Академический Документы
Профессиональный Документы
Культура Документы
Agriculture and Agri-Food Canada, Paci"c Agri-Food Research Centre, 4200 Highway 97S,
Summerland, B.C., V0H 1ZO (Canada)
(Received July 7, 1998; accepted April 12, 1999)
The yux behavior of polyethersulfone (0.2 lm), polyvinylidene -uoride (0.2 lm), cellulose (0.2 lm, 100 kDa, 30 kDa, 10 kDa), and
polysulfone (0.2 lm, 100 kDa, 30 kDa, 10 kDa) membranes was examined during dead-end ,ltration of apple juice. Membranes with
molecular weight cut-o+ of 30 and 100 kDa had superior -ux performance to 0.2 lm or 10 kDa membranes. A cross-ow system
equipped with various tubular polymeric membranes was also used to clarify apple juice at a temperature of 503C, a crossyow velocity of
3.3 m/s and a transmembrane pressure of 414 kPa. Steady state yuxes increased as the molecular weight cut-ow increased from 9 to
200 kDa. When challenged with P. diminuta, log reduction values between 6 and 7 were obtained with the cross-ow tubular polymeric
system. Membranes between 20 and 200 kDa produced juices with similar initial characteristics that underwent comparable changes
during storage at 4, 25 and 353C over 4}16 wk. The impact of xltration through the 9 kDa membrane was however noticeable on the
physico-chemical properties since the apple juice had a green tint, lower soluble solids, lower yavanol content, and experienced minimal
changes in browning and turbidity.
Keywords: micro"ltration; ultra"ltration; polymeric membrane; apple juice; physicochemical properties; microbial challenge;
sensory evaluation
Introduction
The use of polymeric membranes is widespread for the
clari"cation of apple juice by ultra"ltration. Padilla and
McLellan (1) studied the "ltration of apple juice through
10, 50, 100 and 500 kDa polysulfone hollow "ber membranes. Initial #ux increased with molecular weight cuto! (MWCO) but the "ltered juice from all membranes
had similar acidity, soluble solids and sensory quality.
Although phenolic content was lower with the 500 kDa,
it generally increased with MWCO as did total solids.
The juice from the 100 and 500 kDa membranes had
higher turbidity and brown color than the other membranes. All juices became turbid and browned during
storage at 43 3C over 6 months but no signi"cant changes
were observed at 18 3C. Sheu et al. (2) used 20 and 50 kDa
polysulfone membranes in a plate and frame con"guration to "lter apple juice. The average #ux was 20 to 40
L/m h higher for the 50 than the 20 kDa membrane. Wu
et al. (3) compared 0.1 km ceramic, 50 kDa polysulfone hollow "ber and 5 kDa polysulfone spiral-wound
0023-6438/99/050290#09 $30.00
290
Eqn [1]
where J is the average #ux (kg/ms) observed between concentration factors of 7.5 and 11, *P is the
transmembrane pressure (Pa), k is the permeate viscosity
(Pa ) s), R is the membrane resistance (m/kg), and R is
K
D
the fouling layer resistance (m/kg). Water and juice
#ux for the CE and PS micro"ltration membranes
(0.2 km) were repeated six times for evaluating coe$cients of variation. All other measurements were done in
duplicates.
291
membranes. Only two tubes in parallel were used corresponding to a membrane area of 0.1 m. Both the permeate and retentate (bleed) were returned to the feed
tank which was continuously #ushed with N . The feed
pump was set to deliver 6 L/min and the recirculation
pump was increased over 15 min to the desired cross#ow
velocity (CFV). Cross#ow velocities of 3.3 and 6.7 m/s
corresponded to recirculation rates of 49 and 98 L/min
and pressure di!erentials of 83 and 276 kPa, respectively.
The recycle #ux was continuously monitored using
a graduated cylinder and stopwatch. The system was
allowed to equilibrate for 30 to 50 min before increasing
the transmembrane pressure (TMP) by adjusting the
retentate outlet valve.
Prior to batch concentration runs and microbial
challenge tests, the membranes were sanitized by circulating a 50 mg/L chlorine solution at 50 3C for 30 min
then rinsing with distilled water. The permeate tank
and lines underwent a sterilization treatment at 121 3C
and 104 kPa for 15 min. Sterile N was used to
maintain a positive pressure in the system after
cooling.
Batches of apple juice (200 to 240 L) were "ltered through
the above mentioned membranes. The operating conditions for these batch concentration runs were 3.3 m/s
CFV, 414 kPa TMP, and 50 3C. The feed pump provided
a #owrate of 6 L/min and the feed tank was continuously
#ushed with N . The #ux was monitored using an elec
tromagnetic #owmeter (Model M053724010R100A, ABB
Kent-Taylor, Rochester, NY, U.S.A.) as the permeate was
separately collected in a SS tank. The juice was processed
to a concentration of three times for the 9 kDa membrane and 10 times for the other membranes. Prior to
juice "ltration, the water #ux was measured under the
same conditions. The membrane and fouling layer resistances were calculated using Eqn [1]. The "ltration unit
was cleaned-in-place using a solution of 0.1 to 0.15
g/100 mL Ultrasil 10 (Klenzade, Mississauga, ON,
Canada) with 100 to 200 mg/L free chlorine. Following
a rinse with water, the cleaning cycle was repeated a second time.
Analytical measurements
Samples were analysed for color, turbidity, viscosity,
soluble solids, titratable acidity, #avanols and protein.
Brown color was measured at an absorbance of 420 nm
using a Beckman DU 640 spectrophotometer (Beckman
Instruments, Inc., Fullerton, CA, U.S.A.). Color was also
assessed spectrophotometrically with a CIE L*, a* and
b* Color Determination and Matching program Version
1.0 (Beckman Instruments, Inc.). Values were calculated
for standard illuminant C and the CIE 1964 Supplementary Standard Observer. Turbidity was determined
with a Hach Ratio/XR turbidimeter (Model 43900, Hach
Co., Loveland, CO, U.S.A.). A Brook"eld LVDV-II#
viscometer with a UL adapter (Brook"eld Engineering
Laboratories, Inc., Stoughton, MA, U.S.A.) was used to
measure viscosity at a shear rate of 73 s\. Soluble solids
were assessed with a Reichert Abbe Mark II digital
refractometer (AO Scienti"c Instruments, Bu!alo, NY,
U.S.A.). Juice samples (10 g) were titrated with 0.1
N NaOH to an endpoint of pH 8.1 using a Metrohm 686
Titroprocessor and 665 Dosimat (Metrohm Ltd. Switzerland) and titratable acidity was expressed as g malic acid
per 100 mL juice. Flavanol content was determined by
the acidi"ed vanillin method of Broadhurst and Jones
(11) using (-)-epicatechin (Sigma Chemical Co., St. Louis,
MO, U.S.A.) as standard. Initial protein content was
measured using the Kjeldahl method. Juice samples (5 g)
were dried at 70 3C in a vacuum oven (104 kPa) prior to
digestion. Nitrogen was measured with a Technicon
AutoAnalyzer II (Technicon Industrial Systems,
Tarrytown, NY, U.S.A.) using a colorimetric assay based
on the reaction of ammonia, sodium salicylate, sodium
nitroprusside and sodium hypochlorite in a bu!ered alkaline medium which produced an ammonia-salicylate
complex with an absorbance maximum at 660 nm. A factor of 6.25 was used to convert nitrogen concentration to
292
Sensory Analysis
Di!erences between juices "ltered through the various
membranes were compared using triangle tests. Eighteen
judges were selected from sta! at the Paci"c Agri-Food
Research Centre. Juices were stored at !30 3C after
initial processing. Prior to sensory evaluation, the juices
were thawed at 4 3C. Juice samples (30 mL) were presented to each judge in covered black wine glasses with
random three-digit codes. The juices were allowed to
equilibrate at room temperature for 30 min before presentation. Judges were asked to smell and then taste a set
of three glasses in the order given before selecting the
odd sample. The triangle tests were completely randomized for the odd sample and the order of presentation.
The level of signi"cance was determined according to
Larmond (12).
293
Table 1 Membrane resistance (R ), fouling layer resistance (R ) and total resistance (R ) for apple juice "ltration
K
D
2
with a stirred cell system.
Membrane
Resistance?@
R
K
(;10 m/kg)
R
D
(;10 m/kg)
R
2
(;10 m/kg)
3.9
17.5
38.4
38.8
189.1
143.5
492.0
86.1
216.2
1118.3
1054.7
1233.7
1064.1
1088.6
624.4
760.9
1050.4
747.2
701.7
345.2
1058.6
1251.2
1102.4
1127.4
813.5
904.4
1542.4
833.3
917.9
1463.5
9 kDa membrane
Initial
After 1 h at 25 3C, 2 m/s
CFV and 207 kPa TMP
After 1 h at 25 3C, 3.3 m/s
CFV and 414 kPa TMP
25 kDa membrane
Initial
After 1 h at 25 3C, 2 m/s
CFV and 207 kPa TMP
After 1 h at 25 3C, 3.3 m/s
CFV and 414 kPa TMP
Microbial counts@
Retentate
(cfu/L)
Permeate
(cfu/L)
14.0;10
13.3;10
1.2;10
11.0;10
3.3;10
12.1;10
11.6;10
3.5;10
7.9;10
1.2;10
294
vs.
vs.
vs.
vs.
vs.
vs.
Correct
responses?
Level of
signi"cance
9
13
14
7
14
15
NS@
P(0.001
P(0.001
NS
P(0.001
P(0.001
100 kDa
20 kDa
9 kDa
20 kDa
9 kDa
9 kDa
Table 3 Membrane resistance (R ), fouling layer resistance (R ) and total resistance (R ) for apple juice "ltration
K
D
2
with a cross#ow tubular system
Membrane
Resistance?@
R
K
(;10 m/kg)
R
D
(;10 m/kg)
R
2
(;10 m/kg)
128.5
164.3
442.3
699.7
322.6
772.3
1817.4
6670.4
451.1
936.6
2259.7
7370.1
Table 4 Properties of apple juice "ltered through di!erent tubular polymeric membranes
Property?
A
L*
a*
b*
Turbidity (NTU)
Viscosity at 253C (cps)
Soluble solids (3Brix)
Titratable acidity
(g malic acid/100 mL juice)
Flavanol content (mg/L)
Protein content (mg/L)
20 kDa PS
9 kDa PES
0.44
95.9
!5.4
30.6
0.12
1.38
12.7
0.44
0.38
96.2
!4.9
27.7
0.09
1.37
12.3
0.37
0.34
96.6
!4.3
24.8
0.16
1.38
12.2
0.34
0.18
99.0
!4.8
14.3
0.15
1.36
11.4
0.39
66
29
80
29
295
108
23
17
34
Fig. 3 E!ect of storage temperature and time on turbidity of apple juice "ltered through (a) 200 kDa PVDF, (b) 100 kDa PVDF,
(c) 20 kDa PS, and (d) 9 kDa PES membranes. (}}) 35 3C; (}}) 25 3C; (}}) 4 3C
combinations were also found to be signi"cantly di!erent. Judges noticed the largest di!erences between juices
"ltered through the 9 kDa membrane and the other
membranes. They commented that the 9 kDa membrane
juice was thin (low body/mouthfeel/viscosity), had less
#avor and had an o!-#avor (medicinal/metallic). Besides
retaining sugars and #avanols, the 9 kDa membrane may
also have retained other #avor components.
Storage study
The viscosity, soluble solids and titratable acidity of the
juices did not change with either storage temperature or
time. In addition, no microbial growth was observed
during storage of the cold pasteurized juices. However,
turbidity increased over time with higher storage temperatures and membranes of larger MWCOs (Fig. 3). Changes were more pronounced at 35 3C as the rates of
chemical reactions generally increase with temperature.
The 200 kDa membrane had the most turbidity development whereas the 9 kDa membrane had the least turbidity formation. Turbidity has previously been reported to
increase with storage of juice (1).
Haze formation in UF clari"ed apple juice is a potential problem. Polymerization of phenolics and interactions with other components (e.g. proteins) can lead
to turbidity in fruit juice products (16, 17). Evidence
that phenolics could be involved in turbidity development is supported by the #avanol content changes observed during storage (Fig. 4). Flavanol content in all
membrane "ltered juices decreased in a similar fashion
with storage temperature and time. On a comparative
basis, #avanol content values among juices were an indicator of the degree of #avanol polymerization (18). Dur-
Conclusions
Initial testing of di!erent membrane types during deadend "ltration of apple juice indicated that PVDF and PS
membranes gave higher relative #ux than PES and CE
membranes. In addition, 0.2 km or 10 kDa membranes
had higher fouling layer resistances than 30 and 100 kDa
membranes. With tubular polymeric UF membranes, the
#ux for depectinized apple juice improved as the
membrane MWCO increased from 9 to 200 kDa. Juices
296
Fig. 4 E!ect of storage temperature and time on #avanol content of apple juice "ltered through (a) 200 kDa PVDF, (b) 100 kDa
PVDF, (c) 20 kDa PS, and (d) 9 kDa PES membranes. (}}) 35 3C; (}}) 25 3C; (}}) 4 3C
297
Acknowledgements
This study was done in collaboration with Sun-Rype
Products Limited of Kelowna, B.C. with the assistance of
the Industrial Research Assistance Program. The authors
would like to thank Dr M. Cli!, Dr P. Delaquis and
Mr T. Kopp for their assistance.
Written on behalf of the Department of Agriculture and
Agri-Food, Government of Canada. Minister of Public Works and Government Services Canada 1999
References
1 PADILLA, O. I. AND MCLELLAN, M. R. Molecular weight
cut-o! of ultra"ltration membranes and the quality and
stability of apple juice. Journal of Food Science, 54,
1250}1254 (1989)
2 SHEU, M. J., WILEY, R. C. AND SCHLIMME, D. V. Solute and
enzyme recoveries in apple juice clari"cation using ultra"ltration. Journal of Food Science, 52, 732}736 (1987)
3 WU, M. L., ZALL, R. R. AND TZENG, W. C. Micro"ltration
and ultra"ltration comparison for apple juice clari"cation.
Journal of Food Science, 55, 1162}1163 (1990)
4 RAO, M. A., ACREE, T. E., COOLEY, H. J. AND ENNIS, R. W.
Clari"cation of apple juice by hollow "ber ultra"ltration:
#uxes and retention of odor-active volatiles. Journal of Food
Science, 52, 375}377 (1987)
5 HEATHERBELL, D. A., SHORT, J. L. AND STRUBI, P. Apple
juice clari"cation by ultra"ltration. Confructa, 22, 157}169
(1977)
6 PORTER, M. C. Ultra"ltration. In: Porter, M. C. (Ed.), Handbook of Industrial Membrane echnology. New Jersey:
Noyes Publications, Park Ridge, Ch. 3., p. 136}259 (1990)
7 ROG SCH, E. Experience with ultra"ltration in the 1984 season. Confructa Studien, 29(1), 27}31 (1985)
8 FUKUMOTO, L. R., DELAQUIS, P. AND GIRARD, B. Micro"ltration and ultra"ltration ceramic membranes for apple
juice clari"cation. Journal of Food Science, 63, 845}850
(1998)
9 LAU, O. L. Harvest guides for B.C. apples. B.C. Orchardist,
7(7), 1A}20A (1985)
10 ISHII, S. AND YOKOTSUKA, T. Susceptibility of fruit juice to
enzymatic clari"cation by pectin lyase and its relation to
pectin in fruit juice. Journal of Agricultural and Food Chemistry, 21(2), 269}272 (1973)
11 BROADHURST, R. B. AND JONES, W. T. Analysis of condensed tannins using acidi"ed vanillin. Journal of the Science of
Food and Agriculture, 29, 788}794 (1978)
12 LARMOND, E. aboratory Methods for Sensory Evaluation of
Food. Ottawa: Publication 1637, Food Research Institute,
Agriculture Canada, Ontario p. 63 (1977)
13 RIEDL, K., GIRARD, B. AND LENCKI, R. W. In#uence of
membrane structure on fouling layer morphology during
apple juice clari"cation. Journal of Membrane Science, 139,
155}166 (1998)
14 CHERYAN, M. Modelling of ultra"ltration processes. In:
;ltra,ltration Handbook. Technomic Publishing Co., Inc.,
Lancaster, PA. Ch. 4, p. 73}125 (1986)
15 GROHMANN, M. AND FEUERPEIL, H. P. Cold sterile apple
juice-cold sterile "ltrates with tangential #ow "ltration.
Confructa Studien, 31, 171}174 (1987)
16 NAGEL, C. W. AND SCHOBINGER, U. Investigation of the
origin of turbidity in ultra"ltered apple and pear juice
concentrate. Confructa Studien, 29(1), 16}22 (1985)
17 VAN BUREN, J. P. Causes and prevention of turbidity in
apple juice. In: Downing, D. L. (Ed.), Processed Apple Products. New York: Van Nostrand Reinhold, Ch. 5, p. 97}120
(1989)
18 SINGLETON, V. L. Wine Phenols. In: Linskens, H. F. and
Jackson, J. F. (Eds.), =ine Analysis. Berlin: Springer-Verlag,
p. 198 (1988)
298