLYHU
4.3.1
67
40
30
20
(%)
10
68
40
30
20
(%)
10
28
27.5
27
26.5
average
26
25.5
25
4
16
24
E xtrac tiontime(hours )
69
ACID ACTIVATION
70
0.3
0.25
non
0.2
heat
0.15
ac id(20% )
0.1
0.05
0
0
30
60
90
120
150
180
T imeofAds orption(minutes )
Figure 4.4 Regeneration performances curve for various conditions of
deoiled spent bleaching clays.
Graph absorbance against time for 200C heating
value
absorbance(AU)
3.00
2.80
acid activation 10%
2.60
2.20
2.00
0
30
60
90
120
150
180
time(min)
71
72
(a)
(b)
73
4.4. CONCLUSION
The study showed that SC-CO2 gave the best performance in oil yield
and extraction time compare to the conventional method. Average oil
yield is 35% of its original weight. The conditions of applying
temperature and pressure are 80 degree Celsius and 300 bars
respectively.
Observation on several heating and acid sulphuric
concentration combination expel that heating at 200 degrees Celsius
and 30% Acid Sulphuric is the best combination. At 3 hour retention
time, it finally gives the lowest value of absorbance which indicates
the capability of the material in removing the pigment colour when it
is in contact with oil.
REFERENCES
74
5
ION EXCHANGE TECHNOLOGY FOR
WATER AND WASTEWATER
TREATMENT: PRINCIPLES AND
PROGRESS IN MATERIALS
DEVELOPMENT
Mohamed Mahmoud Nasef,
Hamdani Saidi
Zaini Ujang
ABSTRACT
76
5.1 INTRODUCTION
78
Figure 5.2: Strong cation and anion exchange resins based on polystyrene
divinylbenzene copolymer.
5. 2 HISTORICAL PERSPECTIVE
Ion exchange phenomena have been known for many years. The first
examples of ion exchange were discovered by Thompson and Way
(1850) during investigations concerning the way in which soluble
manures were retained for long periods in the soil, instead of being
washed out by rain water. The importance of this discovery (in ion
exchange terms) was not fully understood until later in that decade
when this reaction was found to be reversible. This phenomenon was
caused by certain minerals in the soil as released in the latter half of
the nineteenth century. These minerals, called resins, are based on
tetrahedron structure of silicon and aluminum compounds called
zeolites. In 1905, synthetic zeolites were manufactured and utilized for
water treatment in a form of water softening ever since (Gans, 1905).
Synthetic cation exchange resins were developed during the 1930s
using certain types of coal treated with sulfuric acid (Liebknecht,
1935; Smith, 1935). This was an important evolution due to the fact
that the sulfonated coal would operate in a greater pH range, 1 to 10.
This made the sulfonated coal more versatile enabling it to be used in
many more industrial applications. However, these resins were found
1944
1946
Milestones
Agricultural chemists Harry Thompson & John Way discovered ion
exchange phenomena
German Chemist Eichom reported that ion exchange is a reversible
reaction.
Robert Gans introduced first process to soften water using zeolite (sodium
alumiosilicate)
American company (Permutit) introduced first commercial zeolites.
English chemists Adams and Holmes prepared first synthetic polymer
cation and anion exchangers (Phenol formaldehyde & polyamine
formaldehyde).
can scientist DAlelio developed cation exchange resins based on
polymerization of styrene and divinylbenzene.
Anion exchange resins based on polymerization of styrene and
divinylbenzene were developed.
80
Applications
Production
of
pure
(demineralization of water).
Water softening.
Potable water production.
and
ultrapure
Dealkalization
Fluoride removal.
Removal of organic matter.
Removal colorants.
Oxygen removal.
Removal of Iron.
Removal of manganese.
Removal of cadmium ions from drinking
water.
Removal of nitrate ions.
Removal of ammonia.
Removal of radionuclides from drinking water.
Removal of other harmful ions from drinking
water.
Nuclear industry
82
+A+
R-A+
+H+
(5.1)
+B-
R+B-
+Y(5.3)
[ RB] [Y ]
x
[ RY ] [ A ]
(5.4)
84
(5.5)
) and (2) (
) are
(5.6)
The selectivity coefficients in ion exchange systems are not constant
and vary with the operation conditions such as types of resins,
concentration of feed solution, temperature and the presence of other
ions in the solution. The selectivity coefficient provides a means of
determining what to expect when various ions are involved. However,
the determination of selectivity coefficients is practically complicated
task and is ordinarily not undertaken in the design of waste treatment
systems; most of these parameters can be extracted from
manufacturers data or research literature. More details on ion
exchange kinetics can be found in Korkisch (1989).
Ion transfer takes places in the ion exchange resin (particles) through
the inter-phase boundary in a form of: 1) chemical reaction, 2)
diffusion inside the material, 3) diffusion in surrounding solution and
4) diffusion through the thin film formed around the particles. Ion
exchange process is controlled by the diffusion of counter-ions. The
two rate determining steps are considered: diffusion of ions inside the
material (particle diffusion) and diffusion of ions through the film
(film diffusion).
To achieve an efficient separation, column techniques are applied.
Depending on the type of the functional group, ion exchangers can be
divided into several types: strong acidic, strong basic, weak acidic and
weak basic as discussed next.
86
can be both cation- and anion exchangers and this classifies them
based on the functional groups. Considering the separation function,
ion exchangers can be classified into various categories including ion
exchangers, chelating adsorbents, hydrogels, affinity polymers and
polymer electrolytes.
The majority of strongly acid resins in use today have a styrenedivinylbenzene copolymer bead structure similar to that shown in
Figure 5.2. This crosslinked structure gives the ion exchange resin
bead certain physical properties including particle size and water
88
90
92
The fixed bed column operation is the most usable ion exchange
configuration in industrial applications. It has a basic component of
which the beads column is considered to be analogous of several batch
Figure 5.9 Typical example of ion exchange plant based on fixed bed
column system (Courtesy of Robert Mesick from REMCO Engineering
water systems and controls).
94
Advantages
Disadvantages
Batch system
Conventional
column system
Good throughput
Simple to operate
A wide variety of media are
available
Can be operated at elevated
temperatures and pressures
High decontamination
factors are possible
96
Membrane system
The moving beds are the most economical beds of ion exchange
systems. The principle of this operation relies on bringing the beads
and the solution to flow through the system. The beads are contacted
counter-currently with the exhausting stream and regenerated stream.
The advantage of this operation is featured by continuous product of
uniform quality at less space, capital and labor. However, the
complexity of the design poses a problem during operation.
With the wide number of resin types available in the marketplace, it is
probable that there is more than one technically effective solution that
will meet all the system's design specifications. This is where
experience and knowledge is required to help select the system design
that will do the job expected by the customer under the conditions
existing at the customer site. This experience will include a thorough
knowledge of all available resin types along with their various
98
There are three major factors affection of the selection of the ion
exchangers and the process to apply them. They are 1) waste
characteristics where the concentration of total suspended solids in the
waste should be less than 4 mg/L and the total dissolved salts content
is less than1 to 2 g/L, 2) ion exchange material and system where the
selection of an appropriate material s (resin, hydrogel, or fibers)
depends on the needs of the system. The ion exchange media must be
compatible with the chemical nature of the waste (such as the pH and
type of ionic species present), as well as the operating parameters,
notably temperature and pressure. However, if there are large
concentrations of chemically similar ions in the waste the process of
selection becomes more difficult and 3) cost consideration where the
total cost of operating a process is the sum of the capital costs, the
initial cost of the ion exchange media, the operating costs, and the
costs associated with the treatment and disposal of the spent ion
exchanger. The total costs can be reduced by a frequent regeneration
of the spent ion exchange material instead of using a once through
process.
A good ion exchange system designer not only will design the
system to meet all design specifications but also will utilize resins that
will allow the system to operate at peak efficiency and maximum cost
effectiveness.
Operating principle
Types or resins
Softening
Deionization
Metal removal
Nitrate removal
Nitrates replaced by
chloride
Dealkalization
Bicarbonate and
carbonates replaced by
chloride
Arsenic removal
Arsenic V replaced by
chloride
Dye removal
Solution
purification
Precious metal
Recovery
100
102
104
5.5.5 REMOVAL
OF
HEAVY
INDUSTRIAL WASTE WATER
METALS
FROM
Removal of toxic heavy metal ions such as Cu2+, Pb2+, Ni2+, Cd2+,
Zn2+, Mn2+, Co2+, Hg2+ and Fe3+ from industrial waste water is an
essential step from the standpoint of environmental pollution control.
This is to eliminate the direct toxic effect of such heavy metal ions on
human and animal health and aquatic life. Various ion exchange
materials, which are being researched to reduce the cost of existing
commercial counterparts and to tolerate a wide range of operating
conditions, have various forms (ion exchange resins and membranes,
affinity adsorbents and hydrogels) of grafted and crosslinked
structures based on synthetic or natural polymers containing functional
groups.
Grafting of hydrophilic monomers onto a variety of polymer
films offered various types of membranes having metal ion-binding
capacity (Fang et al. 1998; Hegazy et al. 1999, 2000, Gupta and
Anjum, 2001, Gupta et al 2004). To further enhance the metal
adsorption capacity of the membranes, grafting of binary monomer
mixtures was introduced. Cation/anionic graft copolymer membranes
prepared by radiation grafting of AAc and 4-VP onto low density PE
films showed a good potential for separation of Fe3+ and other heavy
metal ions such as Pb2+, Cd2+ and Cu2+ from contaminated water
resources (Hegazy et al. 1997). The stability of similar membranes
was improved by grafting of AAc and N-VP onto PTFE films. These
membranes were found to have potential for separation of Cu2+, Ni2+,
Pb2+, Cd2+, Zn2+, Mn2+, Co2+, Cr2+ and Fe3+ ions (Hegazy et al. 2000;
2001).
Double (strongly and weakly) acidic graft copolymer
membranes prepared by radiation grafting of styrene/AAc onto low
106
108
110
and phosphate groups. The Cu2+ ions sorption process was found to
occur in two stages: external mass transport occurs in the early stage
and intra-particle diffusion occurs in the long-term stage.
Zhang and Chen investigated crosslinked poly(dimethylaminoethyl methacrylate) starch grafted copolymers containing tertiary
amine groups, as adsorbents for Pb2+ and Cu2+ ions (Zhang and Chen,
2002). The crosslinked graft copolymer starch with 60% degree of
grafting achieved an equilibrium adsorption capacity of 2.09 and 2.12
mmol g1 (dry weight), for for Pb2+ and Cu2+ ions, respectively.
Guo et al (2006) investigated the adsorption of Cu2+ ions on
crosslinked starch phosphate carbamates adsorbent prepared from an
aqueous solution. The adsorbent achieved a maximum adsorption
capacity of 1.60 m mol.g-1 for Cu2+ ions with a regeneration capacity
of above 96% when treated with 1 N HCl solution for 1 h.
The use of biomass has been also reported for developing
biosorbent chelating materials for heavy metals removal. The biomass
of Penicillium chrysogenum was modified by grafting of AAc or
polyethylenimine (PEI) on the surface of ozonepretreated biomass
(Deng and Ting 2005 a,b). However, the preparation process was very
complex and is not cost effective.
Yu et al (2007 a) reported a simple process to prepare a
biosorbent with high sorption capacity by grafting of poly(amic acid),
which was obtained through reaction of pyromellitic dianhydride
(PMDA) and thiourea, onto the biomass (bakers yeast) surface at 50
C for 4 h. The adsorption capacity of the modified biomass increased
15- and 11-folds for Cd2+ and Pb2+ ions respectively compared with
the pristine biomass. The regenerated biomass can be used for at least
4 four times with little loss of uptake capacity. The same authors
extended their workby modification of the surface of dried biomass of
baker's yeast by crosslinking the cystine with GA. The adsorption
capacity of the modified biomass for Cd2+ and Pb2+ ions showed an
increasing trend compared with the pristine biomass due to the
presence of cystine on the biomass surface. The adsorption capacities
for Cd2+ and Pb2+ were 11.63 and 45.87 mg g1, respectively (Yu et al.,
2007 b).
112
TREATMENT
OF
RADIOACTIVE WASTE
WATER
CONTAINING
114
116
118
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Hegazy ,E-S., Kamal, H., Maziad, N. and Dessouki, A. 1999, Nucl.
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Hegazy, E-S., Abd El-Rehim, H., Khalifa, N., Atwa, S. and Shawky,
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6
POTENTIAL OF BIO-PRODUCTS
ADSORPTION BY IMMOBILIZED METAL
ION AFFINITY
MESOPOROUS ADSORBENTS
Azizul Azri Mustaffa
6.1
126
6.2
6.3
Many processes take place at the boundary between two phases, while
others are initiated at the interface. The change in concentration of a
given substance as compared with the neighbouring phase is referred
to as adsorption. The systems can be categorized to the types of phases
in contact such as liquid-gas, solid-liquid and solid-gas (Dabrowski,
2001). Adsorption is a process in which a molecule is transferred from
solution to the surface of a solid where the molecule is bound by
physical and chemical forces. The solid is what we called as
OF
BIO-PRODUCTS
128
130
6.4
132
6.5
134
136
REFERENCES
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Colloid Interfac.,93: 135-224.
Gaberc-Porekar, V. and Menart, V., 2001, Perspectives of
Immobilized-Metal Affinity Chromatography, J. Biochem.
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Harrison, R.G., Todd, P., Rudge, S.R. and Petrides, D.P., 2003,
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Proteins on Mesoporous Molecular Sieve, Mater. Phys. Mech.,
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7
REVERSE MICELLE EXTRACTION
Siti Hamidah Mohd. Setapar
7.1
INTRODUCTION
138
7.2
Water-pool
Surfactant
Hydrophilic Biomolecule
139
aqueous) in which they are present (Yang, 2001). The hydrophilic and
hydrophobic regions are illustrated in Figure 7.2.
Hydrophobic tail
Hydrophilic head
140
141
7.3
Figure 7.3 shows the comparison between normal micelle and reverse
micelle. Water plays a decisive role in the formation of reverse
micelle. The surfactant molecules aggregate at interfaces forming a
middle phase in equilibrium with an excess organic phase and an
excess aqueous phase. The transition from micelle to reverse-micelle
system, as described by Esalah (1997), is generally driven by a
decrease of the surfactant hydrophilicity. Increasing the salinity of the
aqueous constituent by adding a medium-chained alcohol (cosurfactant) decreases the surfactant hydrophilicity.
The structures of biomacromolecules are very sensitive to the
organic solvent involved (Chang et al., 2000). Using reverse micelle
systems can therefore create a suitable environment for solubilising
the biomolecule solutes into the organic solvent region. Reverse
micelle can be formed in an organic phase by a contact method or a
titration method (Rabie et al., 1997). These two methods have been
found to be significantly different with respect to their solubilisation
capacities for water and different solutes such as salts, amino acids,
proteins, antibiotics, etc. Rabie (1997) found that the titration method
had been used widely to form reverse micelle as injection fluids for a
number of tertiary oil recovery processes and also as microreactors in
which guest molecules could be brought to react, often showing
reactivity that differed markedly from that observed in pure solvents.
The titration method on the other hand is a process where an aqueous
142
(a)
(b)
Organic
Phase
Aqueous
Phase
Figure 7.3 Aggregation of surfactants; (a) micelle, and (b) reverse micelle.
143
7.4
SURFACTANTS
144
7.5
SURFACTANT STRUCTURE
145
146
147
148
CMC
Conductivity / mole
Surface
tension
Turbidity
Surfactant concentration
149
REFERENCES
150
151
152
153
154
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Rabie, H. R. and Vera, J. H., 1996, Extraction of Zwitterionic Amino
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Rabie, H. R., Helou, D., Weber, M. E. and Vera, J. H., 1997,
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155
8
LIQUID-LIQUID SEPARATION OF
ANTIBIOTIC WITH REVERSE MICELLES
Siti Hamidah Mohd. Setapar
8.1
INTRODUCTION
158
product, low extraction yield, high solvent losses and clogging of the
equipment.
A reverse micelle extraction process is based on the
distribution of biomolecule between aqueous solution and reverse
micelle organic solution. The biomolecule in aqueous solution is
contacted with organic solution, which spontaneously forms reverse
micelles. This method is a kind of liquid-liquid solvent extraction
technique using reverse micelle as the extractant (Kinugasa et al.,
2003). The reverse micelle extraction technique has a great potential
to be an alternative to the conventional liquid-liquid extraction method
for the separation and purification of penicillin G. Since last few
decades, the technique has received researchers attention due to its
ability to solubilise many biomolecule without causing denaturation of
the product. It has been used successfully and widely in the separation
of proteins Goklen and Hatton, 1987; Aires-Barros and Cabral, 1991;
Brandani et al., 1996; Pires et al., 1996; Su and Lee, 1999; Kinugasa
et al., 2003; Bong et al., 2004; Jun et al., 2004; Noh and Imm, 2005;
Hecht and Peled, 2006; Shen and Yu, 2007), amino acids (Leodidis
and Hatton, 1989; Furusaki and Kishi, 1992; Adachi et al., 2000;
Dovyap et al., 2006), enzymes (Moreno-Hagelsieb et al., 1999, Bong
et al., 2004, Liu et al., 2004, Debnath et al., 2007) and metals
(Nakashio et al., 1992; Ismael and Tondre, 1992; Zhang et al., 2006;
Majumdar and Mahapatra, 2007). Mathew and Juang (2007) stressed
that in the case of protein separation, the reverse micelle technique is
more suitable than the conventional liquid-liquid extraction technique
or other separation method because the transfer of proteins into
solvents often results in the irreversible denaturation and loss of
biological activity.
Although penicillin G is considered as one of the most famous
antibiotics and has been widely investigated in detail for a long time,
surprisingly few studies have been attempted so far on its extraction
by the reverse micelle technique. Perhaps this is due to the difficulty in
the extraction and problem associated with the analysis work. Despite
the drawbacks of the liquid-liquid extraction technique as mentioned
by Chimuka et al. (2004), which include difficult to automate, easily
159
8.2
160
8.3
161
162
2.5
2.0
1.5
1.0
0.5
0.0
0
100
200
300
400
500
163
Concentration of penicillin
in organic phase, [P]rm+o.f g/l
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0
100
200
300
400
500
164
8.3.3 EFFECT OF PH
165
Concentration of penicillin
in the organic phase, [P]rm+o.f g/l
1.8
[S ] = 88 g/l
[S ] = 222 g/l
[S ] = 445g/l
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0
10
12
166
to extract hemoglobin (pI = 6.8) found that in case of the pH << pI, the
biomolecules tend to form a complex that binds to the surfactant. In
this study, we observed precipitation when high initial penicillin G
concentrations were used at low pH. Although extremely low pH
range were used, at [KCl] = 10 g/l and 400 rpm stirring speed, a
transparent two phases system was obtained with a clear interphase
when [P]aq.i < 10 g/l. From the results, it appears that the pH effect is
important for the penicillin G extraction, although the electrostatic
contribution is also relevant for the AOT reverse micelles which
achieved better binding at higher pH values.
167
Concentration of penicillin G
in organic phase, [P]rm+o.f g/l
1.0
[A O T ] = 2 67 g/l
[A O T ] = 2 22 g/l
0.8
0.6
0.4
0.2
0.0
0
20
40
60
80
168
40
without penicilin G
with penicillin G
30
20
10
0
0
20
40
60
80
using CaCl2 the solution became more sensitive to the stirring speed
and tended to emulsify more easily. This caused problems with
169
getting a good phase separation, and even when the phases can be
separated extra time was needed for the solutions to achieve
equilibrium.
8.4
CONCLUSION
REFERENCES
170
171
Goto, M., Ono, T., Horiuchi, A. and Furusaki, S., 1999, Extraction of
DNA by Reversed Micelles. J. Chem. Eng. Japan 32 (1): 123125.
Goto, M., 2006, Recent Advance in Protein Extraction and Chiral
Separation of Biomolecules. Tsinghua Sci. Tech. 11(2): 194201.
Gu, T. Y., 2000, Liquid-Liquid Partitioning Methods for
Bioseparations. In Handbook of Bioseparations Academic
Press, New York. Page 329-364.
Haghtalab, A. and Osfouri, S., 2003, Vacancy Solution Theory for
Partitioning of Protein in Reverse-Micellar System. Separation
Science and Technology 38 (3): 553-569.
Hecht, H. G. and Peled, H. B., 2006, Structure Modifications of AOT
Reverse Micelles due to Protein Incorporation. J. Coll.
Interface Sci. 297: 276-283.
Hu, Z. and Gulari, E., 1996, Extraction of Aminoglycoside Antibiotics
with Reverse Micelles. J. Chem. Technol. Biotechnol. 65: 4548.
Ismael, M. and Tondre, C., 1992, Kinetically Controlled Separation of
Nickel (11) and Cobalt (11) using Micelle-Solubilised
Extractant in Membrane Processes. Langmuir 8: 1039-1041.
Jun,G. L., Jian, M. X., Rui, S., Cheng, L. Y. and Hui, Z. L.,2004,
Reverse Micelles Extraction of Nattokinase from Fermentation
Broth. Biochem. Eng. J. 21: 273-278.
Kilikian, B. V., Bastazin, M. R., Minami, N. M., Goncalves, M. R. and
Junior, A. P., 2000, Liquid-Liquid Extraction by Reversed
Micelles in Biotechnological Processes. Braz. J. Chem. Eng.
17: 29-38.
Kinugasa, T., Kondo, A., Mouri, E., Ichikawa, S., Nakagawa, S.,
Nishii, Y., Watanabe, K. and Takeuchi, H., 2003, Effects of
Ion Species in Aqueous Phase on Protein Extraction into
Reversed Micellar Solution. Sep.Purif. Tech. 31: 251-259.
Leodidis, E. B. and Hatton, T. A., 1989, Specific Ion Effects in
Electrical Double Layers: Selective Solubilization of Cations
in Aerosol-OT Reversed Micelles. Langmuir 5: 741-753.
172
Li, S. Z., Li, X. Y., Cui, Z. F. and Wang, D. Z., 2004, Application of
Ultrafiltration to Improve the Extraction of Antibiotics. Sep.
Purif. Tech. 34: 115-123.
Liu, J. G., Xing, J. M., Shen, R., Yang, C. L. and Liu, H. Z., 2004,
Reverse Micelle Extraction of Nattokinase from Fermentation
Broth. Biochem. Eng. J. 21: 273-278.
Majumdar, T. and Mahapatra, A., 2007, Kinetics of Electron Transfer
Reaction in Micellar and Reverse Micellar Media Reduction
of [Co(NH3)5N3]Cl2 by Iron (II). Coll. Surf. A 302: 360-365.
Mathew, D. S. and Juang, R. S., 2007, Improved Back Extraction of
Papain from AOT Reverse Micelles using Alcohols and a
Counter-Ionic Surfactant. Biochem. Eng. J. 25: 219-225.
Moreno-Hagelsieb, G., Gomez-Puyou, A. and Soberon, X., 1999,
Eschecichia coli TEM 1 E-Lactamase in CTAB Reverse
Micelles: Exchange/Diffusion-Limited Catalysis. FEBS Letters
459: 111-114.
Nabais, A. M. A and Cardoso, J. P., 1999, Purification of
Benzylpenicillin Filtered Broths by Ultrafiltration and Effect
on Solvent Extraction. Bioproc. Biosyst. Eng. 21: 157-163.
Nakashio, F., Goto. M. and Kondo, K., 1992, New Surfactants for
Metal Extraction by Liquid Membrane. In Solvent Extraction
Elsevier Science Publication.
Naoe, K., Nishino, M., Ohsa, T., KAwagoe, M. and Imai, M., 1999,
Protein Extraction using Sugar Ester Reverse Micelles. J.
Chem. Technol. Biotechnol. 74: 221-226.
Nishiki, T., Sato, I., Katoaka, T. and Kato, D., 1993, Partitioning
Behaviour and Enrichment of Proteins with Reversed Micellar
Extraction:1. Forward Extraction of Proteins from Aqueous to
Reversed Micelle Phase. Biotechnol. Bioeng. 42: 596-600.
Noble, M. J. and Varley, J. (1999), Colloidal Gas Asprons Generated
from the Anionic Surfactant AOT for the Separation of
Proteins from Aqueous Solution. J. Chem. Technol.
Biotechnol. 74: 231-237.
173
9
EXTRACTION, IDENTIFICATION AND
SEPARATION OF DJENKOLIC ACID
FROM PITHECELLOBIUM JIRINGAN
SEEDS USING SUPERCRITICAL CARBON
Mohd Azizi Che Yunus
Wahyu B. Setianto
9.1
INTRODUCTION
176
178
Areekul et al. (1976) was conducted the extraction djenkolic acid from
djenkol bean with 70 % ethanol and water. The amount of extracted
djenkolic acid was quantitatively determined by paper
chromatography. It was found that djenkol beans contain 0.3 to 1.3 mg
djenkolic acid. The toxicity of djenkol beans was studied in 5 rhesus
monkeys, 9 albino rats and 22 mice fed with 70% ethanol extract. The
observation showed that the total urinary output decreased and there
was an increase in specific gravity of the urine during the period of
feeding monkeys with djenkol beans. Urinary samples of the
experimental animals were turbid and contained some red cells, white
cell, epithelial cells, albumin and amorphous particles. Out of one
mice showed excreted sharp needle-shaped crystals in the urine on day
3 after feeding. Histological examination of kidneys of rats and mice
showed mild to severe acute tubular necrosis with some glomerular
cell necrosis.
On the toxicity to human, the effects caused tend to vary
among individuals, depends on age, sex and genetic background of the
180
9.2
9.2.1 MATERIAL
Fresh P. Jiringan seeds with commercial maturity (the colour of seed
testa is dark brown) were obtained from a local Kepala Batas market
Penang, Malaysia. The seeds were separated from the fruit, thoroughly
washed with tap water, rinsed with distilled water and then cut into
small pieces (2-3 cm diameter and 1 mm thickness). The seeds were
182
Pump A
Chiller
CO2 tank
Collecting tube
Pump B
Sample cartridge
Extraction Chamber
Modifier reservoir
Controller
Chromatographic separation was carried out using a LiChrospher RP18 column (250 mm x 4.6 i.d. mm, 5m particle size) (Merck
Darmstadt, Germany). The Mobile phase used consists of methanol,
water and acetonitrile (20:70:10 v/v) by applying isocratic methods.
Methanol and acetonitrile were filtered through an FA 0.5 Pm filter
(Millipore) prior to use. The mobile phase was degassed and then
delivered at a flow rate of 0.3 mL/min at temperature 25 o C. The
injection volume of sample used was 15 PL. The peak of djenkolic
9.3
The effects of temperature and pressure on the overall oil yield are
shown in Figure 9.4 and Figure 9.5. The percentage of oil yield was
calculated by the mass of oil extracted per unit mass of sample used.
184
In general, the yield curves as shown in the Figure 9.4 and Figure 9.5
demonstrate similar trends for a range of different pressures at each
constant temperature over 60 minutes extraction time. The overall
extracted oil yield strongly increased with increase in pressure and
temperature. At each constant temperature, the highest overall
extracted oil yield was obtained at higher pressure of 55.16 MPa,
meanwhile the lower pressure of 20.68 MPa generated lowest overall
extraction yield.
186
primrose oil. Their results show that oil recovery above 90 % was
obtained when the extraction pressure was increased to 30.0 MPa, and
even higher yield was recorded when operating at pressures of 50.0
MPa and 70.0 MPa. Bisunadan (1993) also reported similar results on
the extraction of oil from palm oil fruits. The SC-CO2 extraction was
carried out at 300, 400 and 500 bar and 40o, 60o and 80o C. The
results show that the optimum condition for extraction of oil was
obtained at the higher pressure and temperature of 500 bar and 80o C.
At each constant pressure, the highest overall extraction yield
was obtained at highest temperature of 80o C, meanwhile the lowest
temperature of 40o C produced lowest overall extraction yield. These
results show that extraction yields increase with increasing
temperature over pressure ranges from 20.68 MPa to 55.16 MPa. This
is due to fact increase in oil volatility was more dominant than drops
of CO2 density in the temperature range from 40o to 80o C.
Particularly, at constant pressure, the diffusivity of the supercritical
fluid increases with increasing temperature (as the fluids tend towards
a more gas-like state) and as result the extraction rate will increase,
producing a faster extraction to reach asymptotic yield especially
when operating at higher pressure. Another reason is that at constant
pressure, an increase in temperature increases the mass transfer
coefficient, therefore decreases the internal and external mass transfer
resistance.
The trend that the extraction yield increased with increasing
temperature at constant pressure has been found in others studies.
Ozkel et al. (2005) was conducted the extraction yield of hazelnut oil
in SC-CO2 at extraction conditions of 15.0 to 60.0 MPa and 40 o to 60o
C. The extraction yield increased both with pressure and temperature.
It was higher than 50 % at all temperatures at pressure of 60.0 MPa.
Zaidul (2003) reported that the higher pressure range of 34.5 MPa to
48.3 MPa and high temperature of 80o C are preferred to extract palm
kernel oil in SC-CO2. Zhimin and Samuel (2000) showed that the
extraction yield from rice bran at constant pressure of 68.9 MPa were
significantly higher at 55, 60 and 75o C than at lower temperatures.
3.503
Wavelength=210 nm (AZIZI\DJSTAD01)
700 Wavelength=210 nm (AZIZI\7P80T)
600
500
400
Extract oil
3.766
300
0
0
2.5
7.5
10
17.5
20
22.5
23.785
22.725
22.027
20.401
17.353
15
18.672
15.696
12.5
13.571
14.083
11.738
12.868
9.633
7.203
7.835
8.408
8.898
10.173
4.843
5.917
6.318
2.456
2.809
1.841
0.762
100
4.303
3.962
200
min
188
3.503
Wavelength=210 nm (AZIZI\DJSTAD02)
Wavelength=210 nm (AZIZI\4P40T)
250
4.887
150
100
7.5
10
12.5
15
21.594
16.426
13.458
12.161
9.290
8.692
7.852
3.152
3.693
4.078
4.582
2.5
6.460
1.441
0.437
2.440
50
17.5
20
22.5
min
190
5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
P=55.16 MPa
P=48.26 MPa
P=41.37 MPa
P=34.47 MPa
P=27.58 MPa
P=20.68 MPa
30
40
50
60
70
80
90
Temperature, (C)
T=80 C
T=70 C
T=60 C
T=50 C
T=40 C
2
1
0
-1
10
20
30
40
50
60
Pressure, MPa
192
weight containing polar groups call for high fluid densities in order to
make this solute more readily soluble in pure CO2.
It can be seen that the effect of temperature at 40o C does not
significantly apply in this study. This is because no djenkolic acid can
be extract over the pressure ranges and only in trace amount at the
pressure above 41.37 MPa. This is due to the fact that at 40o C the
desorption kinetics of the compounds from the matrix sample are very
slow. As temperature increases desorption is faster thus tending to
increase the solubility of djenkolic acid and hence resulted increase in
djenkolic acid concentration. Furthermore, as summarizes on the
method development for supercritical fluid extraction by Dean (1993)
for the extraction of non-volatile and mild-polar/polar compounds the
recommended extraction temperature must be done at least 15o C
higher than the critical temperature of the fluid.
9.4.
CONCLUSION
The overall extracted oil yield of P.jiringan seeds was increased with
increase in pressure at constant temperature. Likewise, the overall
extracted oil yield also increased with increase in temperatures at
constant pressure. The maximum overall extraction oil yield is 8.06 %,
at the highest supercritical conditions of pressure and temperature of
55.16 MPa and 80o C, respectively. The solubility of P.jiringan oil
increased with increase in temperature under constant pressure.
However, at constant temperature the solubility values were constant
during the entire extraction pressure range from 20.68 MPa to 34.47
MPa. Above 35.0 MPa, the solubility begins to increase until reaching
to maximum solubility value. Meanwhile, at constant temperature of
80o C, the solubility values increased with increase in temperature.
The maximum solubility of P.jiringan oil is 0.26 wt % (2.6 mg oil per
g CO2) under the supercritical condition of pressure and temperature
REFERENCES
Abdullah, H., 1999, Pengendalian lepas tuai buah-buahan dan sayursayuran tropika. Institut penyelidikan dan Kemajuan Pertanian
Malaysia, MARDI, Malaysia.
Areekul, S., Kirdudom, P. and Chaovanapricha, K., 1976, Studies on
djenkol bean possoning (djenkolism) in experimental animals,
194
196
INDEX
Absorbance 68
Adsorbate 128
Antibiotic 16, 23, 132, 154
Biological 12, 23, 131, 155
Biomolecule 17, 24, 131
Bleaching 63, 68
Carbon dioxide 176
Chromatography 15, 16, 131,
177
Countercurrent 3, 54
Crude palm oil 33, 62
Degumming 63
Deodorization 63
Diffusivity 1, 35
Efficiency 12, 33, 47, 79, 99,
141
Energy 2, 11, 100, 142, 143
Equilibrium 3, 7, 20, 37, 81,
99, 126, 139, 158
Free fatty acid 53, 141
Heterogeneous 2, 3, 33
Homogeneous 2, 3, 101
Hydrophobic 20, 129
Hydrothermal 130
Isoelectric 124
Liquid-liquid extraction 6, 11,
20, 135, 155
Mass transfer 3, 21, 32, 38,
44, 182
Membrane 4, 8, 19, 21, 74,
85, 96, 100
Mesoporous 123, 132
Mobile phase 133, 179
Modifier 50, 130, 176
Molecular 1, 51, 129, 142,
187
Permeability 101
Pharmaceutical 12, 15, 18,
131
Protein 161, 173
P-T diagram 37
Reverse micelles 26, 155
198
Rifampicin 133
Selectivity 6, 18, 53, 56, 75,
90
Silica 63, 129
Solubility 1, 19, 41, 55, 128
Supercritical 33, 41, 46, 48,
64, 172
Surfactant 18, 135, 156
Thermal degradation 32
Thermodynamic 1, 7, 48, 138
Viscosity 5, 17, 38
Volatility 6, 182
Zeolite 77, 129
Index