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Journal of Food Engineeting 27 (1996) 191-201

Copyright 0 1995 Elsevier Science Limited


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Filtration of Pectin Extract from Grapefruit Peel and
Viscosity of Pectin Solutions
Nurhan Arslan & Hasan To&u1
Faculty of Engineering, Department of Chemical Engineering, Fu-at University,
23279 Elazlg, Turkey
(Received 4 September 1994; revised version received 3 January 1995;
accepted 31 January 1995)
ABSTRACT
The yield of pectin extracted (85C, pH=2*5, 90 min) by acidi.ed water
in a ratio of 25 parts per part of dry peel from dried grapefruit peel was
21.1% (DM basis).
The pectin extract was vacuum filtered at different temperatures and
under various pressure differences, and the average speciJ ic cake
resistances were determined. The specific cake resistance was highly
dependent on the filtration pressure. The cake compressibility
coeficients at lSC, 25C and 35C were calculated as O-387, 0.379
and 0.379, respectively. The jiltration rate observed at 15C was higher
than that at 25C due to flocculation at low temperature.
The efjects of temperature and concentration on the viscosity of
pectin solutions were examined at six different temperatures between
10C and 60C and four concentration levels between O-3 g/100 ml and
1.4gllOO ml. The activation energy for viscous flow was in the range
2.10-3.77 kcal mol-. Finally, the combined effect of temperature and
concentration on the viscosity was expressed as
r/=852x lop5 exp(-1~6162Cf1~807exp(0~5493C)I RT)
NOTATION
::
C
E,
&
Filter area (m)
Constant of eqn (10) ((g/100 ml)-)
Concentration (g/100 ml)
Activation energy of flow (kcal mol- )
Dimensional constant= 1 kg Pa- s- m-
191
192 N A&an, H. To&d
K
KCI
K,,K,
m
-AP
R
R,
s
t
T
V
VI
Constant of eqn (10) (Pa s)
Constant of eqn (7) (Pa s)
Constants of eqn (1) (Pa s m- and Pa s m-)
Ratio of wet cake to dry cake
Total pressure drop (Pa)
Gas constant (kcal mol- K-l)
Resistance of the filter medium (m-l)
Mass fraction of solid in slurry
Time (s)
Temperature (K or C)
Filtrate volume (m)
Fictitious filtrate volume (m)
Specific cake resistance (m kg-)
Specific cake resistance at unit pressure difference (m kg- Pa-)
Viscosity (Pa s)
Cake compressibility coefficient
Filtrate density (kg m-)
INTRODUCTION
Pectins are common components in the cell wall of fruits and have
important nutritional and technological properties, mainly because of their
ability to form gels. Characteristic structural features for this group of
heteropolysaccharides are 1,4 linked main chain a-D-galactopyranosyluronic
acid residues interspersed with a-L-rhamnopyranosyl residues. Some of the
rhamnose residues are branched with side chains comprising different
amounts of neutral sugar residues, primarily arabinose and galactose
(Westerlund et al., 1991). The carboxyl groups can be partially methylated,
and the C-2 and C-3 hydroxyl groups of the sugar ring can be acetylated
(Valverde et al., 1982).
The major use for pectins is as a gelling agent in jams and preserves.
Pectin is obtained mainly from the waste materials from the production of
apple, orange, grapefruit and lemon juices (Kratchanova et al., 1991). The
pectin content of citrus peel is usually high, 2530% of the dried peel mass
(Huong & Luyen, 1989).
Filtration is one of the major unit operations employed in the food
industry. The gelatinous precipitate of pectin precipitated with ethanol from
an acid extract can be filtered by vacuum filtration at constant pressure
differences. Although there are various methods of filtration (i.e. high
pressure systems, vacuum filtration, ultrafiltration), operational variables
which control filtration rates are the same in general, and the same filtration
theories apply to each of these processes. The effect of the operational
variables on filtration rates can be described easily by mathematical
equations. Pressure is one of the important operating variables (Baymduh et
al., 1989).
The viscosity of pectin is affected by molecular size, degree of
methylation, pH, presence of counter-ions and sucrose (Phatak et al., 1988).
Filtration of pectin extract from grapeffuit peel 193
Viscosity behaviour of pectin solutions changes with concentration and
temperature.
The objectives of this research were to study the filtration of a gelatinous
precipitate of pectin from grapefruit peel at different temperatures and
under various pressure differences and the variation in viscosity of pectin
solution with temperature and concentration.
EXPERIMENTAL
Extraction of pectin from grapefruit peel
Fresh Turkish grapefruit from the Mersin region (citrus paradisi McFad.)
was purchased from a local retail market and peeled. Sun dried grapefruit
peel was ground to 50 mesh in a hammer mill to facilitate washing and
extraction. Before grapefruit peel was utilized for pectin production, the
peel oil was removed by petroleum ether and dried. The peel was heated to
97C in a water bath for about 10 min to inactivate pectin enzymes, washed
extensively with water to remove sugars and flavenoids, filtered through a
suction filter, dried at 50C and sieved. A 50 mesh fraction was used in
experiments; 10 g of dried grapefruit peel were mixed with 250 ml of
0.003 N hydrochloric acid (pH=2*5), preheated to 85C in a water bath. The
mixture was mechanically stirred for 90 min, while maintaining the
temperature at 85C. The liquid phase was then separated from the fruit
mass by filtering. The liquid phase, a turbid pectin extract, was allowed to
cool and settle for several hours. When it reached a temperature of about
37C the pH was raised to about 7.5 by adding 0.1 M sodium phosphate
buffer and 50 mg of protease enzyme (Sigma Chemical Co., P 5147) was
added. The extract was incubated overnight at 37C. The acid extract was
separated by filtering and the pectin was precipitated with an equal volume
of ethanol. The gelatinous precipitate was filtered and the pectin coagulate
was washed once with a hydrochloric acid/ethanol mixture (70% ethanol),
then with 70% ethanol until the reaction was neutral and finally with 96%
ethanol to speed up drying at 50C. The yield of raw pectin was determined
gravimetrically.
Filtration of gelatinous precipitate of pectin
The gelatinous precipitate of pectin was filtered by suction at different
temperatures and under various constant pressure differences. The filtration
equipment consisted of a 1.8 litre jacketed stainless steel filter, vacuum
section and filtrate tank. A schematic diagram of the laboratory set-up is
shown in Fig. 1. The filtration area was 52.8 cm2 and the fabric filter
medium employed in the experiments was a tightly woven (10 weft/cm and
30 warp/cm) synthetic cloth manufactured locally and used in the beet sugar
production industry. A perforated plate, 32.1% of its area consisting of
4 mm diameter holes, was covered with the fabric filter medium and placed
on the base of the stainless steel filter. Experiments were conducted at least
in duplicate, at different temperatures (15C 25C and 35C), under various
pressure differences (0.24 x lo5 Pa, O-43 x lo5 Pa and 0.79 x lo5 Pa). Water
194 h! A&an, H. To&d
14
Fig. 1.
3,
Schematic diagram of laboratory set-up (1, circulating water bath; 2, mixer;
thermometer; 4, feed tank; 5, valve; 6, jacketed stainless steel filter; 7, funnel; 8,
vacuum section; 9, vacuum pump; 10, vacuum manometer; 11, pressure control valve
(by-pass); 12, filtrate tank; 13, graduated glass level indicator; 14, filtrate outlet
valve).
from a constant temperature bath at the filtration temperature was
circulated through the jacket of the stainless steel filter to maintain the
constant temperature during filtration. Pectin extract was heated to the
filtration temperature and filtered under vacuum. During constant-pressure
filtration, the variation in filtrate volume with time was recorded after the
first 100 ml of filtrate was discarded.
Viscosity determination of pectin solution
Samples of 0.3, 0.6, 1.1 and 1.4 g of dried pectin were dissolved in 100 ml of
0.9% NaCl solution. The viscosities of pectin solutions at different
concentrations were determined at 10C intervals from 10C to 60C by
means of an Ubbelohde viscosimeter No. 13 (capillary no: Ic, ID: 0.84 mm).
Densities of solutions were measured using a pycnometer. All of the
experiments were replicated.
RESULTS AND DISCUSSION
Yield of pectin
The yield of pectin extracted using the extraction process described above
was 21.1% (DM basis). The yield, degree of esterification and gel strength
Filtration of pectin extract from grapefruit peel
195
of the pectin obtained depend on the type of raw material used (variety,
processing conditions) and the extraction method (Kratchanova et al., 1991).
Anhydrogalacturonic acid content, degree of esterification, ash content and
optical rotation of pectin from the grapefruit peel studied were 74-O%,
68*2%, 56% and +216, respectively.
Filtration of pectin extract
The filtration rate equation for constant-pressure filtration is written
(Bennett & Myers, 1988) as
dVdt=( -AP)l(K,V+K,)
(I)
Equation (1) can be integrated analytically, since - AP, K1 and K2 are
constant. The result is
where
and
t/V=K, V/2( - AP) +&/( - AP)
K1 =spqal( 1 -ms)A 2g,
(2)
(3)
&=Rmy~IAgc
(4)
in which dV/dt is the rate of change of the filtrate volume with respect to
time (the filtration rate), V is the filtrate volume, t is the time, -AP is the
pressure difference across the filter, s is the mass fraction of solid in the
slurry, p is the filtrate density, y is the filtrate viscosity, x is the specific cake
resistance, m is the ratio of wet cake to dry cake, A is the filtration area, R,
is the filter medium resistance, and g, is the dimensional constant; R, may
be expressed in terms of the resistance of a hypothetical layer of cake which
corresponds to the collection of a hypothetical volume of filtrate l/m:
R,=spaV,,,l(l -ms)A
(5)
It should be noted that the intercept of eqn (2) is difficult to determine
accurately because of the large potential experimental error in observing the
time of the start of filtration and the time-volume relationship during the
first moments when the filtration rate is high. The value of R, calculated
from the intercept may vary appreciably from test to test, and will always be
different from the value measured with clean medium in a permeability test
(Perry & Green, 1984).
The experimental t/V for various pressure differences were plotted versus
V to obtain the values of the constants K, and K2 in eqn (2) (Figs 2-4).
The increased filtration rate (V/t) at 15C compared with the filtration
rate at 25C was due to flocculation at low temperature. The filtration rate
at 35C was higher than the filtration rate at 25C.
The constants from eqns (l)-(5) were calculated from the experimental
data and are shown in Table 1.
The densities and the viscosities of filtrates at 15C, 25C and 35C were
1.267 x lo3 kg mp3, 1.251 x lo3 kg mp3, 1.242 x lo3 kg rnh3 and 4.18 mPa s,
2.85 mPa s, 2.60 mPa s, respectively. All the experiments were done in
196 h! Arslan, H. To@ul
8-
0 100 200 300 4
v w
0
Fig. 2. Plot of t/V versus I/ for pectin extracts filtered at 0.24 x lo5 Pa pressure
difference at different temperatures: temperature (C): (0) 15; (m) 25; (*) 35.
or
0
I I I
100
V2gl,
300 4 0
Fig. 3. Plot of t/V versus V for pectin extracts filtered at 0.43 x 10 Pa pressure
difference at different temperatures: temperature (C): (0) 15; (w) 25; (+) 35.
duplicate. The maximum variation in the experiments was about _+6% in
the filtrate volumes.
Under experimental conditions, the variation in fictitious filtrate volume
resulted from the properties of the filter cake and the turbulence caused by
rapid rate of flow (Foust et al., 1960).
Filtration of pectin extract from grapefruit peel 197
0 100 200 3cn3
v w
Fig. 4. Plot of t/V versus V for pectin extracts filtered at 0.79 x lo5 Pa pressure
difference at different temperatures: temperature (C): (0) 15; (m) 25; (+) 35.
TABLE 1
Calculated Values of K, and K2, c1 and V,,, Obtained from an Analysis of the
Experimental Filtration Data
- AP (Pa) Experimental data
Temperatures (C)
0.24 x 10 K, x 10W5 (Pa s rn- )
K2 x lo- (Pa s rn-)
!z x lo- (m kg-)
V, (ml)
S x 10
m
r2
0.43 x 10
0.79 x lo5
K1 x lo- (Pa s mph)
Kz x lo- (Pa s m-)
cx x lo- (m kg-)
V, (ml)
S x lo2
m
r2
K1 x 1O-5 (Pa s rn~-)
K, x I O- (Pa s rn-)
n x lo- (m kg-)
V, (ml)
s x lo2
m
r2
15 2.5 35
1.004
0.279
258
27.8
2.0
1.10
0.994 1
1.153
0.3 12
3.28
27.1
1.X
1.51
0.9987
1.541
0.263
4.03
17.1
Go
0.9986
1.254 0.62)
0.209 WOO6
2.67 2.65
16.7 1.0
2.9 2.0
7.25 1.13
0.9979 0.9954
1.326 0.705
0.297 0.089
3.34 3.32
22.4 12.6
2.5 1.7
7.79 4.28
0.9985 0.9975
1.697 1.157
0.264 0.125
4.13 4.10
15.6 10.8
2.0 1.7
18.89 17.78
0.9988 0.9989
198 h! Arslan, H. To&d
It can be seen from Table 1 that specific cake resistance is a strong
function of applied pressure difference, indicating the highly compressible
character of the filter cake. The data could be correlated as
cl=/?( -AP)
(6)
in which p is the specific cake resistance at unit pressure difference (m kg-
Pa-) and v is the cake compressibility coefficient.
The logarithm of specific cake resistances at a given temperature was
plotted versus the logarithm of pressure difference (Fig. 5). The values of
the constants in eqn (6) for each temperature are given in Table 2.
Viscosity of pectin solution
The viscosity of pectin solutions at different concentrations and
temperatures are given in Table 3.
It can be seen that, as would be expected, the higher the temperature the
lower the viscosity, and the viscosity increases with concentration.
Diluted organic solutions (true solutions) are generally Newtonian in
character (Kirk & Othmer, 1970). It has been reported (Chou & Kokini,
1987) that hot break tomato paste pectin solutions at concentrations of 2%
26. 2 1 I I I
10. 0 10. 4 10. 8 11. 2
I n( - AP)
Fig. 5. Plot of In a versus In (- AP) for different temperatures: temperature (C):
(0) 35; (w) 25; (*) 15.
TABLE 2
Values of the Constants /3 and v at Different Temperatures
Temperature (C) j (mkg- Pa _ ) V r2
1.5 5-20 x lo9 0.387 0.9970
25 5.82 x lo9 0.379 0.9988
35 5.77 x lo9 o-379 O-9987
Filtration of pectin extract from grapefruit peel 199
TABLE 3
Relationship between Viscosity and Concentration of Pectin Solutions at Different
Temperatures
Cone. (g/100 ml)
10C 20C
1 (mpa s)
30C 40C 50C 60C
0.3 2.03 1.84 1.66 150 1.29 1.17
0.6 3.03 2.74 2.43 2.07 1.77 1.60
1.1 654 4.99 3.77 3.38 2.80 2.69
1.4 7.75 5.57 4.70 3.81 3.22 2.80
TABLE 4
Values of Arrhenius-type Constants E, and K0 for Pectin Solutions at Different
Concentrations
Cont.
CgllOO ml)
E,
{kcal mol-)
K0
Pa s)
r2
0.3 2.10 4.98 x lo- 5 0.9902
0.6 2.52 3.57 x lop5 0.9880
1.1 3.46 1.34 x lop5 0.9624
1.4 3.77 0.91 x lop5 0.9888
or lower and citrus pectin solutions at concentrations of 3% or lower were
Newtonian. Therefore, it has been assumed that the pectin solutions studied
were Newtonian.
The effect of temperature on the viscosity
The viscosity of liquids usually decreases with an increase in temperature.
The influence of temperature on viscosity can be described by an Arrhenius-
type equation (Ibarz et al., 1992):
q=K, exp(E,/RT)
(7)
where q is the viscosity, K0 is a constant, E, is the activation energy of flow,
R is the gas constant, and T is the absolute temperature in K.
The logarithm of the experimental viscosity at a given concentration was
plotted versus l/T to obtain the values of the constants E, and K0 in eqn (7).
These are given in Table 4.
The activation energies of flow increased with concentration while K0
decreased. Their relationship with concentration were fitted to the following
equations including the concentration
E,=1+307 exp(Oe5493C)
(8)
Z&,=8.52 x 1O-5 exp( - 1.6162C)
(9)
200 N A&an, H. To&d
TABLE 5
Effect of Concentration on Viscosity at Different Temperatures. Values of the
Constants K and Al for Pectin Solutions at Different Temperatures
T (C)
K (Pa s)
AI ((g/100 ml) -)
r2
10 1.42 x 1O-3 1.273 0.9801
20 1.41 x 1o-3 1.042 0.9696
30 1.32 x 1O-3 0.934 0.9894
Zk? 1.04 1.20 x x lo- lo- 0.843 0.869 0.9789 0.9847
60 0.95 x lop3 0.834 0.9538
where the concentration, the activation energy of flow and constant & were
expressed in g/100 ml, kcal mol- and Pa s, respectively. The correlation
coefficients of eqns (8) and (9) were O-991 and 0.990, respectively. The
constants of eqns (8) and (9) are applicable only in the range of
temperatures and concentrations studied.
The effect of concentration on the viscosity
The viscosity of most fluids increases with concentration. Change of viscosity
with concentration can be described by an exponential type equation (Rao et
al., 1984):
q=Kexp(AIC)
(10)
where K and A1 are constants, and C is the concentration.
To evaluate these constants, the experimental viscosity-concentration
data were fitted to the linearized form of eqn (10) by the least-squares
method. The estimates of the parameters of the exponential equation at
different temperatures are summarized in Table 5. From the results, it can
be observed that constants K and A1 decrease with temperature.
The combined effect of temperature and concentration on the viscosity
It is useful to get a simple equation describing the combined effect of
temperature and concentration on the viscosity of pectin solutions. This was
obtained by combining eqns (7), (8) and (9):
~=8*52 x lo- exp( - 1*6162C+ l-807 exp(05493C)IRT)
(11)
where C is the concentration in g/100 ml, T is the temperature in K, v is the
viscosity of pectin solution in Pa s, and R is the gas constant in kcal mol-
K-l.
REFERENCES
Baymdrrh, L., Gzilgen, M. & Ungan, S. (1989). Modeling of apple juice filtrations.
J. Food Sci., 54 (4) 1003-6.
Bennett, C. 0. & Myers, J. E. (1988). Momentum, Heat, and Mass Transfer, 3rd edn.
McGraw-Hill Fong and Sons Printers Pte Ltd, Singapore.
Filtration of pectin extract from grapefruit peel 201
Chou, T. D. & Kokini, J. L. (1987). Rheological properties and conformation of
tomato paste pectins, citrus and apple pectins. J. Food Sci., 52 (6), 1658-64.
Foust, A. S., Wenzel, L. A., Clump, C. W., Maus, L. & Andersen, L. B. (1960).
Principles of Unit Operations. John Wiley, New York, London.
Huong, D. M. & Luyen, D. V. (1989). Optimization of pectin extraction from dried
peel of citrus grandis. Polym. Bull., 22, 599-602.
Ibarz, A., Pagan, J. & Miguelsanz, R. (1992). Rheology of clarified fruit juices. II:
blackcurrant juices. J . Food Engng, 15, 63-73.
Kirk, D. E. & Othmer, D. F. (1970). Encyclopedia of Chemical Technology, Vol. 21,
3rd edn. John Wiley, New York.
Kratchanova, M., Benemou, C. & Kratchanov, C. (1991). On the pectic substances
of mango fruits. Carbohydr: Polym., l&271-82.
Perry, R. H. & Green, D. (1984). Penys Chemical Engineers Handbook, 3rd edn.
McGraw-Hill Kosaido Printing Co., Ltd, Japan.
Phatak, L., Chang, C. K. & Brown, G. (1988). Isolation and characterization of
pectin in sugar-beet pulp. J . Food Sci., 53 (3), 830-3.
Rao, M. A., Cooley, M. J. & Vitali, A. A. (1984). Flow properties of concentrated
juices at low temperatures. Food Technol., 38 (3), 113-19.
Valverde, C. V., Blanco, I. & Hidalgo, E. R. (1982). Substances in fresh, dried,
desiccated, and oleaginous Spanish fruits. J . Agric. Food Chem., 30, 832-5.
Westerlund, E., Aman, P., Andersson, R. & Andersson, R. E. (1991). Chemical
characterization of water-soluble pectin in papaya fruit. CarbohydK Polym., 15,
67-78.