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REVERSE OSMOSIS AND ULTRAFILTRATION IN THE FOOD INDUSTRY: REVIEW

T.I. Hedrick Professor Emeritusa a Department of Food Science and Human Nutrition, Michigan State University,

To cite this Article Hedrick Professor Emeritus, T.I.(1983) 'REVERSE OSMOSIS AND ULTRAFILTRATION IN THE FOOD

INDUSTRY: REVIEW', Drying Technology, 2: 3, 329 352 To link to this Article: DOI: 10.1080/07373938308959835 URL: http://dx.doi.org/10.1080/07373938308959835

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DRYING TECHNOLOGY, 2 ( 3 ) , 329-352 (1983-84)

REVERSE OSMOSIS AND ULTRAFILTRATION I N THE FOOD INDUSTRY: REVIEW

T. I.Hedrick, Professor Emeritus Department o f Food Science and Human N u t r i t i o n Michigan State U n i v e r s i t y

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Key Words and Phrases: cheese; concentration; energy; f o u l i n g ; membrane; pore size; processing; s o l u t i o n ; whey.

INTRODUCTION Although membranes usage p o s s i b i l i t i e s have been known f o r more than 100 years research and commercial growth has been p r i n c i p a l l y d u r i n g t h e l'ast two decades. Future p o t e n t i a l i s large. Most k i n d s

o f membranes and r e 1ated processing a p p l i c a t i o n s have some features i n c o m n . i n r e c e n t years. Pressure membrane processing has grown r a p i d l y

The t r e n d o f i n c r e a s i n g conventional energy costs

i s an i n d i c a t i o n t h a t membrane systems w i l l expand more r a p i d l y i n importance i n the immediate f u t u r e . Consequently comnercial

a p p l i c a t i o n s o f reverse osmosis (RO) and u l t r a f i l t r a t i o n (UF) which u t i l i z e h y d r o s t a t i c pressure membranes a r e sure t o increase. types o f membranes r e t a i n small molecules and concentrate o r f r a c t i o n a t e components i n l i q u i d on the basis o f m l e c u l a r size. Both

Copyrieht @ 1984 by Marcel Dekker, Inc.

330
Range f o r RO i s 0.0001 t o 0.001 mm and 0.001 t o 0.02 f o r UF.

HEDRICK

The RO

membrane r e j e c t s organic molecules w i t h molecular weight g r e a t e r than 200 b u t has a lower weight l i m i t f o r inorganic s a l t s . U F has

o n l y a small r e j e c t i o n of molecules w i t h molecular weight l e s s than 500.

UF osmotic pressures are l e s s important than RO o s m o t i f

Depending on t h e type o f membrane reverse osmosis a1 lows

pressures.

passage o f water o r o t h e r hydrogen bonding solvents b u t r e s t r i c t s t h e passage o f s a l t s .

UF membrane pore s i z e also determines t h e

Since

molecule s i z e o f t h e p a r t i c l e s t h a t can pass through.

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p r o t e i n s have l a r g e molecules t h e UF membranes r e t a i n them. A s i g n i f i c a n t advantage o f R O and UF i s t h e low energy requirement compared t o conventional concentration systems. They

use approximately one-tenth t o one-hundreth as much energy as heat evaporation. L i t t l e o r no detrimental change i n t h e sensory ( l o s s

o f v o l a t i l e s ) , n u t r i t i o n a l o r f u n c t i o n a l qua1 i t i e s o f food products need occur d u r i n g R O and UF processing. R O o r UF. No chemicals are added b y

R e s u l t i n g water permeate f o r R O may be o f acceptable This u s u a l l y i s an a d d i t i o n a l

q u a l i t y f o r reuse i n t h e p l a n t . saving.

Objectives o f t h i s a r t i c l e are two f o l d . general i n f o r m a t i o n on RO and UF.

One i s t o present
.

Another i s t o e l u c i d a t e on t h e

applications o f R O and UF f o r usage i n food processing. GENERAL APPLICATIONS A p p l i c a t i o n s o f RO and UF are i n c r e a s i n g and many uses are i n t h e food and r e l a t e d i n d u s t r i e s (Table 1). RO uses i n c l u d e t h e

concentration o f m i l k and m i l k by-products such as cheese wheys,

Table 1 .

Food Plant Applications of RO and UF.

Membranes

Concentration of Milk and Related Products Evaporated milk Condensed whole milk Sweetened condensed milk Condensed skim milk Creams Cheddar cheese Quarg cheese Ricotta cheese Feta -cheese Mozzarella cheese Camembert cheese Cottage Cheese Neufchatel and s o f t cheese Blue cheese Yogurt Ice cream mixes Ice milk and shake mixes Sweet wheys Acid wheys Whey proteins Baby foods Dietetic foods Lactose Glucose Galactose Churned buttermilk , Butter o i 1 s Cultured milk drinks Processed cheeses

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Non-Dairy Foods and Beverages Concentration Fruit and Vegetable Juices Apple Cranberry Grape Grapefruit Lemon Carrot Lime Orange Pineapple Prune Tomato Others Soups Corn syrup Sucrose solutions Maple sap Egg white Coffee & tea Fish protein Beer and wines Miscellaneous Uses Vegetable e x t r a c t s Enzyme recovery Single c e l l recovery S o l ~ d sfrom equipment rinsing Blood protein Cleaning compounds recovery Water quality improvement Candy rinsings f o r sugar recovery Waste water treatment

332

HEDRICK P r o t e i n s are recovered f r o m sweet and a c i d wheys

skim m i l k , etc.

t h a t are by-products from t h e manufacture o f the numerous kinds o f cheeses. Wheys a r e p r e t r e a t e d w i t h pressure membranes f o r l a c t o s e

used i n alcohol o r beer production. Many f r u i t jucies, e.g., apple, cherry, grape, cranberry,

pineapple, orange and others are concentrated by reverse osmosis. Vegetable juices, f o r e x m p l e tomato, are concentrated by RO. l i q u i d s such as coffee, b r i n e s from p i c k l e s and o l i v e s are concentrated.
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Other

Reduction of water i n l i q u i d foods i s necessary i n

A

p r e s e r v a t i o n methods i n c l u d i n g drying, f r e e z i n g and canning. lower volume f o r processing, freezing, dehydration, canning, packaging, t r a n s p o r t j n g and storage decreases t h e t o t a l costs,. Other a p p l i c a t i o n s are t h e concentration o f maple sap and egg white. T o t a l s o l i d s o f blood from butchering animals i s

concentrated and used. Up t o 67% o f t h e water 'is removed from waste water i n food plants. Sea water and o t h e r s a l t c o n t a i n i n g s o l u t i o n s a r e processed Brines are concentrated.

by RO f o r usable water and t h e s a l t .

Bacteria, spores, viruses and enzymes can be separated from liquids. Other organic m a t e r i a l s e.g., starches i n f l u i d s a r e R O o r IJF a r e a p p l i e d t o

separated by t h e pressure membrane systems. t h e concentration o f a n t i b i o t i c s .

Recently special membranes have

been used f o r various o i l s i n aqueous f l u i d s . R O and

UF systems are being a p p l i e d t o c u l t u r e d products

yogurt and koumiss. Fermented l i q u o r s and sugars Other a p p l i c a t i n s are t o potato, beet and f i s h

manufacture e.g.,

can be f r a c t i o n a t e d .

REVERSE OSMOSIS AND ULTRAFILTRATION

333

waste waters.

A d d i t i o n a l i n d u s t r i a1 uses i n c l u d e p u l p and paper I n electroplating

r i n s i n g s and treatment o f o t h e r p l a n t wastes.

heavy metals and other r i n s e water contaminants are reduced such as gold. copper, zinc, n i c k e l , cyanides and chromic acid. be p u r i f i e d b y a membrane pressure system. R O AND UF MEMBRANES AND APPARATUS Both RO and W are simple means f o r separating permeate t h a t r e s u l t i n a concentrated s o l u t i o n . R O and UF membranes should have Vaccines can

mechanical, thermal and chemical s t a b i l i t y i n a d d i t i o n t o adequate

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f u n c t i o n i n g c h a r a c t e r i s t i c s w i t h creep r e s i s t a n c e f o r t h e intended polution. transfer. Membrane pressure d i f f e r e n c e i s t h e main f o r c e f o r R O needs a higher pressure than UF f o r optimum action.

C e l l u l o s e acetate was t h e f i r s t comnercial l y used membrane f o r RO. The a p p l i c a t i o n was t o p u r t f y sea water (18). Modifications

w i t h improvements have been developed p a r t i c u l a r l y f o r new and special purposes. C e l l u l o s e acetate membrane should be used a t Following c e l l u l o s e acetate were Others are c e l l u l o s e

<30c and pH w i t h i n 2 t o 8 (35).

c e l l ulose p r o p i n a t e and c e l l u l o s e butyrate.

e s t e r s o f melhacryl i c and/or a c r y l i c acids, p o l y a c r y l o n i t r i t e and i t s copolymers, polyamides and polyurethanes. o f f e r resistance t o internal fouling. Anisotropic membranes

Asymmetric polyimide

membranes are applied t o both RO and UF f o r non-aqueous l i q u i d s . Composite membranes are dense but t h i n f i l m s on another microporus substrate. Membranes f o r UF are polymers o f polymethyl methacrylates, p o l y v i n y l c h l o r i d e , polystrene, p o l y a c r y l o n i t r i l e , nylons and r i g i d

334

HEDRZCK
B a r r i e r l a y e r s seem t o have u l t r a f i n e pores w i t h Water f l u x values are
'

c e l l u l o s e esters.

a diameter o f .0000001 t o .000002 cm.

g e n e r a l l y 40 t o 400/cm a t 0.35 t o 3.51 ~ ~ / c m 2 .Rarely does t h e . pressure exceed 7.03 ~ ~ / c m A~ polymer f o r UF membrane must r e t a i n i t s ultramicroporosity during fabrication. stress.

I t a l s o i s needed f o r

A minimum o f o x i d a t i o n and h y d r o l y t i c d e t e r i o r a t i o n d u r i n g

use and c l e a n i n g e s p e c i a l l y w i t h a c i d i c o r a l k a l i n e c o n d i t i o n s i s important. I n RO and

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UF usage t h e membranes are mounted on apparatus w i t h

A p o r t i o n o f t h e processing l i q u i d i s f o r c e d

two s o l u t i o n areas.

through t h e h i g h pressure area o f t h e membrane.

Amount o f s o l v e n t

forced through t o t h e lower pressure area depends on several factors. Solvents may be reused. FACTORS AFFECTING RETENTION Size o f t h e membrane pores i s a basic f a c t o r i n r e t e n t i o n b u t t h e r e are others. Hydrogen bonding capacity and/or d i e l e c t r i c Thin f i l m s

constant o f s o l u t e and s o l v e n t i n f l u e n c e t h e r e j e c t i o n .

o f some polymers may r e j e c t e l e c t r o l y t e s from aqueous s o l u t i o n s . Hydrogen bonding a b i l i t y and/or d i e l e c t r i c constant o f t h e s o l u t e may a f f e c t r e j e c t i o n p r o p e r t i e s . t o reject eletrolytes. Most products, e s p e c i a l l y foods, have a d i r e c t r e l a t i o n s h i p between v i s c o s i t y and t o t a l s o l i d s content. influenced b y v i s c o s i t y . Shear r a t e a l s o i s T h i n f i l m s o f some polymers tend

As a r e s u l t , v i s c o s i t y u s u a l l y l i m i t s t h e

p r a c t i c a l c o n c e n t r a t i o n t h a t can be a t t a i n e d i n commercial processing. I n RO t h e h y d r o s t a t i c pressure must exceed t h e osmotic

R W E R S E OSMOSIS AND ULTRAFILTRATION

pressure o f t h e product being concentrated. among samples o f i d e n t i c a l product. A l i q u i d permeation equation i s :

335
I t may vary some even

One exception i s r e f i n e d sugar.

J =

AP An

= water f l u x through membrane

Rm = r e s i s t a n c e o f t h e membrane t o water

permeation
AP = h y d r o s t a t i c pressure d i f f e r e n c e across

t h e membrane
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A x = osmotic pressure d i f f e r e n c e across t h e

membranes COMMERCIAL MEMBRANES Hollow f i b e r s i n RO have a h i g h permeable surface area. r e l a t e d t o f i b e r diameter.

It is

Hollow f i b e r s o f f e r p o t e n t i a l o f a Membrane Major

t h i n membrane w a l l and thus high permeation f l o w r a t e . support i s n o t necessary because o f i n h e r e n t strength.

disadvantage i s t h a t a f i l t e r i s needed t o remove suspended particles.

Various k i n d s o f comnerci'al membrane permeators are: ( a ) hollow f i b e r w i t h s h e l l - s i d e feed t h a t i s used f o r RO. cost, low holdup and compact. i n s i d e f i b e r feed. Advantages a r e low

( b ) Another i s hollow f i b e r w i t h

I t i s used fok

UF w i t h t h e advantage o f being

compact, low holdup, low cost an~d i s a f f e c t e d very l i t t l e by c e r t a i n c l e a n i n g procedures. Both kinds f o u l e a s i l y and are n o t easy t o

336 clean. ( c ) Tubular ( r e g u l a r k i n d ) has been used e x t e n s i v e l y

HEDRICK

i n c l u d i n g f o r l i q u i d foods. t o replace.

A tube i n t h e system i s n o t d i f f i c u l t They can be

The tubes are r e l a t i v e l y easy t o clean.

o r i e n t e d i n and around e x i s t i n g equipment.

Disadvantages are a u n i t

r e q u i r e s moderate1y 1arge f l o o r space, i s r e 1a t i v e l y expensive and has a h i g h holdup per u n i t area o f membrane. (d) H e l i c a l t u b u l a r

apparatus i s e a s i l y cleaned and r e q u i r e s o n l y moderate f l o o r space p e r meter 2. Holdup i s h i g h p e r u n i t o f membrane area. (e)

Spiral-wound u n i t i s compact w i t h low f l o o r space and low holdup per

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u n i t o f membrane area.

The surface plugs e a s i l y and i t i s d i f f i c u l t ( f ) The conventional p l a t e and

t o clean f o r l i q u i d food usage.

frame u n i t has a low holdup p e r u n i t of area and low f l o o r space needs.

I t i s r e l a t i v e l y expensive and'may p l u g r a p i d l y on surfaces

This u n i t i,s n o t easy t o clean a f t e r food

w f t h s o l u t i o n stagnation. product uses.

( 9 ) P l a t e and frame ( t h i n channel ) handles viscous

solutio,ns well, has' low holdup per u n i t o f area and a h i g h conversion d u r i n g each pass i s possible. F l o o r space needs a r e low.

Disadvantages a r e expensive, may be d i f f i c u l t t o clean p r o p e r l y due t o design and s i n g l e membrane replacement i s d i f f i c u l t o r impossible. GENERAL OPERATING CONSIDERATIONS Operating f a c t o r s t h a t a f f e c t RO and UF operations are flow pressure and f l o w r a t e , amount o f s o l u t e c o n c e n t r a t i o n i n solvent, temperature, pH, k i n d and amount o f f o u l i n g , compaction. and membrane

Processing o p e r a t i o n may be b a t c h o r continuous and

s i n g l e o r m u l t i p l e stage. Compared t o the evaporation method R O has less equipment Investment lower o p e r a t i n g c o s t s simpler i n s t a l l a t i o n and lower

REVERSE OSMOSIS AND ULTRAFILTRATION

337

l a b o r needs w i t h the'automatic c o n t r o l s .

P r i n c i p a l disadvantage i s

t h a t the degree o f concentration i s m r e l i m i t e d f o r example t o 25% s o l i d s w i t h whey. Equipment can include automatic c o n t r o l s f o r

degree o f concentraton, temperature, pH and f l o w pressure. C o r r e c t i v e a c t i o n may be appropriate f o r v a r i a t i o n s i n product composition and c h a r a c t e r i s t i c s , processing procedure i n r e l a t i o n t o p l a n t conditions ( c u r r e n t and f u t u r e ) , f o u l i n g c o n d i t i o n s and cleaning procedure, qua1 i t y and composition o f p l a n t water and costs.
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Temperature o f product should be h i g h without damage t o the For most membranes t h e maximum i s Optimum

s p e c i f i c membrane and product.

5 5 ' ~ but it i s varies according t o t h e s p e c i f i c membrane. processing temperature i s approximately 40c f o r RO.

Temperature

i s i n f l u e n c e d by membrane d u r a b i l i t y , p r o t e i n s t a b i l i t y t o c o n t r o l f o u l i n g and growth o f microorganisms. u s u a l l y optimum f o r permeation (32). 30-90KgIcm w i t h 50 f o r m i l k products. Kglcm.
A h i g h product f l o w r a t e i s

RO pressure range g e n e r a l l y i,s

Range f o r

UF

i s 0.7-7.0

Products pH range i s 2.9 t o 5 . 6 and 4 . 6 i s preferable. FOULING AND CLEANING

F o u l i n g i s t h e accumulatiion o f m a t e r i a l on t h e membrane surfaces. An example i s whey p r o t e i n and casein i n the gel deposits Another i s a viscous l a y e r t h a t Increasing t h e pressure

t h a t r e s i s t r e m v a l by f l u i d shear.

i s n o t e a s i l y removed by f l u s h i n g (17.36).

between i n l e t f l o w and concentrate p o r t i s i n d i c a t i v e o f f o u l i n g .

It i s a major cause o f f l o w r a t e d e c l i n e and thus t h e processing

capacity.

Upstream f i l t e r s and adequate pretreatment o f t h e l i q u i d Other precautions should

are important t o reduce t h e f o u l i n g rate.

i n c l u d e good water q u a l i t y and i n h i b i t i o n o f growth o f

338

HEDRICK

microorganisms on membrane d u r i n g i d l e periods.

Among t h e products

processed foods a r e g e n e r a l l y one o f t h e main c o n t r i b u t o r t o fouling. Whey can be a serious cause (31). Pretreatment o f whey i s

common b u t some treatments reduce f o u l i n g i n UF and r e s u l t i n more f o u l i n g I n RO. Under some conditions f o u l i n g can be reduced by pH

c o n t r o l and/or a d d i t i o n o f a c a l c i u m sequestering compound f o r example t o a sweet type whey. exchange pretreatment. Casein whey f o u l i n g i s reduced by i o n

C e l l u l o s e acetate membranes l o s e water

p e r m e a b i l i t y d u r i n g r e g u l a r use and are susceptable t o

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m i c r o b i o l o g i c a l and enzymatic action.

Turbulence promoters under

c e r t a i n c o n d i t i o n s increased permeation 10-15%. Cleaning r e s t o r e s t h e normal flow r a t e o f t h e product through t h e membrane and reduced microbio1ogical contamination i f c l e a n i n g and s a n i t i z i n g are p r o p e r l y conducted (26). Frequency of c l e a n i n g

depends on t h e f o u l i n g r a t e and p o s s i b l y t h e Government regulations. food products. I n t e r v a l s may v a r y from a few hours t o one day f o r For non-foods t h e c l e a n i n g i n t e r v a l s may range from Factors t h a t

a day t o a month depending on t h e product p r o p e r t i e s .

i n f l u e n c e t h e cleaning cycles f o r food processing membranes are ( a ) t h e s p e c i f i c membrane and i t s d u r a b i l i t y ; ( b ) nature and amount o f deposits on membrane surfaces; ( c ) .water hardness; ( d ) k i n d o f d e t e r g e n t ( s ) and s e n i t i z e r and t h e i r concentration; ( e ) pH o f t h e c l e a n i n g s o l u t i o n (2.0-9.0); ( f ) temperature o f s o l u t i o n ; ( g ) p u r i t y
(h) contact time o f c l e a n i n g and

o f r i n s e water and i t s temperature;

,

r i n s i n g steps and (i) s t a t e and f e d e r a l r e g u l a t i o n s . Rinse water should be low i n minerals, f r e e o f s o l i d p a r t i c l e s and have a good m i c r o b i o l o g i c a l q u a l i t y . Some membranes e.g.,

REVERSE OSMOSIS AND ULTRAFILTRATION

339

c e l l u l o s e a c e t a t e a r e susceptable t o m i c r o b i o l o g i c a l and enzymic actions. A cornnon washing procedure i s ( a ) 40 t o 5 0 ' ~ water

r i n s e ; back p r e s s u r e f l u s h i n g e s p e c i a l l y f o r RO p r o c e s s i n g i s e f f e c t i v e f o r c e r t a i n kinds o f fouli'ng; (b) c i r c u l a t i o n o f a 4 0 ' ~ detergent s o l u t i o n e.g., 0.5% p l u s water s o f t i n g compound i f needed;

( c ) 3 0 ' ~ water r i n s e ; ( d ) s a n i t i z i n g w i t h s o l u t i o n h a v i n g 20-100

ppm o f a v a i l a b l e c h l o r i n e pH 7.0-9.0 and a t 2 1 - 3 2 0 ~ f o r 10 t o 15 Formaldehyde on t h e A

min. ; ( e ) r i n s i n g t h o r o u g h l y w i t h 2 0 - 5 0 ' ~ water. s o l u t i o n s may b e used as a s a n i t i z e r .

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Nature of d e p o s i t s

membrane may n e c e s s i t a t e changes i n t h e cle,aning procedure.

d e p o s i t may be more e f f e c t i v e l y removed w i t h 0.5% enzyme e.g., t r y p s i n and f a t t y r e s i d u e w i t h l i p a s e . Most e f f e c t i v e and

e f f i c i e n t c l e a n i n g may r e q u i r e a l t e r i n g t h e procedure w i t h changing p l a n t conditions.

F I N FOOD PLANTS APPLICATION OF RO AND U

Comnercial a p p l i c a t i o n s of R O and expanding.

UF i n food p l a n t s have been

Table 1 shows a l i s t o f uses i n food p l a n t s .

A n i s o t r o p i c c e l l u l o s e a c e t a t e i s one o f t h e most c o m n p r e s s u r e membranes used f o r p r o c e s s i n g d a i r y products.

Whey
One o f t h e f i r s t a p p l i c a t i o n s o f R O t o d a i r y products involved cheese whey.
I t was concentrated b y RO (25,32,41)

o r concentrated

and f r a c t i o n a t e d w i t h

UF (9,11,14,20).

Whey has 5 t o 6% t o t a l

s o l i d s c o n s i s t i n g ' o f 4.4 and D . l t o 0.6 s a l t s .

t o 5.2% lactose, 0.12 t o 0.6 t o t a l n i t r o g e n

Tubular module i s c o r m n b u t s p i r a l t y p e a l s o i s used.

One o f

several procedures c o n s i s t s o f c o n c e n t r a t i n g t h e whey t o 15 t o 20% t o t a l s o l i d s (maximum 25%) followed by conventional steam evaporation t o t h e intended concentration. Cost o f t h i s method i s R O

i s approximately one-half t h e cost by steam evaporation.

moisture r e d u c t i o n o f whey i s f e a s i b l e p r i o r t o t r a n s p o r t a t i o n f o r comnercial uses. Permeate from UF f r a c t i o n a t i o n can be r e l a t i v e l y f r e e o f whey p r o t e i n s b u t i t contains n e a r l y a l l t h e ash and lactose. Retentate

contains 20-272 t o t a l s o l i d s 'and 14 t o 15% whey p r o t e i n t h a t has a1 1

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t h e e s s e n t i a l amino acids w i t h a p r o t e i n e f f i c i e n c y r a t i o o f 3.15.

A c r y s t a l c l e a r p r o t e i n s o l u t i o n from whey has been processed t h a t

i s heat and a c i d stable.

I t i s e s p e c i a l l y useful f o r t h e

f o r t i f i c a t i o n o f flavored beverages. S p e c i f i c whey membrane processing d e t a i l s v a r y according t o various f a c t o r s (34) e.g., t y p e o f whey (sweet o r acid), f a t and

p a r t i c u l a t e content, intended use o f processed whey, number o f processing stages etc. I n general t h e procedure includes h e a t i n g
pH adjustment t o 4.6 t o 5.5,

whey t o 8 0 ' ~ for. 10-15 sec.,

c l a r i f i c a t i o n t o r e m v e cheese and p r o t e i n p a r t i c l e s and separation t o remove f a t and c o i n c i d e n t a l l y a p o r t i o n o f t h e microorganisms. Whey i s pumped. a t 35.15 t o 42.18 Kg/cm 2 through f o r example, c e l l u l o s e a c e t a t e membrane t h a t i s o n e - t h i r d o f a micron t h i c k w i t h porous support m a t e r i a l t h a t p e r m i t s passage o f water f r o m t h e whey. C i r c u l a t j o n v e l o c i t y v a r i e s among p l a n t s , b u t 0.5 meter per

second i s c o m n .

UF remove a p o r t i o n o f t h e lactose, s a l t s and water.

Reduced

REVERSE OSMOSIS AND ULTRAFILTRATION

34 1

permeation r a t e can be caused by: ( a ) concentration p o l a r i z a t i o n ; ( b ) accumulation o f p r o t e i n , f a t and o t h e r m a t e r i a l s on t h e meibrane surfaces; ( c ) increase i n r e t e n t a t e c o n c e n t r a t i o n and (d) lack o f adequate turbulence i n t h e f l o w p a t t e r n . Skim M i l k and Whole M i l k A p p l i c a t i o n of RO and UF t o skim m i l k and whole m i l k has been expanding. Skim m i l k concentrated by UF has b e t t e r heat s t a b i l i t y Higher p r o t e i n

a t r e t o r t o r u l t r a h i g h temperature treatments (38).

and lower l a c t o s e of t h e concentrate improves t h e n u t r i t i o n a l

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qua1it y compared t o conventional condensed m i 1k

.
Fat content i s

F o r pressure membrane processing, t h e skim m i l k should have a normal f r e s h m i l k pH w i t h no developed a c i d i t y .

lowered to 0.02% by separation (7) and t h e m i l k pasteurized b u t t h e temperature-time treatment i s maintained below p r o t e i n destabilization. Actual temperature v a r i e s w i t h t h e season i n areas
RO i s used t o increase

where t h e feeds f o r t h e m i l k cows change. t o t a l s o l i d s t o 20 t o 25%.

P r o t e i n content w i l l vary from 3.1 t o

6.4% (34).

U F i s a means o f standardizing t h e p r o t e i n f o r numerous

purposes i n c l u d i n g d i e t e t i c purposes, i n f a n t formulas,.etc. Pasteurized, homogenized whole m i 1k i s concentrated by UF t o approximately 8.6% p r o t e i n and 21.5% t o t a l s o l i d s (42). i s 7 t o 9% p r o t e i n and 2 0 t o 25% t o t a l s o l i d s . The range

An a l t e r n a t i v e

procedure i s t o concentrate ,skim m i l k b y UF and then standardize t o t h e f a t content o f whole m i l k w i t h cream and p o s s i b l y water depending upon t h e intended purpose. Yogurt and S i m i l a r Cultured D a i r y Products M i l k i s concentrated t o 15% t o t a l s o l i d s by RO.
I t i s heated t o

95'~ for

, l o minutes,

cooled t o 4 5 ' ~ and inoculated w i t h 1 t o 3%

yogurt culture. viscous.

M i x t u r e i s incubated a t 43 t o 4 5 ' ~ u n t i l

Membrane processed yogurt has equal o r m r e v i s c o s i t y than Cultured

t h a t made u s i n g m i l k w i t h added d r y m i l k s o l i d s (5).

b u t t e r m i l k , acidolphus and o t h e r c u l t u r e d d a i r y beverages a l s o are made w i t h membrane processed m i l k s (13). Low Lactose M i l k Products U F economically lowers t h e l a c t o s e i n m i l k f o r people who have a low l a c t o s e tolerance.
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Enzyme a c t i o n may be needed f o r a d d i t i o n a l P r o t e i n content also may be

r e d u c t i o n depending on t h e needs.

standardized t o a higher content f o r improved n u t r i t i o n a l q u a l i t y . For low l a c t o s e c u l t u r e d d a i r y prod;cts such as, y o g u r t one Cream

procedure i s t o reduce t h e l a c t o s e i n skim m i l k by UF (15). and water i s used t o standardize t h e f a t (1.0, p r o t e i n (3.0 t o 5.0%)

2.0 o r 3.5%) and t h e Product

t o t h e desired s p e c i f i c contents.

i s p a s t e u r i zed, cooled t o t h e incubat i o n temperature, i n o c u l a t e d w i t h t h e y o g u r t c u l t u r e and incubated. Desired a c i d i t y e.g. pH 4.5

i s developed and t h e yogurt r e f r i g e r a t e d . growth use t h e l a c t o s e f r o m t h e cream.

C u l t u r e organisms d u r i n g

Despite t h e low l a c t o s e w i t h Yogurt may be

proper care t h e f l a v o r , body and t e x t u r e are good.

stored a t 50c up t o s i x weeks w i t h 1i t t l e o r no increase i n acidity. 0.60%.

A low l a c t o s e c u l t u r e d b u t t e r m i l k , acidolphus m i l k and other

F i n a l l a c t o s e c o n t e n t can be c o n t r o l l e d t o w i t h i n 0.25 t o

c u l t u r e d d a i r y beverages can be produced u s i n g t h e low l a c t o s e m i l k base and f o l l o w i n g t h e customary procedure.

REVERSE OSMOS IS AND ULTRAFILTRATION

CHEESES General Pressure membrane p r o c e s s i n g i s a p p l i e d t o t h e m i l k f o r t h e manufacture o f h a r d cheeses (1,28,29), sweet c u r d types. pasteurized. s o f t cheeses (23) and a c i d o r

I n general skim m i l k i s concentrated by RO and

P r o t e i n percentage i s increased and l a c t o s e reduced b y Cream and water a r e added report that t o

UF t o t h e c o n t e n t o f a s p e c i f i c cheese.

t o s t a n d a r d i z e t h e composition.

Authors (1,22,23)

t h e standardized c o n c e n t r a t e a r e i n c o r p o r a t e d rennet, s a l t and t h e

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s t a r t e r microorganisms. be added also.

Protease and l i p a s e enzymes may o r may n o t

I t i s coated

Curd i s molded i n t o t h e usual shape.

o r packaged and r i p e n e d a t t h e usual temperature and h u m i d i t y w i t h t h e necessary p r e c a u t i o n s . S o f t t y p e cheeses may o r may n o t be

r i p e n e d depending o n t h e s p e c i f i c kind. Not a1 1 pressure membrane t r e a t e d mi lk and/or processing procedure r e s u l t i n a cheese t h a t complies w i t h t h e s p e c i f i c l e g a l composition standards.
Two a l t e r n a t i v e s a r e t o increase t h e s o l i d s
.

composition b y a d d i t i o n a l m o i s t u r e r e m v a l w i t h conventional e q u i p m n t o r added d r y mi 1 k. R O and UF have been a p p l i e d t o various cheeses t h a t a r e n o t mentioned below. Quarg and o t h e r s . Cheddar Manufacture o f Cheddar cheese (4) and s i m i l a r k i n d s such as Colby ( 2 ) c o n s i s t s of s t a n d a r d i z i n g t h e R O and UF r e n t e n t a t e p r e v i o u s l y r e p o r t e d i n t h e CHEESE (General) s e c t i o n o f t h i s A few a r e

, Brick

(Z), F e t a (10). R i c o t t a (24),

They a r e lower i n volume o f p r o d u c t i o n and sales.

344

HEDRICK

article.

Legal standards f o r Cheddar r e q u i r e n o t more than 39% Salt

moisture and n o t l e s s than 50% f a t i n t h e t o t a l s o l i d s . content n o r m a l l y i s w i t h i n 1 t o 2%.

Ift h e RO and UF processing

r e s u l t i n a r e t e n t a t e t h a t does n o t meet the l e g a l composition t h e moisture can be reduced b y conventional means o r d r y m i l k added. Whey s o l i d s UF r e t e n t a t e i s added t o Cheddar cheese s o l u t e f o r higher y i e l d s (1). Process Cheese Process Cheddar cheese i s made w i t h o u t enzyme treatment o f t h e
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UF concentrated skim m i l k p l u s cream and 60% ripened cheddar (37). M i x t u r e also has s a l t and an e m u l s i f i e r added a f t e r d i s s o l v i n g i n water. The product i s heated t o 7 5 ' ~ f o r 10 minutes and
I t i s cooled o v e r n i g h t a t room temperature;

packaged.

Other

researchers have used UF whole m i l k r e t e n t a t e s w i t h curd f o r process cheese (6). Another procedure (37) i s t o add 0.01% protease and .0.00005% l i p a s e enzymes t o a pasteurized, homogenized and cooled ( 4 5 ' ~ ) mixture.
I t i s h e l d 24 hours.

E m u l s i f i e r i s dissolved i n water, M i x t u r e i s heated t o

d r y r e t e n t a t e and Cheddar cheese are added. 7 5 ' ~ f o r 10 min.,

packaged and cooled a t room temperature.

Composition can comply w i t h l e g a l standards. Fresh S o f t Cheese

Manufacture o f f r e s h s o f t cheese ( 2 3 , 3 ) i s accomplished by adding rennet and l a c t i c c u l t u r e t o a standardized r e t e n t a t e a t 21 t o 3 2 ' ~ and h e l d u n t i l t h e pH i s 4.7. cream mixed i n t o it. Curd i s s t i r r e d and sweet

Product i s homogenized a t a low pressure.

REVERSE OSMOSIS AND ULTRAFILTRATION

345

cooled t o 5 ' ~ and packaged.

Average composition i s r o u g h l y 7.0% V a r i a t i o n s o f s o f t cheese

protein, 7.5% f a t and 19.2% t o t a l solids.

c o n s i s t o f o m i t t i n g t h e cream and r e p l a c i n g it w i t h skim m i l k o r m i l k w i t h 1%. 2 o r 3.5% f a t . Advantages o f RO 'and UF process f o r s o f t f r e s h cheese are s u b s t a n t i a l l y less rennet i s needed also, l e s s c u l t u r e , less equipment space, less l a b o r and t h e equipment can be a u t o m a t i c a l l y c o n t r o l l e d f o r t h e manufacturing operations. t o the manufacture of cottage cheese.
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S i m i l a r b e n e f i t s apply

Mold Cured Cheeses Various k i n d s o f m l d cured cheeses can be manufactured w i t h m i l k concentrated by UF. The more important one are Danish Blue Cow

(12), French Roquefort, I t a l i a n Gorgonzola and E n g l i s h S t i l t o n .

o r goat m i l k i s s h o r t time h i g h temperature pasteurized and cream removed b y separation. t o a r a t i o o f 4.4:l. Skim m i l k f o r Danish Blue i s u l t r a f i l t r a t e d Temperature g r a d u a l l y i s increased from 5 ' ~

a t t h e beginning of UF t o 40c when approximately one-half t h e moisture i s removed. I n l e t pressure i s (3.66 t o 4.50/cm 2 ). The

concentrated skim m i l k i s standardized with,cream and homogenized a t 3 6 ' ~ w i t h 154.66 Kg/cm 2

Product i s cooled t o the s e t t i n g

temperature and t h e usual procedure f o r t h e s p e c i f i c type o f m l d cheese i s followed. q u a l i t y i s good. With good manufacturing and r i p e n i n g care the

Y i e l d i s an' e x t r a 6 t o 12% compared t o the Rennet use i s reduced 50% o r more and t h e v a t

conventional cheese.

c a p a c i t y i s increased b y a f a c t o r o f 3.5. Camembert Authors (22,23) reported t h a t Camembert was made w i t h r e t e n t a t e

346

HEDRICK
Lactic culture

from goat m i l k b u t a l s o can be made w i t h cow m i l k .

i s added t o t h e pressure membrane r e t e n t a t e and t h e m i x t u r e warmed t o 30'~. i n 1 hour. When pH i s 5.7 rennet i s added t o form a dippable curd Curd i s formed i n t o 240 gm c y l i n d e r s t h a t are 10.2 cm i n S i m i l a r volume o f b l o c k shape may be

diameter and 3.8 cm t h i c k . formed.

Curd i s l i g h t l y s a l t e d w i t h a f i n e s i t e s a l t granules and Curd i s ripened a t 1 4 ' ~ f o r After ripening

the customary c u l t u r e mold are added.

a couple o f months w i t h 88% r e l a t v i e humidity.

surface slime i s removed and the cheese wrapped o r packaged.

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Mozzarel 1 a

UF r e t e n t a t e i s standardized t o 33.6% t o t a l s o l i d s w i t h d r y
retentate. P l a s t i c cream w i t h 69% f a t i s added t o increase t h e A f t e r h e a t i n g t o 6 5 ' ~ and Rennet (18 m1/450

t o t a l s o l i d s t o 45.0% (4,16).

homogenf zing, temperature i s reduced t o 32'~.

kg o f m i l k ) , s a l t and Streptococcus cremoris (5%) are added and thoroughly mixed. Curd i s h e l d a t 3 2 ' ~ u n t i l pH i s approximately

corresponding osmotic pressure of 8 4 . 3 6 - 9 1 . 3 9 / ~ ~ / c m ~ . T o t a l s o l i d s a t t a i n e d b y RO ranges up t o 30 t o 35%. temperature i s 40C and the optimum pH i s 4.5. Maximum Sugars and organic Aroma

acids have much affect on t h e osmotic pressure o f the j u i c e s . molecules c o n t r i b u t e l i t t l e t o t h e osmotic pressure. Selected

pressure membranes can rermve low molecular weight acids and s a l t s w h i l e r e t a i n i n g sugars and higher molecular weight compounds. Tight

membranes a r e used t o r e t a i n alcohols, water s o l u b l e e s t e r s and other compounds. O i l s o l u b l e aromatic compounds such as i n orange

j u i c e are r e t a i n e d w i t h open type membranes.

REVERSE OSMOSIS AND ULTRAFILTRATION

347

P r e f i l t e r i n g orange j u i c e f o r UF w i l l increase f l u x r a t e s d u r i n g subsequent c o n c e n t r a t i o n . P r o t e i n s , gums and p e c t i c compounds f o r m

a g e l p o l a r i z e d l a y e r on r e v e r s e osmosis membranes and cause f l u x r a t e t o be s u b s t a n t i a l l y l i m i t e d . Hydrocol l o i d s i n c r e a s e t h e

v i s c o s i t y o f j u i c e s t h e r e b y r e q u i r i n g an increased pumping pressure f o r recirculation. Maple Sap Maple sap f o r comnercial uses fold.
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i s concentrated 30 t o . 4 0

C e l l u l o s e a c e t a t e membranes a r e used w i t h a pressure a t 42.18 F i f t y t o 80% o f t h e m o i s t u r e i s removed w i t h o u t Completion o f t h e t o t a l

~ g / c m * (39,40).

l o s s o f t h e c h a r a c t e r i s t i c precursors.

s o l i d s i n c r e a s e b y t h e customary thermal process s u p p l i e s enough h e a t t o e s t a b l i s h t h e t y p i c a l maple f l a v o r from t h e p r e c u r s o r s i n t h e sap. Temperature o f t h e sap d u r i n g R O must be c o n t r o l l e d as i t Proper balance between

i n f l u e n c e s t h e usage p e r i o d o f t h e membrane.

usable p e r i o d o f t h e membrane and t h e maximum permeation r a t e due t o t h e adverse e f f e c t s o f h i g h sap temperatures i s important.

A second

i m p o r t a n t f a c t o r i s t h e d e s t r u c t i o n o f microorganisms i n t h e system w i t h a good s a n i t i z i n g procedure a f t e r each usage. Membrane should

be s a n i t i z e d j u s t b e f o r e use f o l l o w e d b y a s t e r i l e water r i n s e t o

remove t h e s a n i t i z e r f r o m membrane surfaces. P o r t i o n o f t h e water removed b y RO c o s t s r o u g h l y 1/20 as much as by heat evaporation. Egg White Egg w h i t e can be concentrated w i t h o u t s i g n i f i c a n t changes i n t h e functional properties.
I t has a low osmotic pressure o f 4.9 Kg/m

348

HEDRICK
P r o t e i n content averages 10.7%. Total

w i t h average t o t a l s o l i d s .

s o l i d s c o n t a i n 0.38% f r e e glucose and 0.3b% sodium c h l o r i d e . Egg w h i t e i s concentrated by RO w i t h a s t r u c t u a l l y supported semipermeable memberane. must'be k e p t t o a minimum. preventing shear damage. To m a i n t a i n good whippabi 1it y shear damage Proper equipment design i s important i n Pressure pumps and r e c i r c u l a t i o n pumps

used i n t h e membrane processing must be s a t i s f a c t o r y t o c o n t r o l shearing t h e egg white. C e l l u l o s e acetate membranes are used f o r

I n c r e a s i n g t h e t o t a l s o l i d s o f t h e egg white.
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Processing d e t a i 1s i n c l u d e a d j u s t i n g temperature t o 21 t o 2 2 ' ~ and pH t o 7.0 w i t h a food grade acid, reducing v i s c o s i t y by slowing s t i r r i n g , s t r a i n i n g out t h e p a r t i c l e s and proper pumping f o r product flow through t h e RO mmbranes. s o l i d s (19,30) Egg white i s concentrated up t o 30% Up t o

and w i t h e x c e l l e n t f u n c t i o n a l p r o p e r t i e s (33).

h a l f t h e glucose I s removed w i t h t h e water.

UF membranes are used

t o concentrate egg w h i t e w i t h o u t adversely a f f e c t i n g t h e whipping p r o p e r t y ( 33 )

.
A few o f t h e many

Other A p p l i c a t i o n s ' p o t e n t i a l f o r expanding t h e i n d u s t r i a l use o f RO and U F for f l u i d s t h a t n o t y e t have been discussed i s vast. are: (a) concentration o f vegetable j u i c e s ;

(b) another i s vegetable

e x t r a c t (33); UF can be used f o r recovery o f p r o t e i n s f r o m peanut, soybeans, etc. e x t r a c t s p l u s p u r i f y i n g t h e p r o t e i n by i s o l a t i o n from t o x i c substances; ( c ) e x t r a c t s o f f i s h p r o t e i n s ; (d) c o n c e n t r a t i o n o f s i n g l e c e l l s from t h e c u l t u r e medium f o r animal feeds and human food; ( e ) separation and/or c o n c e n t r a t i o n o f animal

REVERSE OSMOSIS AND ULTRAFILTRATION products f o r example, g e l a t i n e x t r a c t , blood f o r food o r animal feeds and r e d c e l l s f r o m the blood plasma; ( f ) removal o f small s o l i d p a r t i c l e s from beverage such as beer and wine; ( g ) c o f f e e and t e a e x t r a c t s f o r powder production and (h) many others.
RO has

p r a c t i c a l a p p l i c a t i o n s i n t h e treatment o f food p l a n t wastes (8). SUMMARY

F pressure membranes have been developed and I n sumnary RO and U

e x t e n s i v e l y studied experimentally.
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P o t e n t i a l f o r comnercial

a p p l i c a t i o n s i n t h e f o o d and r e l a t e d i n d u s t r i e s t o concentrate and p o s s i b l y p u r i f y l i q u i d products i s huge and j u s t beginning. Advantages a r e less processing c o s t t o concentrate; l e s s thermal changes i n t h e product and reduced l o s s o f v o l a t i l e compounds compared t o t h e conventional steam method t h a t has a higher temperature and a aqueous phase change. REFERENCES 1. Brown, R.J. and C.A. Ernstrom. 1982. I n c o r p o r a t i o n o f u l t r a f i l t r a t i o n concentration whey s o l i d s i n t o Cheddar cheese f o r i n c r e a s i n g y i e l d . J. D a i r y Sci. 65:2391. Bush, C.S., C.A. Caroutte, C.H. Amundson and N.F. Olson. 1983. Manufacture o f Colby and B r i c k cheeses from u l t r a f i l t r a t e r e d m i l k . J. D a i r y Sci. 66:415. Chapman, H.R., Valerie, F.A. Glover and P.J. Skudder. 1974. Use o f m i l k concentrated by u l t r a f i l t r a t i o n f o r making hard cheese, s o f t cheese and yogurt. J. Soc. D a i r y Tech. 27(3) :151. Covacevich, H.R. and F.V. Kowsikowski. 1978. Mozzarella and Cheddar cheese manufacture by u l t r a f i l t r a t i o n p r i n c i p l e s . J. D a i r y Sci. 61:701. Davies, F.L., P.A. Shankar and H.M. Underwood. 1977. The use of milk.concentrated by reverse osmosis f o r t h e manufacture o f yogurt. J. Soc. D a i r y Tech. 30(1):23.

2.

3.

4.

5.

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