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Journal of Food Engineeting 27 (1996) 191-201 Copyright 0 1995 Elsevier Science Limited Printed in Great Britain.

All rights reserved 0260-8774/96 $15.00 f0.00 0260-8774(95)00002-X

Filtration of Pectin Extract from Grapefruit Peel and Viscosity of Pectin Solutions
Nurhan Arslan & Hasan To&u1
Faculty of Engineering, Department of Chemical Engineering, 23279 Elazlg, Turkey Fu-at University,

(Received

4 September

1994; revised version received 3 January accepted 31 January 1995)

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 speciJic 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-3g/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 viscositywas expressed as r/=852x lop5 exp(-1~6162Cf1~807exp(0~5493C)IRT)

NOTATION
Filter area (m) Constant of eqn (10) ((g/100 ml)-)

::

C E, &

Concentration (g/100 ml) Activation energy of flow (kcal mol- ) Dimensional constant= 1 kg Pa- s- m191

192

N A&an, H. To&d 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 Viscosity (Pa s) Cake compressibility coefficient Filtrate density (kg m-)

K KCI K,,K, m -AP R R, s t T V VI

(m kg- Pa-)

INTRODUCTION in the cell wall of fruits and have Pectins are common components 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).

Filtrationof pectin extractfrom 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. Schematic diagram of laboratory set-up (1, circulating water bath; 2, mixer; 3, 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).

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. from

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 Yield of pectin

AND DISCUSSION

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 extractfrom 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 (Bennett & Myers, 1988) as dVdt=( Equation (1) can be integrated constant. The result is
t/V=K,

for

constant-pressure

filtration

is written (I)

-AP)l(K,V+K,) analytically, since - AP)

- AP, K1 and K2 are (2)

V/2( - AP) +&/(

where K1 =spqal( 1 -ms)A and


&=Rmy~IAgc (4)

2g,

(3)

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-

100

200 v w

300

4 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 100

300

4 0

V2gl,

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 extractfrom grapefruit peel

197

100 v w

200

3cn3

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 - AP (Pa)

Values

of K, and K2, c1 and V,,, Obtained Experimental Filtration Data Experimental data
15

from an Analysis Temperatures (C) 2.5 1.254 0.209 2.67 16.7 2.9 7.25 0.9979 1.326 0.297 3.34 22.4 2.5 7.79 0.9985 1.697 0.264 4.13 15.6 2.0 18.89 0.9988

of the

35 0.62) WOO6 2.65 1.0 2.0 1.13 0.9954 0.705 0.089 3.32 12.6 1.7 4.28 0.9975 1.157 0.125 4.10 10.8 1.7 17.78 0.9989

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 K1 x lo- (Pa s mph) Kz x lo- (Pa s m-) cxx lo- (m kg-) V, (ml) S x lo2 m r2 K1 x 1O-5 (Pa s rn~-) K, x IO- (Pa s rn-) n x lo- (m kg-) V, (ml) s x lo2 m r2

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

0.43 x 10

0.79 x lo5

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 (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

cl=/?( -AP)

and The viscosity of pectin solutions at different concentrations 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%

26.21 10.0

I 10.4

I 10.8 In(-AP)

I 11.2

Fig. 5. Plot of In a versus In (- AP) for different temperatures:


(0) 35; (w) 25; (*) 15.

temperature

(C):

TABLE 2
Values of the Constants Temperature (C) 1.5 25 /3 and v at Different Temperatures
V r2

j (mkg- Pa _ ) 5-20 x lo9 5.82 x lo9 5.77 x lo9

0.387

0.9970

35

0.379 o-379

0.9988 O-9987

Filtration of pectin extractfrom grapefruitpeel

199

TABLE 3 Relationship between Viscosity and Concentration of Pectin Solutions at Different Temperatures Cone. (g/100 ml) 10C 0.3 0.6 1.1 1.4 2.03 3.03 654 7.75 20C 1.84 2.74 4.99 5.57 1(mpa s) 30C 1.66 2.43 3.77 4.70 40C 150 2.07 3.38 3.81 50C 1.29 1.77 2.80 3.22 60C 1.17
1.60

2.69 2.80

TABLE 4 Values of Arrhenius-type Constants E, and K0 for Pectin Solutions at Different Concentrations Cont.
CgllOOml)

E, {kcal mol-) 2.10 2.52 3.46 3.77

K0 Pa s) 4.98 x lo- 5 3.57 x lop5 1.34 x lop5 0.91 x lop5

r2 0.9902 0.9880 0.9624 0.9888

0.3 0.6 1.1 1.4

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 Arrheniustype equation (Ibarz et al., 1992): (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) Z&,=8.52 x 1O-5 exp( - 1.6162C) (8) (9) q=K, exp(E,/RT)

200

N A&an, H. To&d TABLE 5 of Concentration on Viscosity at Different Temperatures. Values Constants K and Al for Pectin Solutions at Different Temperatures K (Pa s) 1.42 x 1O-3 1.41 x 1o-3 1.32 x 1O-3 1.04 x lo- 1.20 0.95 x lop3 AI ((g/100 ml) -) 1.273 1.042 0.934 0.843 0.869 0.834

Effect

of the
r2

T (C)
10 20 30 Zk? 60

0.9801 0.9696 0.9894 0.9847 0.9789 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): (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.

~=8*52 x lo-

exp( - 1*6162C+ l-807 exp(05493C)IRT)

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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.

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